Note: Descriptions are shown in the official language in which they were submitted.
CA 02372892 2005-07-14
DETERGENT COMPOSITIONS COMPRISING POLYMERIC SUDS VOLUME AND
SUDS DURATION ENHANCERS.
FIELD OF THE INVENTION
The present invention relates to polymers, mixtures thereof suitable for use
as
suds volume and suds duration enhancers in detergent compositions.
BACKGROUND OF THE INVENTION
The formulation of laundry detergents and other cleaning compositions presents
a
considerable challenge, since modem compositions are required to remove a
variety of
soils and stains from diverse substrates. Thus, laundry detergents, hard
surface cleaners,
shampoos and other personal cleansing compositions, detergent compositions
suitable for
use in automatic dishwashers, and the like, all require the proper selection
and
combination of ingredients in order to function effectively. In general, such
detergent
compositions will contain one or more types of surfactants which are designed
to loosen
and remove soils and stains. However, the removal of body soils, greasy/oily
soils and
certain food stains quickly and efficiently can be problematic.
The presence of suds cleaning operation has long been used as a sigoal that
the
detergent continues to be eff'ective. However, depending upon the
circurnstances, the
presence of suds or the lack thereof, has no bearing upon the efficacy of the
detergents.
Therefore, the eonsumer has come to rely upon a somewhat erroneous sig.nal,
the lack or
absence of soap suds, to indicate the need for additional detergent. In many
instances the
consumer is adding an additional amount of detergent far in excess of the
amount
necessary to thoroughly clean.
The lack of suds typically compels the consumer to add additional detergent
when
a sufficient amount still remains in solution to effectively remove the soil
and grease.
However, effective grease cuttumg and cleaning materials do not necessarily
produce a
substantial amount of corresponding suds. Furthermore, suds offer a visually
appealling
experience durring the wash process and effectively cover the dirty wash
water.
Accordingly, there remains a need in the art for detergent compositions which
have an enduring suds level while maintaining effective cleaning. The need
exists for a
composition which can maintain a high level of suds as long as the composition
is
effective. Indeed, there is a long felt need to provide a cleaning composition
which can
be use efficiently by the consumer such that the consumer uses only the
necessary
amount of detergent to fully accomplish the cleaning task.
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CA 02372892 2007-10-19
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in that it has been
surprisingly discovered that certain polymers serve as suds duration and suds
volume
extenders. The effective polymers of the present invention provide both
increased suds
volume and suds duration when formulated in a detergent composition.
A first aspect of the present invention relates to a detergent composition
comprising:
a) a polymeric suds stabilizer selected from the group consisting of: i) a
polymer
comprising at least one monomeric unit of the formula:
R2
R
R3
A-(Z)z- 0
wherein each of R', RZ and R3 are independently selected from the group
consisting of
hydrogen, C, to C6 alkyl, and mixtures thereof; L is 0; Z is -(CH2)-; z is an
integer selected
from 2 to 12; A is NR4R5, wherein each of R4 and RS are independently selected
from the
group consisting of hydrogen, C1 to Cg alkyl, and mixtures thereof, or NR4R5
form a
heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing
additional
hetero atoms, optionally fused to a benzene ring, and optionally substituted
by C1 to C8
hydrocarbyl; ii) a proteinaceous suds stabilizer having an isoelectric point
from 7 to 11.5;
ii) a zwitterionic polymeric suds stabilizer; and iii) mixtures thereof; and
wherein said
polymeric suds stabilizer has a molecular weight of from 1,000 to 2,000,000
daltons; b) a
detersive surfactant; c) an amine oxide; and d) the balance carriers and
optionally other
adjunct ingredients.
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CA 02372892 2004-07-20
The present invention further relates to proteinaceous materials in the form
of
peptides, polypeptides, peptide copolymers, and mixtures thereof which are
suitable for
use in detergents wherein the formulator desires to extend the amount and
duration of
suds.
A second aspect of the present invention relates to detergent compositions
suitable
for use in hand dishwashing, said compositions comprising:
a) an effective amount of a zwitterionic polymeric suds stabilizer;
b) an effective amount of a detersive surfactant; and
c) the balance carriers and other adjunct ingredients;
The present invention further relates to zwitterionic polymeric materials
which
are suitable for use in detergents wherein the forrnulator desires to extend
the amount and
duration of suds.
A third aspect of the present invention relates to detergent compositions
comprising:
a) an effective anlount of a polymeric suds stabilizer, said stabilizer
comprising:
i) units capable of having a cationic charge at a pH of from about 4 to
about 12;
provided that said suds stabilizer has an average cationic charge density
from about 0.05 to about 5 units per 100 daltons molecular weight at a pH
of from about 4 to about 12;
b) an effective amount of a detersive surfactant; and
c) the balance carriers and other adjunct ingredients;
These and other aspects, features and advantages will become apparent to those
of
ordinary skill in the art from a reading of the following detailed description
and the
appended claims.
In the description of the invention various embodiments and/or individual
features are disclosed. As will be apparent for the skilled practitioner all
combinations of
such embodiments and features are possible and can result in preferred
executions of the
invention.
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All percentages, ratios and proportions herein are by weight, unless otherwise
specified. All temperatures are in degrees Celsius (oC) unless othenWise
specified.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to polymers which provide increased suds volume
and increase suds duration. The present invention also relates to detergent
compositions
comprising polymers which provide extended suds volume and suds duration
without
sacrificing the grease cutting ability of said liquid detergent compositions.
The detergent
compositions of the present invention comprise suds boosting polymers selected
from (i)
polymers comprising at least one mononleric unit; (ii) proteinaceous suds
stabilizer; (iii)
zwitterionic polymeric suds stabilizer; and (iv) polymers comprising units
capable of
having a cationic charge.
In addition, the polymers of the present invention act together with
surfactants
and other adjunct ingredients to provide for efficient grease cutting and anti-
redepositon
of grease.
(i) polymers comprising at least one nionomeric unit
In one aspect of the present invention the polymeric suds stabilizers comprise
at
least one nlonomeric unit of the formula:
Rz
Rt
3
A-(Z)z-I- 0
wherein each of R1, R` and W are independently selected from the group
consisting of
hvdrogen, C, to Cc, alkyl, and niixtures thereof, preferably hydrogen, C, to
C3 alkyl, more
preferably, hydrogen or methyl. L is selected from the group consisting of a
bond, 0,
NR6, SR7 R8 and mixtures thereof, preferably, 0, NR6, wherein R6 is selected
from the
group consisting of hydrogen, C1 to Cx alkyl and mixtures thereof, preferably,
hydrogen,
Cl to C3, and mixtures thereof, more preferably hvdrogen, methyl; each of R7
and Rg are
independently hydrogen, 0, C, to C8 alkyl and mixtures thereof, preferably,
hydrogen, C1
to C3, and mixtures thereof, more preferably hydrogen or methyl. By "0", an
oxygen
linked via a double bond is meant, such as a carbonyl group. Furthermore this
means
that when either or both R7R' is "0", SR7Rg can have the following structures:
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0 R8 0
II I II
-s- -s- -S-
R7 O O
, or
Alternatively, SR7 R8 form a heterocyclic ring containing from 4 to 7 carbon
atoms,
optionally containing additional hetero atoms and optionally substituted. For
example
SR7 R$ can be:
S/ \S/ S/ S/ S/ S/ S/
6 or
NH , N NR
However, it is preferred that SR7 Rg, when present, is not a heterocycle.
When L is a bond it means that there is a direct link, or a bond, between the
carbonyl carbon atom to Z, when z is not zero. For example:
CH3 \
~N-(CH2CH20)3 O 0 N-(CH2 2 O
CH
3
~ =
When L is a bond and z is zero, it means L is a bond from the carbonyl atom to
A. For
example:
N O
ON O
HN N ^ J C
Z is selected from the group consisting of: -(CH2)-, (CH2-CH=CH)-, -(CH2-
CHOH)-, (CH2-CHNR6)-, -(CH2-CHR14-O)- and mixtures thereof, preferably -(CH2)-
.
R14 is selected from the group consisting of hydrogen, CI to C6 alkyl and
mixtures
thereof, preferably hydrogen, methyl, ethyl and mixtures thereof; z is an
integer selected
from about 0 to about 12, preferably about 2 to about 10, more preferably
about 2 to
about 6.
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A is NR4R5. Wherein each of R4 and R5 are is independently selected from the
group consisting of hydrogen, C1-C8 linear or branched alkyl, alkyleneoxy
having the
formula:
-(RlOO)yRll
wherein R10 is C2-C4 linear or branched alkylene, and mixtures thereof; R11 is
hydrogen, C1-C4 alkyl, and mixtures thereof; y is from 1 to about 10.
Preferably R4 and
R5 are independently, hydrogen, C, to C4 alkyl. Alternatively, NR4R5 can form
a
heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing
additional
hetero atoms, optionally fused to a benzene ring, and optionally substituted
by C, to C8
hydrocarbyl. Examples of suitable heterocycles, both substituted and
unsubstituted, are
indolyl, isoindolinyl imidazolyl, imidazolinyl, piperidinyl pyrazolyl,
pyrazolinyl,
pyridinyl, piperazinyl, pyrrolidinyl, pyrrolidinyl, guanidino, amidino,
quinidinyl,
thiazolinyl, morpholine and mixtures thereof, with morpholino and piperazinyl
being
preferred. Furthermore the polymeric suds stabilizer has a molecular weight of
from
about 1,000 to about 2,000,000 preferably from about 5,000 to about 1,000,000,
more
preferably from about 10,000 to about 750,000, more preferably from about
20,000 to
about 500,000, even more preferably from about 35,000 to about 300,000
daltons. The
molecular weight of the polymeric suds boosters, can be determined via
conventional gel
permeation chromatography.
While, it is preferred that the polymeric suds stabilizers (i), be selected
from
homopolymer, copolymers and terpolymers, other polymers (or multimers) of the
at least
one monomeric unit, the polymeric suds stabilizers can also be envisioned via
polymerization of the at least one monomeric unit with a wider selection of
monomers.
That is, all the polymeric suds stabilizers, (i) can be a homopolymers,
copolymers,
terpolymers, etc. of the at least one monomeric unit, or the polymeric suds
stabilizer can
be copolymers, terpolymers, etc. containing one, two or more of the at least
one
monomeric unit and one, two or more monomeric units other than the at least
one
monomeric unit. For example a suitable homopolymer is:
rR'J
R4
R5 / N - (CH2)Z- O O
wherein R1, R4, R5 and z are as hereinbefore defined. For example a suitable
copolymer
is:
(i)
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rR'J
R4
O
R5 / N - (CH2)Z- O
wherein R1, R4, R5 and z are as hereinbefore defined; and
(ii)
R1
B-L O
wherein R' and L are as hereinbefore defined, and B is selected from the group
consisting of hydrogen, C, to C8 hydrocarbyl, NR4R5, and mixtures thereof;
wherein each of R4 and R5 are independently selected from the group consisting
of hydrogen, C1 to C8 alkyl, and mixtures thereof, or NR4R5 form a
heterocyclic
ring containing from 4 to 7 carbon atoms, optionally containing additional
hetero
atoms, optionally fused to a benzene ring, and optionally substituted by C, to
C8
hydrocarbyl;
wherein ratio of (i) to (ii) is from about 99:1 to about 1:10.
Some preferred examples of
R
B- L O
are:
O ~ O
O O O O, HO O or
HO O
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For example a copolymer can be made from two monomers, G and H, such that G
and H are randomly distributed in the copolymer, such as
GHGGHGGGGGHHG.....etc.
or G and H can be in repeating distributions in the copolymer, for example
GHGHGHGHGHGHGH .......etc.,
or
GGGGGHHGGGGGHH.....etc.,
The same is true of the terpolymer, the distribution of the three monomers can
be
either random or repeating.
For example a suitable polymeric suds stabilizer, which is a copolymer is:
R~
R4
RS,N - (CH2)z- O 0
i)
wherein Rl, R4, R5 and z are as hereinbefore defined; and
R1 Ri
R13 ' --~*
N.R1a p
ii) either 0 or R -(Z)z
wherein Rl Z and z are as hereinbefore defined, each of R12 and R13 are
independently selected from the group consisting of hydrogen, C, to C8 alkyl
and
mixtures thereof, preferably, hydrogen, CI to C3, and mixtures thereof, more
preferably hydrogen, methyl, or RlZ and R13 form a heterocyclic ring
containing
from 4 to 7 carbon atoms; and R15 is selected from the group consisting of
hydrogen, C1 to C8 alkyl and mixtures thereof, preferably, hydrogen, C, to C3,
and
mixtures thereof, more preferably hydrogen, methyl,
wherein ratio of (i) to (ii) is from about 99:1 to about 1:10.
Some preferred at least one monomeric units, which can be additionally
combined together to from copolymers and terpolymers include:
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WO 00/71652 CA 02372892 2001-11-01 pCT/US00/14564
CH3 CH3CH2
I N
O
CH3'~ NO O CH3CH2 O H2N 0 O
O O
N O N
NH or /
An example of a preferred homopolymer is 2-dimethylaminoethyl methacrylate
(DMAM) having the formula:
CH3
CH3-"N~~O
Some preferred copolymers include:
copolymers of
CH3
CH ~NO OCH3~N O
3 I
CH3
CH3
N~~ O
CH3 HO O
CH3
N~\O HO O
and CH3
An example of a preferred copolymer is the (DMA)/(DMAM) copolymer having
the general formula:
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CA 02372892 2004-07-20
CH3
CH30 , N o CH3~-N ~,,~o o
I
CH3
wherein the ratio of (DMA) to (DMAM) is about 1 to about 10, preferably about
1 to
about 5, more preferably about 1 to about 3.
An example of a preferred copolymer is the (DMAM)/(DMA) copolymer having
the general formula:
CH3
N CH3~
CH3~ O 0 N
CH3
wherein the ratio of (DMAM) to (DMA) is about I to about 5, preferably about 1
to
about 3.
The detergent compositions according to the first aspect of the present
invention
comprise at least an effective amount of the polymeric suds stabilizers, (i)
described
herein, preferably from about 0.01% to about 10%, more preferably from about
0.05% to
about 5%, most preferably from about 0.1 % to about 2% by weight, of said
composition.
What is meant herein by "an effective amount polymeric suds stabilizers " is
that the suds
volume and suds duration produced by the presently described compositions are
sustained for an increased amount of time relative to a composition which does
not
comprise one or more of the polymeric suds stabilizer described herein.
Additionally, the
polymeric suds stabilizer can be present as the free base or as a salt.
Typical counter ions
include, citrate, maleate, sulfate, chloride, etc.
(ii) Proteinaceous Suds Stabilizer
The proteinaceous suds stabilizers of the present invention can be peptides,
polypeptides, amino acid containing copolymers, and mixtures thereof. Any
suitable
amino acid can be used to form the backbone of the peptides, polypeptides, or
amino acid
containing copolymers of the present invention provided at least 10% to about
40% of
said amino acids which comprise the peptides are capable of being protonated
at a pH of
from 7 to about 11.5.
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The proteinaceous suds stabilizers of the present invention comprise at least
about
10% by weight of one or more amino acid residues, preferably amino acid
residues
having a proton accepting or proton donor moiety. The proteinaceous suds
stabilizers
can comprise any other amino acid compatible units which provide for extended
suds
formation and suds volume.
For the purposes of the present invention the term "peptide" and "polypeptide"
stand equally well for polymers which comprise 100% amino acids as described
herein
below and which have a molecular weight of at least about 1500 daltons. For
the
purposes of the present invention the term "amino acid containing co-polymers"
is
defined as "polymeric material comprising at least about 10% by weight of one
or more
amino acids as defined herein provided said polymeric material has a molecular
weight
of at least about 1500 daltons".
The preferred proteinaceous suds stabilizers according to the present
invention
have an isoelectric point of form 7 to about 11.5, preferably from about 8.5
to about 11.5,
more preferably form about 9.5 to about 11.
In general, the amino acids suitable for use in forming the proteinaceous suds
stabilizers of the present invention have from 2 to 22 carbon atoms, said
amino acids
having the formula:
R2 R R2 0
H2N ( i )x-C-(C)y-C-OH
R2 R1 R2
wherein R and R1 are each independently hydrogen, C 1-C6 linear or branched
alkyl, C 1-
C6 substituted alkyl, and mixtures thereof. Non-limiting examples of suitable
moieties
for substitution on the C1-C6 alkyl units include amino, hydroxy, carboxy,
amido, thio,
thioalkyl, phenyl, substituted phenyl, wherein said phenyl substitution is
hydroxy,
halogen, amino, carboxy, amido, and mixtures thereof. Further non-limiting
examples of
suitable moieties for substitution on the R and R1 C 1-C6 alkyl units include
3-
imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl, 2-piperidinyl, 3-
piperidinyl, 4-
piperidinyl, 1-pyrazolyl, 3-pyrazoyl, 4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl, 3-
pyrazolinyl,
4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,
piperazinyl, 2-
pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, and mixtures thereof.
Preferably R1 is
hydrogen and at least 10% of R units are moieties which are capable of having
a positive
or negative charge at a pH of from about 7 to about 11.5. Each R2 is
independently
hydrogen, hydroxy, amino, guanidino, C 1-C4 alkyl, or comprises a carbon chain
which
can be taken together with R, Rl any R2 units to form an aromatic or non-
aromatic ring
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having from 5 to 10 carbon atoms wherein said ring may be a single ring or two
fused
rings, each ring being aromatic, non-aromatic, or mixtures thereof. When the
amino
acids according to the present invention comprise one or more rings
incorporated into the
amino acid backbone, then R, R1, and one or more R2 units will provide the
necessary
carbon-carbon bonds to accommodate the formation of said ring. Preferably when
R is
hydrogen, R1 is not hydrogen, and vice versa; preferably at least one R2 is
hydrogen.
The indices x and y are each independently from 0 to 2.
An example of an amino acid according to the present invention which contains
a
ring as part of the amino acid backbone is 2-aminobenzoic acid (anthranilic
acid) having
the formula:
C O2H
H2N
wherein x is equal to 1, y is equal to 0 and R, R1, and 2 R2 units from the
same carbon
atom are taken together to form a benzene ring.
A further example of an amino acid according to the present invention which
contains a ring as part of the amino acid backbone is 3-aminobenzoic acid
having the
formula:
H2N QCO2H
wherein x and y are each equal to 1, R is hydrogen and R1 and four R2 units
are taken
together to form a benzene ring.
Non-limiting examples of amino acids suitable for use in the proteinaceous
suds
stabilizers of the present invention wherein at least one x or y is not equal
to 0 include 2-
aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, b-alanine, and b-
hydroxyaminobutyric acid.
The preferred amino acids suitable for use in the proteinaceous suds
stabilizers of
the present invention have the formula:
R 0
I II
H2N (CH2)x- ~ -(CHZ)y-C-OH
R1
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wherein R and R1 are independently hydrogen or a moiety as describe herein
above
preferably R1 is hydrogen and at least from about 10% to about 40% of R units
comprise
a moiety having a positive charge at a pH of from about 7 to about 11.5.
More preferred amino acids which comprise the proteinaceous suds stabilizers
of
the present invention have the formula:
R O
I II
H2N-C-C-OH
H
wherein R is hydrogen, C 1-C6 linear or branched alkyl, C 1-C6 substituted
alkyl, and
mixtures thereof. R is preferably C1-C6 substituted alkyl wherein preferred
moieties
which are substituted on said C 1-C6 alkyl units include amino, hydroxy,
carboxy, amido,
thio, C1-C4 thioalkyl, 3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-
imidazolinyl, 2-
piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazoyl, 4-
pyrazoyl, 5-pyrazoyl,
1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-
pyridinyl, 4-
pyridinyl, piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino,
phenyl,
substituted phenyl, wherein said phenyl substitution is hydroxy, halogen,
amino, carboxy,
and amido.
An example of a more preferred amino acid according to the present invention
is
the amino acid lysine having the formula:
NH2
O
I I
HZN-C-C-OH
H
wherein R is a substituted C1 alkyl moiety, said substituent is 4-imidazolyl.
Non-limiting examples of preferred amino acids include alanine, arginine,
asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine,
histidine,
isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine,
threonine,
tryptophan, tyrosine, valine, and mixtures thereof. The aforementioned amino
acids are
typically referred to as the "primary a-amino acids", however, the
proteinaceous suds
stabilizers of the present invention may comprise any amino acid having an R
unit which
together with the aforementioned amino acids serves to adjust the isoelectric
point of the
proteinaceous suds stabilizers to a range of from about 7 to about 11.5. For
example,
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further non-limiting examples of amino acids include homoserine,
hydroxyproline,
norleucine, norvaline, ornithine, penicillamine, and phenylglycine, preferably
ornithine.
R units preferably comprise moieties which are capable of a cationic or
anionic charges
within the range of pH from about 7 to about 11.5. Non-limiting examples of
preferred
amino acids having anionic R units include glutamic acid, aspartic acid, and g-
carboxyglutamic acid.
For the purposes of the present invention, both optical isomers of any amino
acid
having a chiral center serve equally well for inclusion into the backbone of
the peptide,
polypeptide, or amino acid copolymers. Racemic mixtures of one amino acid may
be
suitably combined with a single optical isomer of one or more other amino
acids
depending upon the desired properties of the final proteinaceous suds
stabilizer. The
same applies to amino acids capable of forming diasteriomeric pairs, for
example,
threonine.
1. Polyamino Acid Proteinaceous Suds Stabilizer
One type of suitable proteinaceous suds stabilizer according to the present
invention is comprised entirely of the amino acids described herein above.
Said
polyamino acid compounds may be naturally occurring peptides, polypeptides,
enzymes,
and the like, provided said compounds have an isoelectric point of from about
7 to about
11.5 and a molecular weight greater than or equal to about 1500 daltons.
Preferably the
proteinaceous suds stabilizers of the present invention which are comprised
entirely of
amino acids, comprise from about 10% to about 40% by weight, of amino acids
which
are capable of being protonated at a pH of from about 7 to about 11.5. An
example of a
polyamino acid which is suitable as a proteinaceous suds stabilizer according
to the
present invention is the enzyme lysozyme.
An exception may, from time to time, occur in the case where naturally
occurring
enzymes, proteins, and peptides are chosen as proteinaceous suds stabilizers.
Without
wishing to be limited by theory, the unique secondary, tertiary, or quaternary
structure of
said naturally occurring polypeptides may permit their use even though the
amount of
protonatable amino acids within the pH range of from about 7 to about 11.5 is
outside the
range of from about 10% to about 40% by weight. For example an enzyme having
an
isoelectric point in the range of from about 7 to about 11.5 which only
comprises 5% by
weight amino acids having R units which are protonated at a pH of from about 7
to about
11.5 may suitably serve as an effective proteinaceous suds stabilizer
according to the
present invention.
Another class of suitable polyamino acid compound is the synthetic peptide
having a molecular weight of at least about 1500 daltons and further
comprising from
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about 10% to about 40% by weight of amino acids capable of being protonated at
a pH of
form about 7 to about 11.5. In addition, said polyamino acid peptides must
have an
isoelectric point of form 7 to about 11.5, preferably from about 8.5 to about
11.5, more
preferably form about 9.5 to about 11. An example of a polyamino acid
synthetic peptide
suitable for use as a proteinaceous suds stabilizer according to the present
invention is
the copolymer of the amino acids lysine, alanine, glutamic acid, and tyrosine
having an
average molecular weight of 52,000 daltons and a ratio of lys:ala:glu:tyr of
approximately 5:6:2:1.
Without wishing to be limited by theory, the presence of one or more cationic
amino acids, for example, histidine, ornithine, lysine and the like, is
required to insure
increased suds stabilization and suds volume. However, the relative amount of
cationic
amino acid present, as well as the resulting isoelectric point of the
polyamino acid, are
key to the effectiveness of the resulting material. For example, poly L-lysine
having a
molecular weight of approximately 18,000 daltons comprises 100% amino acids
which
have the capacity to possess a positive charge in the pH range of from about 7
to about
11.5, with the result that this material is ineffective as a suds extender and
as a greasy
soil removing agent.
2. Peptide Copolymers
Another class of materials suitable for use as proteinaceous suds stabilizers
according to the present invention are peptide copolymers. For the purposes of
the
present invention "peptide copolymers" are defined as "polymeric materials
with a
molecular weight greater than or equal to about 1500 daltons having an
isoelectric point
of from about 7 to about 11.5 wherein at least about 10% by weight of said
polymeric
material comprises one or more amino acids".
Peptide copolymers suitable for use as proteinaceous suds stabilizers may
include
segments of polyethylene oxide which are linked to segments of peptide or
polypeptide
to form a material which has increased suds retention as well as
formulatability.
Nonlimiting examples of amino acid copolymer classes include the following.
A. Polyalkyleneimine copolymers.
Polyalkyleneimine copolymers comprise random segments of polyalkyleneimine,
preferably polyethyleneimine, together with segments of amino acid residues.
For
example, tetraethylenepentamine is reacted together with polyglutamic acid and
polyalanine to form a copolymer having the formula:
CA 02372892 2004-07-20
H
[HN-R]n+1-[7`l-RIm [N-Rln NH (Glu)i (Ala)j
x Y z
wherein m is equal to 3, n is equal to 0, i is equal to 3, j is equal to 5, x
is equal to 3, y is
equal to 4, and z is equal to 7.
However, the formulator may substitute other polyamines for
polyalkyleneimines,
for example, polyvinyl amines, or other suitable polyamine which provides for
a source
of cationic charge at a pH of from 7 to abut 11.5 and which results in a
copolymer having
an isoelectric point of from about 7 to about 11.5.
The formulator may combine non-amine polymers with protonatable as well as
non-protonatable amino acids. For example, a carboxylate-containing homo-
polymer
may be reacted with one or more amino acids, for example, histidine and
glycine, to form
an amino acid containing amido copolymer having the formula:
CO2H CO--GIy CO-His
x y z
wherein said copolymer has a molecular weight of at least 1500 daltons and a
ratio of x
y: z of approximately 2 : 3 : 6.
The detergent compositions according to the second aspect of the present
invention comprise at least an effective amount of one or more proteinaceous
suds
stabilizers described herein, preferably from about 0.3% to about 5%, more
preferably
from about 0.4% to about 4%, most.preferably from about 0.5% to about 3% by
weight,
of said composition. What is meant herein by "an effective amount of
proteinaceous
suds stabilizer" is that the suds produced by the presently described
compositions are
sustained for an increased amount of time relative to a composition which does
not
comprise a proteinaceous suds stabilizer described herein.
(iii) zwitterionic polymeric suds stabilizers
The zwitterionic polymeric suds stabilizers of the present invention comprise
monomeric units which have at least one moiety capable of sustaining a
negative charge
at a pH of from about 4 to about 12 and at least one moiety capable of
sustaining a
positive charge within the same pH range. The zwitterionic polymers may be
homopolymers or copolymers, each of which may be suitably crosslinked.
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The polymeric suds stabilizers of the present invention are zwitterionic
polymers.
For the purposes of the present invention the term "zwitterionic polymer" is
defined as "a
polymeric material comprised of one or more monomers wherein each monomer has
one
or more moieties capable of sustaining a positive or negative charge at a pH
of from
about 4 to about 12 such that the number of positively charged moieties is
equal to the
number of negatively charged moieties at the isoelectric point of said
polymer."
The polymeric suds stabilizers of the present invention are homopolymers or
copolymers wherein the monomers which comprise said homopolymers or copolymers
contain a moiety capable of being protonated at a pH of from about 4 to about
12, or a
moiety capable of being de-protonated at a pH of from about 4 to about 12, of
a mixture
of both types of moieties.
A preferred class of zwitterionic polymer suitable for use as a suds volume
and
suds duration enhancer has the formula:
R1 R2
I I
(R)x-(CH)y (CH)z
n
wherein R is C 1-C 12 linear alkylene, C 1-C 12 branched alkylene, and
mixtures thereof;
preferably C1-C4 linear alkylene, C3-C4 branched alkylene; more preferably
methylene
and 1,2-propylene. R' and R2 are defined herein after. The index x is from 0
to 6; y is 0
or 1; z is 0 or 1.
The index n has the value such that the zwitterionic polymers of the present
invention have an average molecular weight of from about 1,000 to about
2,000,000
preferably from about 5,000 to about 1,000,000, more preferably from about
10,000 to
about 750,000, more preferably from about 20,000 to about 500,000, even more
preferably from about 35,000 to about 300,000 daltons. The molecular weight of
the
polymeric suds boosters, can be determined via conventional gel permeation
chromatography.
Anionic Units
R1 is a unit capable of having a negative charge at a pH of from about 4 to
about
12. Preferred R1 has the formula:
-(L)i-(S)j-R3
wherein L is a linking unit independently selected from the following:
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WO 00/71652 PCT/US00/14564
0 0 0 0
II II II II
-O-C-NR'- -C-O- -O-C- -O-C-O- -0-
, 5 'and
mixtures thereof, wherein R' is independently hydrogen, C1-C4 alkyl, and
mixtures
thereof; preferably hydrogen or alternatively R' and S can form a heterocycle
of 4 to 7
carbon atoms, optionally containing other hetero atoms and optionally
substituted.
Preferably the linking group L can be introduced into the molecule as part of
the original
monomer backbone, for example, a polymer having L units of the formula:
O
I I
-C-O-
can suitably have this moiety introduced into the polymer via a carboxylate
containing
monomer, for example, a monomer having the general formula:
i C02H R2
(R)x-(CH)y-(CH)z
When the index i is 0, L is absent.
For anionic units S is a "spacing unit" wherein each S unit is independently
selected from C 1-C 12 linear alkylene, C 1-C 12 branched alkylene, C3-C12
linear
alkenylene, C3-C12 branched alkenylene, C3-C12 hydroxyalkylene, C4-C12
dihydroxyalkylene, C6-C10 arylene, C8-C12 dialkylarylene, -(R50)kR5-,
-(R50)kR6(OR5)k-, -CH2CH(OR7)CH2-, and mixtures thereof; wherein R5 is C2-C4
linear alkylene, C3-C4 branched alkylene, and mixtures thereof, preferably
ethylene, 1,2-
propylene, and mixtures thereof, more preferably ethylene; R6 is C2-C12 linear
alkylene,
and mixtures thereof, preferably ethylene; R7 is hydrogen, C1-C4 alkyl, and
mixtures
thereof, preferably hydrogen. The index k is from 1 to about 20.
Preferably S is C1-C12 linear alkylene, -(R50)kR5-, and mixtures thereof. When
S is a-(R50)kR5- unit, said units may be suitably formed by the addition an
alkyleneoxy
producing reactant (e.g. ethylene oxide, epichlorohydrin) or by addition of a
suitable
polyethyleneglycol. More preferably S is C2-C4 linear alkylene. When the index
j is 0
the S unit is absent.
R3 is independently selected from hydrogen, -CO2M, -SO3M, -OSO3M,
-CH2P(O)(OM)2, -OP(O)(OM)2, units having the formula:
-CRgR9R10
wherein each R8, R9, and R10 is independently selected from the group
consisting of
hydrogen, -(CH2)mRl1, and mixtures thereof, wherein R11 is -CO2H, -SO3M,
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-OSO3M, -CH(CO2H)CH2CO2H, -CH2P(O)(OH)2, -OP(O)(OH)2, and mixtures
thereof, preferably -CO2H, -CH(CO2H)CH2CO2H, and mixtures thereof, more
preferably -CO2H; provided that one R8, R9, or R10 is not a hydrogen atom,
preferably
two R8, R9, or R10 units are hydrogen. M is hydrogen or a salt forming cation,
preferably hydrogen. The index m has the value from 0 to 10.
Cationic Units
R2 is a unit capable of having a positive charge at a pH of from about 4 to
about
12. Preferred R2 has the formula:
-(Ll)i'-(S)j'-R4
wherein L1 is a linking unit independently selected from the following:
O 0 0
II II II
-C-O- , -O-C- , -O-C-O- ,
O R' R' O R' O R'
II I I II I II I
-C-N- , -N-C- , -N-C-N- ,
R' S R' O R' R' O
I II I II I I II
-N-C-N-, -0-C-N-, -N-C-O- ,
R' R' R'
I I I
and mixtures thereof; wherein R' is independently hydrogen, C1-C4 alkyl, and
mixtures
thereof; preferably hydrogen or alternatively R' and S can form a heterocycle
of 4 to 7
carbon atoms, optionally containing other hetero atoms and optionally
substituted.
Preferably L1 has the formula:
O H H O
II I I II
-C-N- or -N-C-
When the index i' is equal to 0, L1 is absent.
For cationic units S is a "spacing unit" wherein each S unit is independently
selected from C 1-C 12 linear alkylene, C 1-C 12 branched alkylene, C3-C12
linear
alkenylene, C3-C12 branched alkenylene, C3-C12 hydroxyalkylene, C4-C12
dihydroxyalkylene, C6-C10 arylene, C8-C12 dialkylarylene, -(R5O)kR5-,
-(R5O)kR6(OR5)k-, -CH2CH(OR7)CH2-, and mixtures thereof; wherein R5 is C2-C4
linear alkylene, C3-C4 branched alkylene, and mixtures thereof, preferably
ethylene, 1,2-
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WO 00/71652 PCT/US00/14564
propylene, and mixtures thereof, more preferably ethylene; R6 is C2-C12 linear
alkylene,
and mixtures thereof, preferably ethylene; R7 is hydrogen, Cl-C4 alkyl, and
mixtures
thereof, preferably hydrogen. The index k is from 1 to about 20.
Preferably S is C1-C12 linear alkylene, and mixtures thereof. Preferably S is
C2-
C4 linear alkylene. When the index j' is 0 the S unit is absent.
R4 is independently selected from amino, alkylamino carboxamide, 3-imidazolyl,
4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl, 2-piperidinyl, 3-piperidinyl, 4-
piperidinyl,
1-pyrazolyl, 3-pyrazoyl, 4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl, 3-pyrazolinyl,
4-
pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,
piperazinyl, 2-
pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, and mixtures thereof,
preferably
dialkylamino having the formula:
-N(Rl 1)2
wherein each R11 is independently hydrogen, C1-C4 alkyl, and mixtures thereof,
preferably hydrogen or methyl or alternatively the two R11 can form a
heterocycle of 4 to
8 carbon atoms, optionally containing other hetero atoms and optionally
substituted.
An example of a preferred zwitterionic polymer according to the present
invention has the formula:
X CO2
I I
CHZ-CH-CH-CH
0=C
n
NH
CH2CH,CH2N+H(CH3)2
wherein X is C6, n has a value such that the average molecular weight is from
about
5,000 to about 1,000,000 daltons.
Further preferred zwitterionic polymers according to the present invention are
polymers comprising monomers wherein each monomer has only cationic units or
anionic units, said polymers have the formula:
R1 R2
I I
(R)x-(CH)y (R)x-(CH)z
nl n2
wherein R, Rl, x, y, and z are the same as defined herein above; nl + n2 = n
such that n
has a value wherein the resulting zwitterionic polymer has a molecular weight
of form
about 5,000 to about 1,000,000 daltons.
CA 02372892 2004-07-20
An example of a polymer having monomers with only an anionic unit or a
cationic
unit has the forrnula:
C02
CH, -CN CH2 -CH
nl C=0 n2
NH
CH2CH2CH,N+H(CH3)2
wherein the sum of n' and n2 provide a polymer with an average molecular
weight of from
about 5,000 to about 750,000 daltons.
Another preferred zwitterionic polymer according to the present invention are
polymers which have limited crosslinking, said polymers having the formula:
RI R2 Ri
I 1 I
(R)x---((-H)y-(CH)7 [R_Y_H_]
n,
'
i
I
(I}~.
RT2
,
(~)),
LJ
RI R1 R2
(R)x-(CH)y,-(CH) [(R)x(CH)y(CH)z
n2
wherein R is C,-Cl2 linear alkylene, Ci-C12 branched alkylene, and mixtures
thereof; R' is a
unit capable of having a negative charge at a pH of from 4 to 12; R2 is a unit
capable of
having a positive charge at a pH of from 4 to 12; R12 is a C,-CI2 linear
alkylene amino
alkylene having the formula:
-R13-N-R13
L', and mixtures thereof, wherein each R13 is independently L', ethylene, and
mixtures
thereof; each S is independently selected from C,-C,Z linear alkylene, C1-C12
branched
alkylene, C3-C12 linear alkenylene, C3-C12 branched alkenylene, C3-C12
hydroxyalkylene,
C4-C 12 dihydroxyalkylene, C6-Clo arylene, C8-C12 dialkylarylene, -(R50)kR5-,
-(RSO)kR6(ORS)k-, -CH2CH(OR7)CH2-, and mixtures thereof; L' is a linking unit
independently selected from the following:
21
CA 02372892 2004-07-20
~ ~ ~
-C-o- , -o-C- , -o-C-o- ,
0 x R' O R' O R'
II I i ii I II I
-C-N-, -N-C-, -N-C-N-,
, ' , ~
R ~ R O R R li
-N-C-N-, -0-C-N-, -N-C-O-,
R' R' R'
I I I
and mixtures thereof; n' + n2 has a value such that said zwitterionic polymers
suds stabilizer
has an average molecular weight of from 1,000 to 2,000,000 daltons; n' is
equal to n" and
further n' + n" is less than or equal to 5% or the value n' + n2; x is 0 to 6;
y is 0 or 1; and z
is0or1.
The zwitterionic polymers of the present invention may comprise any
combination
of monomer units, for example, several different monomers having various R'
and R2
groups can be combined to form a suitable suds stabilizer. Alternatively the
same R1 unit
may be used with a selection of different R2 units and vice versa.
The detergent compositions according to the third aspect of the present
invention
comprise at least an effective amount of one or more zwitterionic polymeric
suds stabilizers
described herein, preferably from about 0.01% to about 10%, more preferably
21a
CA 02372892 2004-07-20
from about 0.05% to about 5%, most preferably fi-om about 0.1 % to about 2% by
weight,
of said composition. What is meant herein by "an effective amount of
zwitterionic
polymeric suds stabilizer" is that the suds produced by the presently
described
compositions are sustained for an increased amount of time relative to a
composition
which does not comprise a zwitterionic polymeric suds stabilizer described
herein.
Additionally, the polymeric suds stabilizer can be present as the free base or
as a salt.
Typical counter ions include, citrate, maleate, sulfate, chloride, etc.
(iv) polvmers comprising units capable of having a cationic chary
ge
The fourth aspect of the present invention relates to polymeric materials
which
provide enhanced suds duration and enhanced suds volume when formulated into
detergent compositions. The polymeric material may comprise any material
provided the
final polymers have an average cationic charg,e density of from about 0.05 to
about 5
units per 100 daltons molecular weight at a pH of from about 4 to about 12.
Preferably
the average cationic charge density is from about 0.5 to about 3 units per 100
daltons
molecular weight.
It is preferred that the polymeric suds stabilizer (a) further comprises:
ii) units capable of having an anionic charge at a pH of from about 4
to about 12;
iii) units capable of having an anionic cllarge and a cationic charge at
a pH of from about 4 to about 12;
iv) units having no charge at a pH of from about 4 to about 12; and
v) mixtures of units (i), (ii), (iii), and (iv);
The polymeric suds stabilizers of the according to the fourth aspect of the
present
invention are polymers which contain units capable of having a cationic charge
at a pH of
from about 4 to about 12, provided that the suds stabilizer has an average
cationic charge
density from about 0.05 to about 5 units per 100 daltons molecular weight at a
pH of
from about 4 to about 12. Additionally, the polymeric suds stabilizer can be
present as
the free base or as a salt. Typical counter ions include, citrate, maleate,
sulfate, chloride,
etc.
For the purposes of the present invention the term "cationic unit" is defined
as "a
moiety which when incorporated into the structure of the suds stabilizers of
the present
invention, is capable of maintaining a cationic charge within the pH range of
from about
4 to about 12. The cationic unit is not required to be protonated at every pH
value within
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WO 00/71652 PCT/US00/14564
the range of about 4 to about 12." Non-limiting examples of units which
comprise a
cationic moiety include lysine, ornithine, the monomeric unit having the
formula:
CH3
CH2-CH2-CH-CH
0=C
NH
CH2CH2CH2N+H(CH3)2.
the monomeric unit having the formula:
H CH3
, +
CH3= N ~/~ O O
the monomeric unit having the formula:
CH3
CH2-CH2-CH-CH
0=C
NH
CH2CHZCH2N+(CH3)3
the monomeric unit having the formula:
CH3 CO2H
I
CH2-CH-CH-CH
0=C
NH
CHZCHZCH2N+H(CH3)2
and the monomeric unit having the formula:
CH3 COZH
I
CHZ-CH-CH-CH
0=C
NH
CH2CH2CH2HN(CH3)3
the latter of which also comprises a moiety capable of having an anionic
charge at a pH
of about 4 to about 12.
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For the purposes of the present invention the term "anionic unit" is defined
as "a
moiety which when incorporated into the structure of the suds stabilizers of
the present
invention, is capable of maintaining an anionic charge within the pH range of
from about
4 to about 12. The anionic unit is not required to be de-protonated at every
pH value
within the range of about 4 to about 12." Non-limiting examples of units which
comprise
a anionic moiety include, acrylic acid, methacrylic acid, glutamic acid,
aspartic acid, the
monomeric unit having the formula:
COZ-
I
CHZ-CH2-CH-CHZ
and the monomeric unit having the formula:
CH3 C02
I I
CH2-CH-CH-CH
0=C
NH
I
CH2CH2CHZN(CH3)2
the latter of which also comprises a moiety capable of having a cationic
charge at a pH of
about 4 to about 12. This latter unit is defined herein as "a unit capable of
having an
anionic and a cationic charge at a pH of from about 4 to about 12."
For the purposes of the present invention the term "non-charged unit" is
defined
as "a moiety which when incorporated into the structure of the suds
stabilizers of the
present invention, has no charge within the pH range of from about 4 to about
12." Non-
limiting examples of units which are "non-charged units" are styrene,
ethylene,
propylene, butylene, 1,2-phenylene, esters, amides, ketones, ethers, and the
like.
The units which comprise the polymers of the present invention may, as single
units or monomers, have any pKa value.
The following are non-limiting examples of suitable polymeric materials
according to the present invention. The following examples are presented in
"classes",
however, the formulator may combine any suitable monomers or units to form a
polymeric suds stabilizer, for example, amino acids may be combined with
polyacrylate
units.
The polymeric suds stabilizers according to the fourth aspect of the present
invention also include polymers comprising at least one monomeric unit of the
formula:
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WO 00/71652 PCTIUSOO/14564
R2
R1
R3
A-(Z)Z-L O
wherein each of R1, R2,R3, R4, L, Z, z, and A are hereinbefore defined.
Furthermore,
suitable polymers include copolymers of
R
R3
A-(Z)z-I- 0
and
RI
B-L O
wherein R' L and B are as hereinbefore defined, and
copolymers of
R2
R~
R3
A-(Z)z-1- 0
and
R~ R
R13 ' -11~*
~N.Ri2 O
Rl s /
either 0 or - z
wherein R1, R12, R13, Z and z are as hereinbefore defined,
The suds stabilizers according to the fourth aspect of the present invention
can be
proteinaceous suds stabilizers, as herein before described, including
peptides,
polypeptides, amino acid containing copolymers, terpolymers etc., and mixtures
thereof.
Any suitable amino acid can be used to form the backbone of the peptides,
polypeptides,
or amino acid, wherein the polymers have an average cationic charge density
from about
0.05 to about 5 units per 100 daltons molecular weight at a pH of from about 4
to about
12.
CA 02372892 2004-07-20
In general, the amino acids suitable for use in forming the proteinaceous suds
stabilizers of the present invention have the formula:
R2 R R2 0
H2N (C),-C-(C):y-C-OH
R2 R1 R2
wherein R, R1, R2, x and y and are as hereinbefore defined.
The polymeric suds stabilizers of the fourth aspect of the present invention
present invention may be homopolynlers or copolymers wherein the monomers
which
comprise said homopolymers or copolymers contain a moiety capable of being
protonated at a pH of from about 4 to about 12, or a moiety capable of being
de-
protonated at a pH of from about 4 to about 12, of a mixture of both types of
moieties.
These suitable zwitterionic polymers are hereinbefore defined.
A Preferred class of suitable for use as a suds volume and suds duration
enhancer
has the formula:
R1 R2
I I
(R)x!(CH)y-(CH)z
n
wherein R, R1, R2, x, y, z, and n are hereinbefore defined. Furthermore, other
suitable
anionic, cationic and, zwitterionic monomers are also herein before described.
Cationic Charge Density
For the purposes of the present invention the term "cationic charge density"
is
defined as "the total number of units that are protonated at a specific pH per
100 daltons
mass of polymer, or otherwise stated, the total number of charges divided by
the dalton
molecular weight of the monomer unit or polymer."
For illustrative purposes only, a polypeptide comprising 10 units of the amino
acid lysine has a molecular weight of approximately 1028 daltons, wherein
there are 1 l-
NH2 units. If at a specific pH within the range of &om about 4 to about 12, 2
of the -NHZ
units are protonated in the form of -NH3+, then the cationic charge density is
2 cationic
charge units = by 1028 daltons molecular weight = approximately 0.2 units of
cationic
charge per 100 daltons molecular weight. This would, therefore, have
sufficient cationic
charge to suffice the cationic charge density of the present invention, but
insufficient
molecular weight to be a suitable suds enhancer.
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Polymers have been shown to be effective for delivering sudsing benefits in a
hand dishwashing context, provided the polymer contains a cationic moiety,
either
permanent via a quaternary nitrogen or temporary via protonation. Without
being limited
by theory, it is believed that the cationic charge must be sufficient to
attract the polymer
to negatively charged soils but not so large as to cause negative interactions
with
available anionic surfactants.
The cationic charge density may be determined as follows, where the cationic
charge density is defined as the amount of cationic charge on a given polymer,
either by
permanent cationic groups or via protonated groups, as a weight percent of the
total
polymer at the desired wash pH. For example, with the terpolymer, DMAM/
hydroxyethylacrylate (HEA)/acrylic acid (AA) where the ratio of monomers is 1
mole of
DMAM for 3 moles of HEA for 0.33 moles of AA, we have experimentally
determined
the pKa, see hereinafter as to how pKa is measured, of this polymer to be 8.2.
Thus, if
the wash pH is 8.2, then half of the available nitrogens will be protonated
(and count as
cationic) and the other half will not be protonated (and not be counted in the
"cationic
charge density"). Thus, since the Nitrogen has a molecular weight of
approximately 14
grams/mole, the DMAM monomer has a molecular weight of approximately 157
grams/mole, the HEA monomer has a molecular weight of approximately 116
grams/mole, and the AA monomer has a molecular weight of approximately 72
grams/mole, the cationic charge density can be calculated as follows:
Cationic Charge Density = (14/157+116+116+116+72) * 50% = 0.0132 or 1.32%.
Thus, 1.32% of the polymer contains cationic charges. Otherwise stated, the
cationic
charge density is 1.32 per 100 daltons molecular weight.
As another example, one could make a copolymer of DMAM with
hydroxyethylacrylate (HEA), where the ratio of monomers is 1 mole of DMAM for
3
moles of HEA. The DMAM monomer has a molecular weight of approximately 157 and
the HEA monomer has a molecular weight of 116 grams/mole. In this case the pKa
has
been measured to be 7.6. Thus, if the wash pH is 5.0, all of the available
nitrogens will
be protonated. The cationic charge density is then calculated:
Cationic Charge Density = 14/(157+116+116+116) * 100% = 0.0277, or 2.77%.
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Thus, the cationic charge density is 2.77 per 100 daltons molecular weight.
Notice that
in this example, the minimum repeating unit is considered 1 DMAM monomer plus
3
HEA monomers.
Alternatively, the cationic charge density can be determined as follows: where
the cationic charge density is defined as the total number of charges divided
by the dalton
molecular weight of the polymer at the desired wash pH. It can be calculated
from the
following equation
Y n; rCr
Cationic Charge Density
ym;
.i
where n; is the number of charged unit. f is the fraction of unit being
charged. In the case
of protonated species (AH), f can be calculated from the measured pH and pKa.
1 O pKa- pH
f (Ax+)- 1 + 10pKa-pH
In the case of deprotonated anionic species (A-)
1 O pH- pKa
f(A ) 1 + 1OpH-pKa
C; is the charge of the unit, m; is the dalton molecular weight of the
individual monomer
units.
For example, with polyDMAM, we have experimentally determined the pKa, see
hereinafter as to how pKa is measured, of this polymer to be 7.7. Thus, if the
wash pH is
7.7, then half of the available nitrogens will be protonated (and count as
cationic) f(AH+)
= 0.5 and the other half will not be protonated (and not be counted in the "
cationic
charge density"). Thus, since the DMAM monomer has a molecular weight of
approximately 157 grams/mole, the cationic charge density can be calculated:
Cationic Charge Density =(1 *0.5/157) = 0.00318 or 0.318%.
Thus, at the wash pH of 7.7, polyDMAM has a cationic charge density of 0.318
charge
per 100 dalton molecular weight. As another example, one could make a
copolymer of
DMAM with DMA, where the ratio of monomers is 1 mole of DMAM for 3 moles of
DMA. The DMA monomer has a molecular weight of 99 grams/mole. In this case the
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WO 00/71652 PCTIUSOO/14564
pKa has been measured to be 7.6. Thus, if the wash pH is 5.0, all of the
available
nitrogens will be protonated. The cationic charge density is then calculated:
Cationic Charge Density = 1/(157+99+99+99) = 0.0022, or 0.22%.
At the wash pH of 5.0, a copolymer of DMAM with DMA has a charge density of
0.22
charge per 100 dalton molecular weight. Notice that in this example, the
minimum
repeating unit is considered 1 DMAM monomer plus 3 DMA monomers.
A key aspect of this calculation is the pKa measurement for any protonatable
species which will result in a cationic charge on the heteroatom. Since the
pKa is
dependent on the polymer structure and various monomers present, this must be
measure
to determine the percentage of protonatable sites to count as a function of
the desired
wash pH. This is an easy exercise for one skilled in the art. Based on this
calculation,
the percent of cationic charge is independent of polymer molecular weight.
The pKa of a polymeric suds booster is determined in the following manner.
Make at least 50 mls of a 5% polymer solution, such as a polymer prepared
according to
any of Examples 1 to 5 as described hereinafter, in ultra pure water(i.e. no
added salt).
At 25 C, take initial pH of the 5% polymer solution with a pH meter and
record when a
steady reading is achieved. Maintain temperature throughout the test at 25 C
with a
water bath and stir continuously. Raise pH of 50 mis of the aqueous polymer
solution to
12 using NaOH (1N, 12.5M). Titrate 5 mis of 0.1N HCl into the polymer
solution.
Record pH when steady reading is achieved. Repeat steps 4 and 5 until pH is
below 3.
The pKa was determined from a plot of pH vs. volume of titrant using the
standard
procedure as disclosed in Quantitative Chemical Analysis, Daniel C. Harris,
W.H.
Freeman & Chapman, San Francisco, USA 1982.
It has been surprisingly found that when a polymeric suds booster of the
present
invention is at its optimum charge density, then reducing the molecular weight
of the
polymeric suds booster increases sudsing performance even in the presence of
composite
and/or greasy soils. Accordingly, then the polymeric suds booster is at its
optimum
charge density, the molecular weight of the polymeric suds booster, as
determined in the
manner described hereinbefore, is preferably in the range of from about 1,000
to about
2,000,000, more preferably from about 5,000 to about 500,000, even more
preferably
from about 10,000 to about 100,000, most preferably from about 20,000 to about
50,000
daltons.
The detergent compositions according to the fourth aspect of the present
invention comprise at least an effective amount of one or more polymeric suds
stabilizers
29
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WO 00/71652 PCTIUSOO/14564
described herein, preferably from about 0.01% to about 10%, more preferably
from about
0.05% to about 5%, most preferably from about 0.1% to about 2% by weight, of
said
composition. What is meant herein by "an effective amount of polymeric suds
stabilizer"
is that the suds produced by the presently described compositions are
sustained for an
increased amount of time relative to a composition which does not comprise a
polymeric
suds stabilizer described herein.
Carriers and other Adjunct ingredients
The carrier and other adjuncts ingredients are those addatives which are
conventionally added to detergent compositions. Typicall the is adjuncts
ingredients may
be selected from the group consisting of: soil release polymers, polymeric
dispersants,
polysaccharides, abrasives, bactericides, tarnish inhibitors, builders,
enzymes, enzyme
stabilizers, opacifiers, dyes, perfumes, thickeners, antioxidants, processing
aids, suds
boosters, buffers, antifungal or mildew control agents, insect repellants,
anti-corrosive
aids, bleach, aqueous liquid carrier, bleach catalysts, bleach activators,
solvent, fabric
softeners, hydrotrope, pH adjusting material dye transfer inhibitors, optical
bleach,
brightener, suds supressors, electrolytes, and chelants.
Surfactants - Suitable detersive surfactants are extensively illustrated in
U.S. 3,929,678,
Dec. 30, 1975 Laughlin, et al, and U.S. 4,259,217, March 31, 1981, Murphy; in
the series
"Surfactant Science", Marcel Dekker, Inc., New York and Basel; in "Handbook of
Surfactants", M.R. Porter, Chapman and Hall, 2nd Ed., 1994; in "Surfactants in
Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987; and in numerous
detergent-
related patents assigned to Procter & Gamble and other detergent and consumer
product
manufacturers.
The detersive surfactant herein includes anionic, nonionic, cationic,
zwitterionic or
amphoteric types of surfactant known for use as cleaning agents, but does not
include
completely foam-free or completely insoluble surfactants (though these may be
used as
optional adjuncts).
The composition will preferably contain at least about 0.01%, more preferably
at
least about 0.1%, even more preferably still, at least about 0.2%, even more
preferably
still, at least about 0.5% by weight of said composition of surfactant. The
composition
will also preferably contain no more than about 90%, more preferably no more
than
about 70%, even more preferably, no more than about 60%, even more preferably,
no
more than about 35% by weight of said composition of surfactant.
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WO 00/71652 PCTIUSOO/14564
Some preferred among the above-identified detersive surfactants are: C9-C20
linear alkylbenzene sulfonates, particularly sodium linear secondary alkyl C
10-C 15
benzenesulfonates though in some regions ABS may be used; olefinsulfonate
salts, that
is, material made by reacting olefins, particularly C 10-C20 a-olefins, with
sulfur trioxide
and then neutralizing and hydrolyzing the reaction product; sodium and
ammonium C7-
C12 dialkyl sulfosuccinates; alkane monosulfonates, such as those derived by
reacting
C8-C20 a-olefins with sodium bisulfite and those derived by reacting paraffins
with S02
and C12 and then hydrolyzing with a base to form a random sulfonate; a-Sulfo
fatty acid
salts or esters; sodium alkylglycerylsulfonates, especially those ethers of
the higher
alcohols derived from tallow or coconut oil and synthetic alcohols derived
from
petroleum; alkyl or alkenyl sulfates, which may be primary or secondary,
saturated or
unsaturated, branched or unbranched. Such compounds when branched can be
random
or regular. When secondary, they preferably have formula CH3(CH2)x(CHOSO3 M+)
CH3 or CH3(CH2)y(CHOSO3 M+) CH2CH3 where x and (y + 1) are integers of at
least
7, preferably at least 9 and M is a water-soluble cation, preferably sodium.
When
unsaturated, sulfates such as oleyl sulfate are preferred, while the sodium
and ammonium
alkyl sulfates, especially those produced by sulfating C8-C 1 g alcohols,
produced for
example from tallow or coconut oil are also useful; also preferred are the
alkyl or alkenyl
ether sulfates, especially the ethoxy sulphates having about 0.5 moles or
higher of
ethoxylation, preferably from 0.5-8; the alkylethercarboxylates, especially
the EO 1-5
ethoxycarboxylates; soaps or fatty acids, preferably the more water-soluble
types;
aminoacid-type surfactants, such as sarcosinates, especially oleyl
sarcosinate; phosphate
esters; alkyl or alkylphenol ethoxylates, propoxylates and butoxylates,
especially the
ethoxylates "AE", including the so-called narrow peaked alkyl ethoxylates and
C6-C12
alkyl phenol alkoxylates as well as the products of aliphatic primary or
secondary linear
or branched Cg-Clg alcohols with ethylene oxide, generally 2-30 EO; N-alkyl
polyhydroxy fatty acid amides especially the C 12-C 1 g N-methylglucamides,
see WO
9206154, and N-alkoxy polyhydroxy fatty acid amides, such as C10-Cl8 N-(3-
31
CA 02372892 2004-07-20
methoxypropyl) glucamide while N-propyl through N-hexyl C 12-C18 glucamides
can be
used for low sudsing; alkyl polyglycosides; amine oxides, preferably
alkyldimethylamine
N- oxides and their dihydrates; sulfobetaines or "sultaines"; betaines; and
gemini
surfactants.
Cationic surfactants suitable for use in the present invention include those
having
a long-chain hydrocarbyl group. Examples of such cationic co-surfactants
include the
ammonium co-surfactants such as alkyldimethylammonium halogenides, and those
co-
surfactants having the formula:
[R2(OR3)y] [R4(OR3)y]2R5N+X-
wherein R2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms
in the
alkyl chain, each R3 is selected from the group consisting of -CH2CH2-,
-CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4
is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl,
benzyl ring
structures formed by joining the two R4 groups, -CH2CHOH-
CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose polymer having a
molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the
same as
R4 or is an alkyl chain wherein the total number of carbon atonis of R2 plus
R5 is not
more than about 18; each y is from 0 to about 10 and the sum of the y values
is from 0 to
about 15; and X is any compatible anion.
Examples of other suitable cationic surfactants are described in following
documents: M.C. Publishing Co., McCutcheon's, Detergents &
Emulsifiers, (North American edition 1997); Schwartz, et al., Surface Active
Agents, Their Chemistry and Technology, New
York: Interscience Publishers, 1949; U.S. Patent 3,155,591; U. S. Patent
3,929,678; U. S.
Patent 3,959,461 U. S. Patent 4,387,090 and U.S. Patent 4,228,044.
Exan7ples of suitable cationic surfactants are those corresponding to the
general
formula:
32
CA 02372892 2004-07-20
+
R3 ~
RZ/~ R4
wherein RI, R2, R3, and R4 are independently selected from an aliphatic group
of from I
to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido,
hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and
X is a salt-
forming anion such as those selected from halogen, (e.g. chloride, bromide),
acetate,
citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate
radicals. The
aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether
linkages,
and other groups such as amino groups. The longer chain aliphatic groups,
e.g., those of
about 12 carbons, or higher, can be saturated or unsaturated. Preferred is
when R1, R2,
R3, and R4 are independently selected from Cl to about C22 alkyl. Especially
preferred
are cationic materials containing two long alkyl chains and two short alkyl
chains or
those containing one long alkyl chain and three short alkyl chains. The long
alkyl chains
in the compounds described in the previous sentence have from about 12 to
about 22
carbon atoms, preferably from about 16 to about 22 carbon atoms, and the short
alkyl
chains in the compounds described in the previous sentence have from I to
about 3
carbon atoms, preferably from 1 to about 2 carbon atoms.
Suitable levels of cationic detersive suriactant herein are from about 0.1% to
about 20%, preferably from about 1% to about 15%, although much higher levels,
e.g.,
up to about 30% or more, may be useful especially in nonionic: cationic (i.e.,
limited or
anionic-free) formulations. One possible use of cationic surfactants is as
grease release
agents. Cationic surfactants can be on their own or in combination with
solvents and/or
solublizing agents. See US Patent 5,552,089.
Another type of useful surfactants are the so-called dianionics. These are
surfactants which have at least two anionic groups present on the surfactant
molecule.
Some suitable dianionic surfactants are further described in WO 98/00498,
WO 98/00503, WO 98/05742, WO 98/05749 and US 5958858.
33
CA 02372892 2004-07-20
Additionally and preferably, the surfactant may be a midchain branched alkyl
sulfate, midchain branched alkyl alkoxylate, or midchain branched alkyl
alkoxylate sulfate.
These surfactants are further described in WO 99/19434, WO 99118929, WO
99/19435, WO
99/18928, WO 99/19448 and WO 99/19449. Other suitable mid-chain branched
surfactants
can be found in WO 97/39087, WO 97/39088, WO 97/39091, WO 98/23712, WO
97/38972, WO 97/39089 and WO 97/39090. Mixtures of these branched surfactants
with
conventional linear surfactants are also suitable for use in the present
compositions.
Another preferred anionic surfactant are the so-called modified alkyl benzene
sulfonate surfactants, or MLAS. Some suitable MLAS surfactants, methods of
making them
and exempliary compositions are further described in WO 99/05243, WO 99/05242,
WO
99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549 and
WO 00/23548.
Suitable levels of anionic detersive surfactants herein are in the range from
about
1% to about 50% or higher, preferably from about 2% to about 30%, more
preferably still,
from about 5% to about 20% by weight of the detergent composition.
Suitable levels of nonionic detersive surfactant herein are from about 1% to
about
40%, preferably from about 2% to about 30%, more preferably from about 5% to
about
20%.
34
CA 02372892 2004-07-20
Suitable levels of cationic detersive surfactant herein are from about 0.1% to
about 20%, preferably from about 1% to about 15%, although much higher levels,
e.g.,
up to about 30% or more, may be useful especially in nonionic : cationic
(i.e., limited or
anionic-free) formulations.
Amphoteric or zwitterionic detersive surfactants when present are usually
useful
at levels in the range from about 0.1% to about 20% by weight of the detergent
composition. Often levels will be limited to about 5% or less, especially when
the
amphoteric is costly.
The anionic surfactants useful in the present invention are preferably
selected from
the group consisting of, linear alkylbenzene sulfonate, alpha olefin
sulfonate, paraffin
sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate,
alkyl sulfonates,
alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates,
taurinates, and
mixtures thereof.
When present, anionic surfactant will be present typically in an effective
amount.
More preferably, the composition may contain at least about 0.5%, more
preferably at
least about 5%, even more preferably still, at least about 10% by weight of
said
composition of anionic surfactant. The composition will also preferably
contain no more
than about 90%, more preferably no nlore than about 50%, even more preferably,
no
more than about 30% by weiglit of said composition of anionic surfactant.
Alkyl sulfate surfactants are another type of anionic surfactant of importance
for
use herein. In addition to providing excellent overall cleaning ability when
used in
combination with polyhydroxy fatty acid amides (see below), including good
grease/oil
cleaning over a wide range of temperatures, wash concentrations, and wash
times,
dissolution of alkyl sulfates can be obtained, as well as improved
formulability in liquid
detergent formulations are water soluble salts or acids of the formula IZOSO3M
wherein
R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a
C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and
M is H
or a cation, e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium,
lithium),
substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and
trimethyl
amrnonium and quatemary ammonium cations, e.g., tetramethyl-ammonium and
CA 02372892 2004-07-20
dimethyl piperdinium, and cations derived fronl alkanolamines such as
ethanolamine,
diethanolamine, triethanolamine, and mixtures thereof, and the like.
Typically, alkyl
chains of C12-16 are preferred for lower wash temperatures (e.g., below about
50 C) and
C16-18 alkyl chains are preferred for higher wash temperatures (e.g., above
about 50 C).
Alkyl alkoxylated sulfate surfactants are another category of useful anionic
surfactant. These surfactants are water soluble salts or acids typically of
the formula
RO(A)mSO 3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group
having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl,
more
preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is
greater
than zero, typically between about 0.5 and about 6, more preferably between
about 0.5
and about 3, and M is H or a cation which can be, for example, a metal cation
(e.g.,
sodium, potassium, lithium, etc.), ammonium or substituted-ammonium cation.
Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated
herein.
Specific examples of substituted ammonium cations include methyl-, dimethyl-,
trimethyl-ammonium and quatemary ammoniuni cations, such as tetramethyl-
ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g.
monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18
alkyl
polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and
C12-C18
alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from
sodium and
potassium. Surfactants for use herein can be made from natural or synthetic
alcohol
feedstocks. Chain lengths represent average hydrocarbon distributions,
including
branching. The anionic surfactant component may comprise alkyl sulfates and
alkyl
ether sulfates derived from conventional alcohol sources, e.g., natural
alcohols, synthetic
alcohols such as those sold under the trade marks of NEODOLTM, ALFOLTM,
LIALTM,
LUTENSOLTM and the like. Alkyl ether sulfates are also known as alkyl
polyethoxylate
sulfates.
Examples of suitable anionic surfactants are given in "Surface Active Agents
and
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such
surfactants
36
CA 02372892 2004-07-20
are also generally disclosed in U.S. Patent 3,929,678, issued December 30,
1975 to
Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
One type of anionic surfactant which can be utilized encompasses alkyl ester
sulfonates. These are desirable because they can be made with renewable, non-
petroleum
resources. Preparation of the alkyl ester sulfonate surfactant component can
be effected
according to known methods disclosed in the technical literature. For
instance, linear
esters of C8-C20 carboxylic acids can be sulfonated with gaseous SO 3
according to "The
Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329.
Suitable starting
materials would include natural fatty substances as derived from tallow, palm,
and
coconut oils, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
applications,
comprises alkyl ester sulfonate surfactants of the structural formula:
0
R3CHCOR4
SO3M
wherein R' is a C8-C20 hydrocarbyl, preferably an. alkyl, or combination
thereof, R4 is a
Cl-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a
soluble salt-
forming cation. Suitable salts include metal salts such as sodium, potassium,
and lithium
salts, and substituted or unsubstituted ammonium salts, such as methyl-,
dimethyl, -
trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and
dimethyl
piperdinium, and cations derived from alkanolamines, e.g. monoethanol-amine,
diethanolamine, and triethanolamine. Preferably, R' is C10-C16 alkyl, and.R4.
is methyl,
ethyl or isopropy]. Especially preferred are the methyl ester sulfonates
wherein R3 is
C14-C16 alkyl.
Other anionic surfactants useful for detersive purposes can also be included
in the
compositions hereof. These can include salts (including, for example, sodium,
potassium, ammoniun-i, and substituted anunonium salts such as mono-, di- and
triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulphonates, CS-C22
primary
or secondary alkanesulphonates, C8-C24 olefinsulphonates, sulphonated
polycarboxylic
acids prepared by sulphonation of the pyrolyzed product of alkaline earth
metal citrates,
37
CA 02372892 2004-07-20
e.g., as described in British patent specification No. 1,082,179, alkyl
glycerol sulfonates,
fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol
ethylene oxide
ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as
the acyl
isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinamates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and
unsaturated C12-
C18 monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6-C14
diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described below),
branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those
of the
formula RO(CH2CH2O)kCH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer
from 0 to 10, and M is a soluble salt-forming cation, and fatty acids
esterified with
isethionic acid and neutralized with sodium hydroxide. Resin acids and
hydrogenated
resin acids are also suitable, such as rosin, hydrogenated rosin, and resin
acids and
hydrogenated resin acids present in or derived from tall oil. Further examples
are given
in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry
and Berch).
A variety of such surfactants are also generally disclosed in U.S. Patent
3,929,678, issued
December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29,
line 23.
Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent
3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14
through
column 16, line 6. Exemplary, non-limiting classes of
useful nonionic surfactants include: alkyl ethoxylate, alkanoyl glucose amide,
C12 -C18
alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl
ethoxylates and C6-
C12 alkyl phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy), and
mixtures thereof.
When present, nonionic surfactant will be present typically in an effective
amount. More preferably, the composition may contain at least about 0.1%, more
preferably at least about 0.2%, even more preferably still, at least about
0.5% by weight
of said composition of nonionic surfactant. The composition will also
preferably contain
no more than about 20%, more preferably no more than about 15%, even more
38
CA 02372892 2001-11-01
WO 00/71652 PCTIUSOO/14564
preferably, no more than about 10% by weight of said composition of nonionic
surfactant.
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols. In general, the polyethylene oxide condensates are preferred. These
compounds
include the condensation products of alkyl phenols having an alkyl group
containing
from about 6 to about 12 carbon atoms in either a straight chain or branched
chain
configuration with the alkylene oxide. In a preferred embodiment, the ethylene
oxide is
present in an amount equal to from about 5 to about 25 moles of ethylene oxide
per mole
of alkyl phenol. Commercially available nonionic surfactants of this type
include
Igepal0 CO-630, marketed by the GAF Corporation; and TritonO X-45, X-114, X-
100,
and X-102, all marketed by the Rohm & Haas Company. These compounds are
commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol
ethoxylates).
The condensation products of aliphatic alcohols with from about 1 to about 25
moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either
be straight or
branched, primary or secondary, and generally contains from about 8 to about
22 carbon
atoms. Particularly preferred are the condensation products of alcohols having
an alkyl
group containing from about 10 to about 20 carbon atoms with from about 2 to
about 18
moles of ethylene oxide per mole of alcohol. Examples of commercially
available
nonionic surfactants of this type include Tergitol0 15-S-9 (the condensation
product of
C11-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol0 24-L-
6
NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene
oxide with a narrow molecular weight distribution), both marketed by Union
Carbide
Corporation; Neodol0 45-9 (the condensation product of C 14-C 15 linear
alcohol with 9
moles of ethylene oxide), Neodol0 23-6.5 (the condensation product of C12-C13
linear
alcohol with 6.5 moles of ethylene oxide), Neodol0 45-7 (the condensation
product of
C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol0 45-4 (the
condensation product of C 14-C 15 linear alcohol with 4 moles of ethylene
oxide),
marketed by Shell Chemical Company, and KyroO EOB (the condensation product of
C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble
Company. Other commercially available nonionic surfactants include Dobanol 91-
80
39
CA 02372892 2004-07-20
marketed by Shell Chemical Co. and Genapol UD-080 marketed by Hoechst. This
category of nonionic surfactant is referred to generally as "alkyl
ethoxylates."
The condensation products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol.. The hydrophobic
portion of
these compounds preferably has a molecular weight of from about 1500 to about
1800
and exhibits water insolubility. The addition of polyoxyethylene moieties to
this
hydrophobic portion tends to increase the wate:r solubility of the molecule as
a whole,
and the liquid character of the product is retained up to the point where the
polyoxyethylene content is about 50% of the total weight of the condensation
product,
which corresponds to condensation with up to about 40 moles of ethylene oxide.
Examples of compounds of this type include certain of the commercially-
available
Pluronic R surfactants, niarketed by BASF.
The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of
these
products consists of the reaction product of ethylenediamine and excess
propylene oxide,
and generally has a molecular weight of frorn about 2500 to about 3000. This
hydrophobic moiety is condensed with ethylene oxide to the extent that the
condensation
product contains from about 40% to about 80% by weight of polyoxyethylene and
has a
molecular weight of from about 5,000 to about 11,000. Examples of this type of
nonionic surfactant include certain of the comniercially available Tetronic
compounds,
marketed by BASF.
Examples of ethylene oxide-propylene oxide block co-polymers suitable for uses
herein are described in greater detail in Pancheri/Mao; U.S. Patent 5,167,872;
Issued
December 2, 1992.
The preferred alkylpolyglycosides have the formula
R2 (C.,H2nOVglycosyl)X
wherein RZ is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about
to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3
to about 10,
CA 02372892 2001-11-01
WO 00/71652 PCT/US00/14564
preferably from about 1.3 to about 3, most preferably from about 1.3 to about
2.7. The
glycosyl is preferably derived from glucose. To prepare these compounds, the
alcohol or
alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a
source of
glucose, to form the glucoside (attachment at the 1-position). The additional
glycosyl
units can then be attached between their 1-position and the preceding glycosyl
units 2-, 3-
4- and/or 6-position, preferably predominantly the 2-position.
Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued
January
21, 1986, having a hydrophobic group containing from about 6 to about 30
carbon atoms,
preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g.,
a
polyglycoside, hydrophilic group containing from about 1.3 to about 10,
preferably from
about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide
units. Any
reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose,
galactose
and galactosyl moieties can be substituted for the glucosyl moieties.
(Optionally the
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or
galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds
can be,
e.g., between the one position of the additional saccharide units and the 2-,
3-, 4-, and/or
6- positions on the preceding saccharide units.
Optionally, and less desirably, there can be a polyalkylene-oxide chain
joining the
hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide
is
ethylene oxide. Typical hydrophobic groups include alkyl groups, either
saturated or
unsaturated, branched or unbranched containing from about 8 to about 18,
preferably
from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a
straight chain
saturated alkyl group. The alkyl group can contain up to about 3 hydroxy
groups and/or
the polyalkyleneoxide chain can contain up to about 10, preferably less than
5,
alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyl,
decyl,
undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and
octadecyl,
di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides,
glucoses, fructosides,
fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-
, tetra-, and
pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
41
CA 02372892 2004-07-20
The ethoxylated glycerol type compound which may be used in the in the instant
composition are manufactured by the Kao Corporation and sold under the trade
mark
Levenol such as Levenol F-200 which has an average EO of 6 and a molar ratio
of coco
fatty acid to glycerol of 0.55 or Levenol V501/2 which has an average EO of 17
and a
molar ratio of tallow fatty acid to glycerol of 1Ø It is preferred that the
molar ratio of the
fatty acid to glycerol is less than 1.7, more preferably less than 1.5 and
most preferably
less than 1Ø The ethoxylated glycerol type compound has a molecular weight
of 400 to
1600, and a pH (50 grams/liter of water) of 5-7. The Levenol compounds are
substantially non irritant to human skin and have a prinlary biodegradabillity
higher than
90% as measured by the Wickbold method Bias-7d. Two examples of the Levenol
compounds are Levenol V-501/2 which has 17 ethoxylated groups and is derived
from
tallow fatty acid with a fatty acid to glycerol ratio of 1.0 and a molecular
weight of 1465
and Levenol F-200 has 6 ethoxylated groups and is derived from coco fatty acid
with a
fatty acid to glycerol ratio of 0.55. Both Levenol F-200 and Levenol V-501/2
are
composed of a mixture of Formula (I) and Formula (II). The Levenol compounds
has
ecoxicity values of algae growth inhibition >100 mg/liter; acute toxicity for
Daphniae
>100 mg/liter and acute fish toxicity >100 ingg/later. The Levenol compounds
have a
ready biodegradability higher than 60% which is the minimum required value
according
to OECD 301B measurement to be acceptably biodegradable. Polyesterified
nonionic
TM
compounds also useful in the instant compositions are Crovol PK-40 and Crovol
PK-70
manufactured by Croda GMBH of the Netherlands. Crovol PK-40 is a
polyoxyethylene
(12) Palm Kemel Glyceride which has 12 EO groups. Crovol PK-70 which is
preferred is
a polyoxyethylene (45) Palm Kernel Glyceride have 45 EO groups. More
information on
these nonionic surfactants can be found in US Patent No 5719114,
Another type of suitable nonionic surfactant comprises the polyhydroxy fatty
acid
amides. These materials are more fully described in Pan/Gosselink; U.S Patent
5,332,528, issued July 26, 1994. These polyhydroxy fatty acid amides have a
general
structure of the formula:
42
CA 02372892 2004-07-20
0
RZCNZ
RI
wherein: R'. is H, CI-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture
thereof, preferably Cl-C4 alkyl, more preferably Cl or C2 alkyl, most
preferably Cl
alkyl (i.e., methyl); and R'` is a C5-C31 hydrocarbyl, preferably straight
chain C7-C19
alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most
preferably
straight chain Cll-C15 alkyl or alkenyl, or mixtures thereof; and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls
directly connected to the chain, or an alkoxylated derivative (preferably
ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing sugar in a
reductive
amination reaction; more preferably Z will be a glycitvl. Suitable reducing
sugars
include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
As raw
materials, high dextrose corn syrup, high fructose corn syrup, and high
maltose corn
syrup can be utilized as well as the individual sugars listed above. These
corn syrups
may yield a mix of sugar components for Z. It should be understood that it is
by no
means intended to exclude other suitable raw materials. Z preferably will be
selected
from the group consisting of -CH2-(CHOH)õ-CH20H, -CH(CH2OH)- (CHOH)n_1-
CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH,,OH, and alkoxylated derivatives
thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic
or aliphatic
monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH,-
(CHOH)4-CHZOH.
R' can be, for exaniple, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-
2-
hydroxy ethyl, or N-2-hydroxy propyl.
R2 -CO-N< can be, for example, cocamide, stearamide, olearrnide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In
general, they can be made by reacting an alkyl amine with a reducing sugar in
a reductive
43
CA 02372892 2004-07-20
amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then
reacting
the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a
condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid
amide
product. Pi-ocesses for making compositions containing polyhydroxy fatty acid
amides
are disclosed, for example, in G.B. Patent Specification 809,060, published
February 18,
1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20,
1960
to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March
8,
1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott.
Examples of such surfactants include the C10-C18 N-methyl, or N-hydroxypropyl,
glucamides. The N-propyl through N-hexyl C12-C16 glucamides can be used for
lower
sudsing performance.
Preferred amides are C8-C20 ammonia amides, monoethanolamides,
diethanolamides, and isopropanolamides.
Another suitable class of surfactants are the alkanol amide surfactants,
including
the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl
moiety
containing from about 8 to about 18 carbon atoms. These materials are
represented by
the formula:
0 (H)m-1
RIC-N\
(R2 11)3-m
wherein R, is a saturated or unsaturated, hydroxy-free aliphatic hydrocarbon
group
having from about 7 to 21, preferably from about 11 to 17 carbon atoms; R2
represents a
methylene or ethylene group; and m is 1, 2, or 3, preferably 1. Specific
examples of such
amides are monoethanol amine coconut fatty acid amide and diethanolamine
dodecyl
fatty acid amide. These acyl moieties may be derived from naturally occurring
glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be
derived
synthetically, e.g., by the oxidation of petroleum or by hydrogenation of
carbon
monoxide by the Fischer-Tropsch process. The monoethanolamides and
diethanolamides
of C 12-14 fatty acids are preferred.
44
CA 02372892 2001-11-01
WO 00/71652 PCT/USOO/14564
Amphoteric Surfactants - Amphoteric surfactants may optionally be incorporated
into the
detergent compositions hereof. These surfactants can be broadly described as
aliphatic
derivatives of secondary or tertiary amines, or aliphatic derivatives of
heterocyclic
secondary and tertiary amines in which the aliphatic radical can be straight
chain or
branched. One of the aliphatic substituents contains at least about 8 carbon
atoms,
typically from about 8 to about 18 carbon atoms, and at least one contains an
anionic
water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent
No. 3,929,678
to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for
examples of
ampholytic surfactants. Preferred amphoteric include C12-C18 betaines and
sulfobetaines ("sultaines"), C10-C18 amine oxides, and mixtures thereof.
When present, amphoteric surfactant will be present typically in an effective
amount. More preferably, the composition may contain at least about 0.1%, more
preferably at least about 0.2%, even more preferably still, at least about
0.5% by weight
of said composition of amphoteric surfactant. The composition will also
preferably
contain no more than about 20%, more preferably no more than about 15%, even
more
preferably, no more than about 10% by weight of said composition of amphoteric
surfactant.
Amine oxides are amphoteric surfactants and include water-soluble amine oxides
containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2
moieties
selected from the group consisting of alkyl groups and hydroxyalkyl groups
containing
from about 1 to about 3 carbon atoms; water-soluble phosphine oxides
containing one
alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected
from the
group consisting of alkyl groups and hydroxyalkyl groups containing from about
1 to
about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety
of from
about 10 to about 18 carbon atoms and a moiety selected from the group
consisting of
alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Preferred amine oxide surfactants have the formula
0
R3(OR4)XN(RS)2
CA 02372892 2004-07-20
wherein R' is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
thereof
containing from about 8 to about 22 carbon atoms; R4 is an alkylene or
hydroxyalkylene
group containing from about 2 to about 3 carbon atoms or mixtures thereof; x
is from 0
to about 3; and each RS' is an alkyl or hydroxyalkyl group containing from
about 1 to
about 3 carbon atoms or a polyethylene oxide group containing from about I to
about 3
ethylene oxide groups. The R5 grdups can be attached to each other, e.g.,
through an
oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C10-C18 alkyl dimethyl
amine
oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
When present, amine oxide surfactant will be present typically in an effective
amount. More preferably, the composition may contain at least about 0.1%, more
preferably at least about 0.2%, even more preferably still, at least about
0.5% by weight
of said composition of amine oxide surfactant. The composition will also
preferably
contain no more than about 20%, more preferably no more than about 15%, even
more
preferably, no more than about 10% by weight of said composition of amine
oxide
surfactant.
Examples of suitable amine oxide surfactants are given in "Surface Active
Agents
and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
Suitable betaine surfactants include those of the general formula:
0
11
RN+(R1 )Z- R2C O-
wherein R is a hydrophobic group selected from alkyl groups containing from
about 10 to
about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms,
alkyl aryl and
aryl alkyl groups containing a similar number of carbon atoms with a benzene
ring being
treated as equivalent to about 2 carbon atoms, and similar structures
interrupted by amino
or ether linkages; each R' is an alkyl group containing from 1 to about 3
carbon atoms;
and Rz is an alkylene group containing from I to about 6 carbon atoms.
Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl
betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine,
tetrad ecyl ami dopropyldimethyl betaine, and dodecyldimethylamrnonium
hexanoate.
46
CA 02372892 2004-07-20
Other suitable amidoalkylbetaines are disclosed in U.S. Patent Nos. 3,950,417;
4,137,191; and 4,375,421; and British Patent GB No. 2,103,236.
Zwitterionic Surfactants - Zwitterionic surfactants can also be incorporated
into the
detergent compositions hereof. These surfactaiits can be broadly described as
derivatives
of secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary
amines, or derivatives of quatemary ammonium, quaternary phosphonium or
tertiary
sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at column 19, line 38 through column 22, line 48 for
examples of
zwitterionic surfactants. Ampholytic and zwitterionic surfactants are
generally used in
combination with one or more anionic and/or nonionic surfactants.
Detersive Enzymes - Enzymes are optionally included in the present detergent
compositions for a variety of purposes, including removal of protein-based,
carbohydrate-based, or triglyceride-based stains from substrates. Recent
enzyme
disclosures in detergents useful herein include chondriotinase (EP 747,469 A);
protease
variants (WO 96/28566 A; WO 96/28557 A; WO 96/28556 A; WO 96/25489 A);
xylanase (EP 709,452 A); keratinase (EP 747,470 A); lipase (GB 2,297,979 A; WO
96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154 A); cellulase (GB
2,294,269 A; WO 96/27649 A; GB 2,303,147 A); thermitase (WO 96/28558 A). More
generally, suitable enzymes include cellulases, hemicellulases, proteases,
gluco-
amylases, amylases, lipases, cutinases, pectinases, xylanases, keratinases,
reductases,
oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
chondriotinases, thermitases, pentosanases, malanases, 13-glucanases,
arabinosidases or
mixtures thereof of any suitable origin, such as vegetable, animal, bacterial,
fungal and
yeast origin. Preferred selections are influenced by factors such as pH-
activity and/or
stability optima, thermostability, and stability to active detergents,
builders and the like.
In this respect bacterial or fungal enzymes are preferred, such as bacterial
amylases and
proteases, and fungal cellulases. A preferred combination is a detergent
composition
having a cocktail of conventional applicable enzymes like protease, amylase,
lipase,
cutinase and/or cellulase. Suitable enzymes are also described in US Patent
Nos.
47
CA 02372892 2001-11-01
WO 00/71652 PCT/US00/14564
5,677,272, 5,679,630, 5,703,027, 5,703,034, 5,705,464, 5,707,950, 5,707,951,
5,710,115,
5,710,116, 5,710,118, 5,710,119 and 5,721,202.
The composition will preferably contain at least about 0.0001%, more
preferably
at least about 0.0005%, even more preferably still, at least about 0.001% by
weight of the
composition of enzyme. The cleaning composition will also preferably contain
no more
than about 5%, more preferably no more than about 2%, even more preferably, no
more
than about 1% by weight of the composition of enzyme.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or otherwise beneficial effect in cleaning compositions. Preferred
detersive
enzymes are hydrolases such as proteases, amylases and lipases. Highly
preferred are
amylases and/or proteases, including both current commercially available types
and
improved types.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The term
"cleaning effective amount" refers to any amount capable of producing a
cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness improving effect
on
substrates such as fabrics, dishware and the like. In practical terms for
current
commercial preparations, typical amounts are up to about 5 mg by weight, more
typically
0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
Stated
otherwise, the compositions herein will typically comprise from 0.001% to 5%,
preferably 0.01 %-1 % by weight of a commercial enzyme preparation. Protease
enzymes
are usually present in such commercial preparations at levels sufficient to
provide from
0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain
detergents it may be desirable to increase the active enzyme content of the
commercial
preparation in order to minimize the total amount of non-catalytically active
materials
and thereby improve spotting/filming or other end-results. Higher active
levels may also
be desirable in highly concentrated detergent formulations.
Proteolytic Enzyme - The proteolytic enzyme can be of animal, vegetable or
microorganism (preferred) origin. The proteases for use in the detergent
compositions
herein include (but are not limited to) trypsin, subtilisin, chymotrypsin and
elastase-type
48
CA 02372892 2004-07-20
proteases. Preferred for use herein are subtilisin-type proteolytic enzymes.
Particularly
preferred is bacterial serine proteolytic enzyme obtained from Bacillus
subtilis and/or
Bacillus licheniformis.
Suitable proteolytic enzymes include Novo Industri A/S Alcalase (preferred),
Esperase , Savinase (Copenhagen, Denmark), Gist-brocades' Maxatase , Maxacal
and Maxapem 15 (protein engineered Maxaca7 ) (Delft, Netherlands), and
subtilisin
BPN and BPN'(preferred), which are commercially available. Preferred
proteolytic
enzymes are also modified bacterial serine proteases, such as those made by
Genencor
international, Inc. (San Francisco, California) which are described in
European Patent
251,446B, granted December 28, 1994 (particularly pages 17, 24 and 98) and
which are
also called herein "Protease B". U.S. Patent 5,030,378, Venegas, issued July
9, 1991,
refers to a modified bacterial serine proteolytic enzyme (Genencor
Internationai) which is
called "Protease A" herein (same as BPN'). In particular see columns 2 and 3
of U.S.
Patent 5,030,378 for a complete description, including amino sequence, of
Protease A
and its variants. Other proteases are sold under the trademarks: Primase,
Durazym,
Opticlean and Optimase. Preferred proteolytic enzymes, then, are selected from
the
group consisting of Alcalase (Novo Industri A/S), BPN', Protease A and
Protease B
(Genencor), and mixtures thereof. Protease B is most preferred.
Of particular interest for use herein are the proteases described in U.S.
Patent No.
5,470,733.
Another preferred protease, referred to as "Protease D" is a carbonyl
hydrolase
variant having an amino acid sequence not found in nature, which is derived
from a
precursor carbonyl hydrolase by substituting a different amino acid for a
plurality of
amino acid residues at a position in said carbonyl hydrolase equivalent to
position +76,
preferably also in combination with one or more amino acid residue positions
equivalent
to those selected from the group consisting of +99, +101, +103, +104, +107,
+123, +27,
+105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216,
+217,
+218, +222, +260, +265, and/or +274 according to the numbering of Bacillus
49
CA 02372892 2004-07-20
amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20,
1995 by
Genencor International (A. Baeck et al. entitled "Protease-Containing Cleaning
Compositions" having U.S. Patent No. 5,679,630).
Useful proteases are also described in PCT publications: WO 95/30010 published
November 9, 1995 by The Procter & Gamble Conipany; WO 95/30011 published
November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published
November 9, 1995 by The Procter & Ganible Company.
Protease enzyme may be incorporated into the compositions in accordance with
the
invention at a level of from 0.0001 % to 2% active enzyme by weight of the
composition.
The composition will preferably contain at least about 0.0001%, more
preferably
at least about 0.0002%, more preferably at least about 0,0005%, even more
preferably
still, at least about 0.001 % of active enzyme by weight of the composition of
protease
enzyme. The composition will also preferably contain no niore than about 2%,
more
preferably no more than about 0.5%, more preferably no more than about 0.1%,
even
more preferably, no more than about 0.05% of active enzyme by weight of the
composition of protease enzyme.
Amylase - Amylases ((x and/or B) can be included for removal of carbohydrate-
based
stains. Suitable amylases are Termamyl (Novo Nordisk), Fungamyl and BAN@
(Novo Nordisk). The enzymes may be of any suitable origin, such as vegetable,
animal,
bacterial, fungal and yeast origin.
The composition will preferably contain at least about 0.0001%, more
preferably
at least about 0.0002%, more preferably at least about 0.0005%, even more
preferably
still, at least about 0.001% of active enzyme by weight of the composition of
amylase
enzyme. The composition will also preferably contain no more than about 2%,
more
preferably no more than about 0.5%, more preferably no more than about 0.1%,
even
more preferably, no more than about 0.05% of active enzyme by weight of the
composition of amylase enzyme.
Amylase enzymes also include those described in W095/26397 and
WO 96/23873. Other specific amylase enzymes for use in the detergent
compositions of the
present invention therefore include:
CA 02372892 2001-11-01
WO 00/71652 PCT/US00/14564
(a) a-amylases characterised by having a specific activity at least 25% higher
than the
specific activity of Termamyl at a temperature range of 25 C to 55 C and at a
pH value
in the range of 8 to 10, measured by the Phadebas a-amylase activity assay.
Such
Phadebas a-amylase activity assay is described at pages 9-10, W095/26397.
(b) a-amylases according (a) comprising the amino sequence shown in the SEQ ID
listings in the above cited reference. or an a-amylase being at least 80%
homologous
with the amino acid sequence shown in the SEQ IDlisting.
(c) a-amylases according (a) obtained from an alkalophilic Bacillus species,
comprising
the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-
Thr-
Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.
A polypeptide is considered to be X% homologous to the parent amylase if a
comparison of the respective amino acid sequences, performed via algorithms,
such as
the one described by Lipman and Pearson in Science 227, 1985, p. 1435, reveals
an
identity of X%
(d) a-amylases according (a-c) wherein the a-amylase is obtainable from an
alkalophilic
Bacillus species; and in particular, from any of the strains NCIB 12289, NCIB
12512,
NCIB 12513 and DSM 935.
In the context of the present invention, the term "obtainable from" is
intended not only to
indicate an amylase produced by a Bacillus strain but also an amylase encoded
by a DNA
sequence isolated from such a Bacillus strain and produced in an host organism
transformed with said DNA sequence.
(e)a-amylase showing positive immunological cross-reactivity with antibodies
raised
against an a-amylase having an amino acid sequence corresponding respectively
to those
a-amylases in (a-d).
(f) Variants of the following parent a-amylases which (i) have one of the
amino acid
sequences shown in corresponding respectively to those a-amylases in (a-e), or
(ii)
displays at least 80% homology with one or more of said amino acid sequences,
and/or
displays immunological cross-reactivity with an antibody raised against an a-
amylase
having one of said amino acid sequences, and/or is encoded by a DNA sequence
which
51
CA 02372892 2004-07-20
hybridizes with the same probe as a DNA sequence encoding an a-amylase having
one of
said amino acid sequence; in which variants
1. at least one amino acid residue of said parent a-amylase has been deleted;
and/or
2. at least one aniino acid residue of said parent a-amylase has been replaced
by a
different amino acid residue; and/or
3. at least one amino acid residue has been inserted relative to said parent a-
amylase;
said variant having an a-amylase activity and exhibiting at least one of the
following properties relative to said parent a-amylase : increased
thermostability,
increased stability towards oxidation, reduced Ca ion dependency, increased
stability and/or a-amylolytic activity at neutral to relatively high pH
values,
increased a-amylolytic activity at relatively high temperature and increase or
decrease of the isoelectric point (pI) so as to better match the pI value for
a-
amylase variant to the pH of the medium.
Said variants are described in WO 96/23873.
Other amylases suitable herein include, for example, a-amylases described in
GB
1,296,839 to Novo; RAPIDASEG, lnternational Bio-Synthetics, Inc. and
TERMAMYL , Novo. FUNGAMYLO from Novo is especially useful. Engineering of
enzymes for improved stability, e.g., oxidative stability, is known. See, for
example J.
Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain
preferred
embodiments of the present compositions can make use of amylases having
improved
stability in detergents such as automatic dishwashing types, especially
improved
oxidative stability as measured against a reference-point of TERMAMYL in
commercial use in 1993. These preferred amylases herein share the
characteristic of
being "stability-enhanced" amylases, characterized, at a minimum, by a
measurable
improvement in one or more of: oxidative stability, e.g., to hydrogen
peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal
stability,
e.g., at common wash temperatures such as about 60oC; or alkaline stability,
e.g., at a pH
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WO 00/71652 PCTIUSOO/14564
from about 8 to about 11, measured versus the above-identified reference-point
amylase.
Stability can be measured using any of the art-disclosed technical tests. See,
for example,
references disclosed in WO 9402597. Stability-enhanced amylases can be
obtained from
Novo or from Genencor International. One class of highly preferred amylases
herein
have the commonality of being derived using site-directed mutagenesis from one
or more
of the Bacillus amylases, especially the Bacillus a-amylases, regardless of
whether one,
two or multiple amylase strains are the immediate precursors. Oxidative
stability-
enhanced amylases vs. the above-identified reference amylase are preferred for
use,
especially in bleaching, more preferably oxygen bleaching, as distinct from
chlorine
bleaching, detergent compositions herein. Such preferred amylases include (a)
an
amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3,
1994, as
further illustrated by a mutant in which substitution is made, using alanine
or threonine,
preferably threonine, of the methionine residue located in position 197 of the
B.
licheniformis alpha-amylase, known as TERMAMYL , or the homologous position
variation of a similar parent amylase, such as B. amyloliquefaciens, B.
subtilis, or B.
stearothermophilus; (b) stability-enhanced amylases as described by Genencor
International in a paper entitled "Oxidatively Resistant alpha-Amylases"
presented at the
207th American Chemical Society National Meeting, March 13-17 1994, by C.
Mitchinson. Therein it was noted that bleaches in automatic dishwashing
detergents
inactivate alpha-amylases but that improved oxidative stability amylases have
been made
by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as
the
most likely residue to be modified. Met was substituted, one at a time, in
positions 8, 15,
197, 256, 304, 366 and 438 leading to specific mutants, particularly important
being
M197L and M197T with the M197T variant being the most stable expressed
variant.
Stability was measured in CASCADE and SUNLIGHT ; (c) particularly preferred
amylases herein include amylase variants having additional modification in the
immediate parent as described in WO 9510603 A and are available from the
assignee,
Novo, as DURAMYL . Other particularly preferred oxidative stability enhanced
amylase include those described in WO 9418314 to Genencor International and WO
9402597 to Novo. Any other oxidative stability-enhanced amylase can be used,
for
53
CA 02372892 2004-07-20
example as derived by site-directed mutagenesis from known chimeric, hybrid or
simple
mutant parent forms of available amylases. Other preferred enzyme
modifications are
accessible. See WO 9509909 A to Novo.
Cellulases usable herein include both bacterial and fungal types, preferably
having a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al,
March 6,
1984, discloses suitable fungal cellulases from Humicola insolens or Humicola
strain
DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas,
and
cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula
Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275
and DE-OS-2.247.832. CAREZYME and CELLUZYME (Novo) are especially
useful. See also WO 91/17243 to Novo.
The composition will preferably contain at least about 0.0001 %, more
preferably
at least about 0.0002%, more preferably at least about 0.0005%, even more
preferably
still, at least about 0.001% of active enzyme by '~Aieight of the composition
of cellulases
andlor peroxidases enzyme. The composition will also preferably contain no
more than
about 2%, more preferably no more than about 0.5%, more preferably no more
than
about 0.1%, even more preferably, no more than about 0.05% of active enzyme by
weight of the composition of cellulases and/or peroxidases enzyme.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of lipase, namely lipases which do not require interfacial activation.
Addition of
cutinases to detergent compositions have been described in e.g. WO-A-88/09367
(Genencor).
Lipase - Suitable lipase enzymes include those produced by microorganisms of
the
Pseudomonas group, such as Pseudonzonas stutzeri ATCC 19.154, as disclosed in
British
Patent 1,372,034. Suitable lipases include those which show a positive
immunological
cross-reaction with the antibody of the lipase, produced by the microorganism
Pseudomonas fluorescens IAM 1057. This lipase is available from Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano,"
hereinafter referred to as "Amano-P". Further suitable lipases are lipases
such as Ml
Lipase and Lipomax (Gist-Brocades). Other suitable commercial lipases
include
54
CA 02372892 2004-07-20
Amano-CES, lipases ex Chronzobacter viscosunz, e.g. Chromobacter viscosuni
var.
lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chroniobacter
viscosum
lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands,
and
lipases ex Pseudomonas gladioli. LIPOLASE't enzyme derived from Humicola
lanuginosa and conunercially available from Novo, see also EP 341,947, is a
preferred
lipase for use herein. Lipase and amylase variants stabilized against
peroxidase enzymes
are described in WO 9414951 A to Novo. See also WO 9205249.
Highly preferred lipases are the D96L lipolytic enzyme variant of the native
lipase
derived from Humicola lanuginosa as described in US Patent No. 5,837,010. (See
also
patent application WO 92/05249 viz. wherein the native lipase ex Humicola
lanuginosa
aspartic acid (D) residue at position 96 is changed to Leucine (L). According
to this
nomenclature said substitution of aspartic acid to Leucine in position 96 is
shown as
D96L.) Preferably the Humicola lanuginosa strain DSM 4106 is used.
In spite of the large number of publications on lipase enzymes, only the
lipase
derived from Humicola lanuginosa and produced in Aspergillus oryzae as host
has so far
found widespread application as additive for washing products. It is available
from Novo
Nordisk under the trademarks Lipolase and Lipolase Ultra , as noted above. In
order
to optimize the stain removal performance of Lipolase, Novo Nordisk have made
a
number of variants. As described in WO 92/05249, the D96L variant of the
native
Humicola lanuginosa lipase improves the lard stain removal efficiency by a
factor 4.4
over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to
2.5 mg
protein per liter). Research Disclosure No. 35944 published on March 10, 1994,
by
Novo Nordisk discloses that the lipase variant (D96L) may be added in an
amount
corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter
of wash
liquor.
The composition will preferably contain at least about 0.0001%, more
preferably
at least about 0.0002%, more preferably at least a'bout 0.0005%, even more
preferably
still, at least about 0.001% of active enzyme by weight of the composition of
lipase
enzyme. The composition will also preferably contain no more than about 2%,
more
preferably no more than about 0.5%, more preferably no more than about 0.1%,
even
CA 02372892 2004-07-20
more preferably, no more than about 0.05% of active enzyme by weight of the
composition of lipase enzyme.
Various carbohydrase enzymes which impart antimicrobial activity may also be
included in the present invention. Such enzymes include endoglycosidase, Type
II
endoglycosidase and glucosidase as disclosed in U.S. Patent Nos. 5,041,236,
5,395,541,
5,238,843 and 5,356,803. Of course, other enzymes having antimicrobial
activity may be
employed as well including peroxidases, oxidases and various other enzymes.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to
McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al,
July 18,
1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful
for
liquid detergent formulations, and their incorporation into such formulations,
are
disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in
detergents
can be stabilized by various techniques. Enzyme stabilization techniques are
disclosed
and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405
and EP
200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also
described,
for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases,
xylanases
and cellulases, is described in WO 9401532 A to Novo.
It is also possible to include an enzyme stabilization system into the
compositions
of the present invention when any enzyme is present in the composition.
Enzyme Stabilizing System - The compositions herein may optionally comprise
from
about 0.001% to about 10%, preferably from about 0.005% to about 8%, most
preferably
from about 0.01% to about 6%, by weight of an enzyme stabilizing system, when
the
composition also contains an enzyme. The enzyme stabilizing system can be any
stabilizing system which is compatible with the protease or other enzymes used
in the
compositions herein. Such stabilizing systems can comprise calcium ion, boric
acid,
propylene glycol, short chain carboxylic acid, boronic acid, polyhydroxyl
compounds and
mixtures thereof such as are described in U.S. Patents 4,261,868, Hora et al,
issued April
56
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14, 1981; 4,404,115, Tai, issued September 13, 1983; 4,318,818, Letton et al;
4,243,543,
Guildert et al issued January 6, 1981; 4,462,922, Boskamp, issued July 31,
1984;
4,532,064, Boskamp, issued July 30, 1985; and 4,537,707, Severson Jr., issued
August
27, 1985 .
The composition will preferably contain at least about 0.001%, more preferably
at
least about 0.005%, even more preferably still, at least about 0.01% by weight
of the
composition of enzyme stabilizing system. The composition will also preferably
contain
no more than about 10%, more preferably no more than about 8%, no more than
about
6% of active enzyme by weight of the composition of enzyme stabilizing system.
Additionally, from 0% to about 10%, preferably from about 0.01% to about 6% by
weight, of chlorine bleach or oxygen bleach scavengers can be added to
compositions of
the present invention to prevent chlorine bleach species present in many water
supplies
from attacking and inactivating the enzymes, especially under alkaline
conditions. While
chlorine levels in water may be small, typically in the range from about 0.5
ppm to about
1.75 ppm, the available chlorine in the total volume of water that comes in
contact with
the enzyme during dishwashing is usually large; accordingly, enzyme stability
in-use can
be problematic.
Suitable chlorine scavenger anions are salts containing ammonium cations.
These
can be selected from the group consisting of reducing materials like sulfite,
bisulfite,
thiosulfite, thiosulfate, iodide, etc., antioxidants like carbonate,
ascorbate, etc., organic
amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt
thereof and
monoethanolamine (MEA), and mixtures thereof. Other conventional scavenging
anions
like sulfate, bisulfate, carbonate, bicarbonate, percarbonate, nitrate,
chloride, borate,
sodium perborate tetrahydrate, sodium perborate monohydrate, percarbonate,
phosphate,
condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate,
tartrate,
salicylate, etc. and mixtures thereof can also be used.
Builders - Detergent builders are optionally included in the compositions
herein. In solid
formulations, builders sometimes serve as absorbents for surfactants.
Alternately, certain
compositions can be formulated with completely water-soluble builders, whether
organic
or inorganic, depending on the intended use.
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Suitable silicate builders include water-soluble and hydrous solid types and
including those having chain-, layer-, or three-dimensional- structure as well
as
amorphous-solid silicates or othcr types, for example especially adapted for
use in non-
structured-liquid detergents. Preferred are alkali metal silicates,
particularly those liquids
and solids having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1, including
solid hydrous
2-ratio silicates marketed by PQ Corp. under the trademark BRITESII.,@, e.g.,
BRITESIL
H20;, and layered silicates, e.g., those described in U.S. 4,664,839, May 12,
1987, H. P.
TM
Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layered
aluminum-
free 8-Na2SiO5 morphology silicate marketed by Hoechst and is preferred
especially in
granular compositions. See preparative methods in German DE-A-3,417,649 and DE-
A-
3,742,043. Other layered silicates, such as those having the general formula
NaMSixO2x-{-1'yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to
4,
preferably 2, and y is a number from 0 to 20, preferably 0, can also or
alternately be used
TM TM TM
herein. Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-
11,
as the a, (3 and y layer-silicate forms. Other silicates may also be useful,
such as
magnesium silicate, which can serve as a crispening agent in granules, and as
a
component of suds control systems.
Also suitable for use herein are synthesized crystalline ion exchange
materials or
hydrates thereof having chain structure and a composition represented by the
following
general formula in an anhydride form: xM2O'ySiO2.zM'O wherein M is Na and/or
K, M'
is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S.
5,427,711,
Sakaguchi et al, June 27, 1995.
Aluminosilicate builders, such as zeolites, are especially useful in granular
detergents, but can also be incorporated in liquids, pastes or gels. Suitable
for the present
purposes are those having empirical formula: [Mz(A102)z(SiO2)v] -xH2O wherein
z and
v are integers of at least 6, M is an alkali metal, preferably Na and/or K,
the molar ratio
of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
Aluminosilicates can be crystalline or amorphous, naturally-occurring or
synthetically
derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel,
et al,
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October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange
materials
are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent
this differs
from Zeolite P, the so-called Zeolite MAP. Natural types, including
clinoptilolite, may
be used. Zeolite A has the formula: Na12[(A102)12(SiO2)12]=xH20 wherein x is
from
20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10) may also be used.
Preferably,
the aluminosilicate has a particle size of 0.1-10 microns in diameter.
Detergent builders in place of or in addition to the silicates and
aluminosilicates
described hereinbefore can optionally be included in the compositions herein,
for
example to assist in controlling mineral, especially Ca and/or Mg, hardness in
wash
water or to assist in the removal of particulate soils from surfaces. Builders
can operate
via a variety of mechanisms including forming soluble or insoluble complexes
with
hardness ions, by ion exchange, and by offering a surface more favorable to
the
precipitation of hardness ions than are the surfaces of articles to be
cleaned. Builder
level can vary widely depending upon end use and physical form of the
composition.
Built detergents typically comprise at least about 1% builder. Liquid
formulations
typically comprise about 5% to about 50%, more typically 5% to 35% of builder.
Granular formulations typically comprise from about 10% to about 80%, more
typically
15% to 50% builder by weight of the detergent composition. Lower or higher
levels of
builders are not excluded. For example, certain formulations can be unbuilt,
that is the
compositions contain no builder such as in some hand dishwashing compositions.
Suitable builders herein can be selected from the group consisting of
phosphates
and polyphosphates, especially the sodium salts; carbonates, bicarbonates,
sesquicarbonates and carbonate minerals other than sodium carbonate or
sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates especially
water-soluble
nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt
form, as
well as oligomeric or water-soluble low molecular weight polymer carboxylates
including aliphatic and aromatic types; and phytic acid. These may be
complemented by
borates, e.g., for pH-buffering purposes, or by sulfates, especially sodium
sulfate and any
other fillers or carriers which may be important to the engineering of stable
surfactant
and/or builder-containing detergent compositions.
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Builder mixtures, sometimes termed "builder systems" can be used and typically
comprise two or more conventional builders, optionally complemented by
chelants, pH-
buffers or fillers, though these latter materials are generally accounted for
separately
when describing quantities of materials herein. In terms of relative
quantities of
surfactant and builder in the present detergents, preferred builder systems
are typically
formulated at a weight ratio of surfactant to builder of from about 60:1 to
about 1:80.
Certain preferred laundry detergents have said ratio in the range 0.90:1.0 to
4.0:1.0, more
preferably from 0.95:1.0 to 3.0:1Ø
P-containing detergent builders often preferred where permitted by legislation
include, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts
of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy
polymeric meta-phosphates; and phosphonates.
Suitable carbonate builders include alkaline earth and alkali metal carbonates
as
disclosed in German Patent Application No. 2,321,001 published on November 15,
1973,
although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and
other
carbonate minerals such as trona or any convenient multiple salts of sodium
carbonate
and calcium carbonate such as those having the composition 2Na2CO3.CaCO3 when
anhydrous, and even calcium carbonates including calcite, aragonite and
vaterite,
especially forms having high surface areas relative to compact calcite may be
useful, for
example as seeds.
Suitable "organic detergent builders", as described herein for use in the
cleaning
compositions include polycarboxylate compounds, including water-soluble
nonsurfactant
dicarboxylates and tricarboxylates. More typically builder polycarboxylates
have a
plurality of carboxylate groups, preferably at least 3 carboxylates.
Carboxylate builders
can be formulated in acid, partially neutral, neutral or overbased form. When
in salt form,
alkali metals, such as sodium, potassium, and lithium, or alkanolammonium
salts are
preferred. Polycarboxylate builders include the ether polycarboxylates, such
as
oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al,
U.S.
3,635,830, January 18, 1972; "TMS/TDS" builders of U.S. 4,663,071, Bush et al,
May 5,
1987; and other ether carboxylates including cyclic and alicyclic compounds,
such as
CA 02372892 2004-07-20
those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and
4,102,903.
Other suitable organic detergent builders are the ether
hydroxypolycarboxylates,
copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-
trihydroxy
benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various
alkali
metal, ammonium and substituted ammonium salts of polyacetic acids such as
ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as
mellitic acid, succinic
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid,
and soluble salts thereof.
Citrates, e.g., citric acid and soluble salts thereof are important
carboxylate
builders e.g., for light duty liquid detergents, due to availability from
renewable resources
and biodegradability. Citrates can also be used in granular compositions,
especially in
combination with zeolite and/or layered silicates. Oxydisuccinates are also
especially
useful in such compositions and combinations.
Where permitted, and especially in the formulation of bars, alkali metal
phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium
orthophosphate can be used. Phosphonate builders such as ethane-l-hydroxy-1,1-
diphosphonate and other known phosphonates, e.g., those of U.S. 3,159,581;
3,213,030;
.3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable
antiscaling
properties.
Certain detersive surfactants or their short-chain homologues also have a
builder
action. For unambiguous formula accounting purposes, when they have surfactant
capability, these materials are summed up as detersive surfactants. Preferred
types for
builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-
hexanedioates and the
related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986.
Succinic acid
builders include the C5-C20 alkyl and alkenyl succinic acids and salts
thereof. Succinate
builders also include: laurylsuccinate, mvristylsuccinate, palmitylsuccinate,
2-
dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl-
succinates
are described in European Patent Application 0,200,263, published
November 5, 1986. Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be
61
CA 02372892 2004-07-20
incorporated into the compositions as surfactant/builder materials alone or in
combination with the aforementioned builders, especially citrate and/or the
succinate
builders, to provide additional builder activity. Other suitable
polycarboxylates are
disclosed in U.S. 4,144,226, Crutchfield et al, March 13, 1979 and in U.S.
3,308,067,
Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.
Other types of inorganic builder materials which can be used have the formula
(Mx)i Cay (C03)z wherein x and i are integers from 1 to 15, y is an integer
from 1 to 10,
z is an integer froin 2 to 25, Mi are cations, at least one of which is a
water-soluble, and
the equation Ei = 1-15(xi multiplied by the valence of Mi) + 2y = 2z is
satisfied such that
the formula has a neutral or "balanced" charge. These builders are referred to
herein as
"Mineral Builders", examples of these builders, their use and preparation can
be found in
US Patent 5,707,959. Another suitable class of inorganic builders are the
Magnesiosilicates, see W097/0179.
Suitable polycarboxylates builders for use herein include maleic acid, citric
acid,
preferably in the form of a water-soluble salt, derivatives of succinic acid
of the formula
R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16,
or
wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone
substituents.
Mixtures of these suitable polycarboxylates builders is also envisioned, such
as a mixture
of maleic acid and citric acid. Specific examples include lauryl succinate,
myristyl
succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate.
Succinate
builders are preferably used in the form of their water-soluble salts,
including sodium,
potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate
monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for
use herein
are saturated or unsaturated C10-18 fatty acids, as well as the corresponding
soaps.
Preferred saturated species have from 12 to 16 carbon atoms in the alkyl
chain. The
preferred unsaturated fatty acid is oleic acid. Other preferred builder system
for liquid
compositions is based on dodecenyl succinic acid and citric acid.
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The composition will preferably contain at least about 0.2%, more preferably
at
least about 0.5%, more preferably at least about 3%, even more preferably
still, at least
about 5% by weight of the composition of builder. The cleaning composition
will also
preferably contain no more than about 50%, more preferably no more than about
40%,
more preferably no more than about 30%, even more preferably, no more than
about 25%
by weight of the composition of builder.
Perfumes - Perfumes and perfumery ingredients useful in the present
compositions
comprise a wide variety of natural and synthetic chemical ingredients,
including, but not
limited to, aldehydes, ketones, esters, and the like. Also included are
various natural
extracts and essences which can comprise complex mixtures of ingredients, such
as
orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic
essence,
sandalwood oil, pine oil, cedar, and the like. Finished perfumes can comprise
extremely
complex mixtures of such ingredients. Finished perfumes typically comprise
from about
0.01% to about 2%, by weight, of the detergent compositions herein, and
individual
perfumery ingredients can comprise from about 0.0001% to about 90% of a
finished
perfume composition.
Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-
1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; ionone methyl;
ionone
gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-
trimethyl-
2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;
4-acetyl-6-
tert-butyl-l,l-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone;
methyl
beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-
isopropyl-
1,1,2,6-tetramethyl indane; 1-dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-
cyclohexene-
1-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-l-al; iso-
hexenyl
cyclohexyl carboxaldehyde; formyl tricyclodecane; condensation products of
hydroxycitronellal and methyl anthranilate, condensation products of
hydroxycitronellal
and indol, condensation products of phenyl acetaldehyde and indol; 2-methyl-3-
(para-
tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic
aldehyde;
amyl cinnamic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
coumarin; decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic
acid
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lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzo-
pyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-
tetramethyl-
naphtho[2,1b]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-
2-ol; 2-
ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-l-o1; caryophyllene
alcohol;
tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl
acetate; and
para-(tert-butyl) cyclohexyl acetate.
Particularly preferred perfume materials are those that provide the largest
odor
improvements in finished product compositions containing cellulases. These
perfumes
include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert-
butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro- 1, 1,6,7-
tetramethyl
naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-
tert-butyl
cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether;
methyl beta-
naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
1,3,4,6,7,8-
hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane; dodecahydro-
3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde; coumarin; cedrol;
vanillin;
cyclopentadecanolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.
Other perfume materials include essential oils, resinoids, and resins from a
variety of sources including, but not limited to: Peru balsam, Olibanum
resinoid, styrax,
labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
Still other
perfume chemicals include phenyl ethyl alcohol, terpineol, linalool, linalyl
acetate,
geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate,
and eugenol.
Carriers such as diethylphthalate can be used in the finished perfume
compositions.
In place of the perfume, especially in microemulsions, the compositions can
employ an essential oil or a water insoluble organic compound such as a water
insoluble
hydrocarbon having 6 to 18 carbon such as a paraffin or isoparaffin such as
isoparH,
isodecane, aipha-pinene, beta-pinene, decanol and terpineol. Suitable
essential oils are
selected from the group consisting of: Anethole 20/21 natural, Aniseed oil
china star,
Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil,
Black pepper
oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor
oil,
White, Camphor powder synthetic technical, Cananga oil (Java), Cardamom oil,
Cassia
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oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil,
Citronella
oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69° C.
(China),
Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil,
Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin
(India),
White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, Isobornyl
acetate,
Isolongifolene, Juniper berry oil, L-methyl acetate, Lavender oil, Lemon oil,
Lemongrass
oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals,
Methyl cedryl
ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk
xylol,
Nutmeg oil, Orange oil, Patchpouli oil, Peppermint oil, Phenyl ethyl alcohol,
Pimento
berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil,
Clary sage,
Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin,
Vetyver oil
(Java), Wintergreen
Hydrotropes - The compositions of the present invention may comprise one or
more
materials which are hydrotropes. Hydrotropes suitable for use in the
compositions herein
include the C 1-C3 alkyl aryl sulfonates, C6-C12 alkanols, C 1-C6 carboxylic
sulfates and
sulfonates, urea, C1-C6 hydrocarboxylates, C1-C4 carboxylates, C2-C4 organic
diacids
and mixtures of these hydrotrope materials. The liquid detergent composition
of the
present invention preferably comprises from about 0.5% to 8%, by weight of the
liquid
detergent composition of a hydrotrope selected from alkali metal and calcium
xylene and
toluene sulfonates.
Suitable Cl-C3 alkyl aryl sulfonates include sodium, potassium, calcium and
ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluene
sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; and
sodium,
potassium, calcium and ammonium substituted or unsubstituted naphthalene
sulfonates
and mixtures thereof.
Suitable Cl-Cg carboxylic sulfate or sulfonate salts are any water soluble
salts or
organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent
groups),
which are substituted with sulfate or sulfonate and have at least one
carboxylic group.
The substituted organic compound may be cyclic, acylic or aromatic, i.e.
benzene
derivatives. Preferred alkyl compounds have from 1 to 4 carbon atoms
substituted with
CA 02372892 2001-11-01
WO 00/71652 PCT/US00/14564
sulfate or sulfonate and have from 1 to 2 carboxylic groups. Examples of this
type of
hydrotrope include sulfosuccinate salts, sulfophthalic salts, sulfoacetic
salts, m-
sulfobenzoic acid salts and diester sulfosuccinates, preferably the sodium or
potassium
salts as disclosed in U.S. 3,915,903.
Suitable C 1-C4 hydrocarboxylates and C 1-C4 carboxylates for use herein
include
acetates and propionates and citrates. Suitable C2-C4 diacids for use herein
include
succinic, glutaric and adipic acids.
Other compounds which deliver hydrotropic effects suitable for use herein as a
hydrotrope include C6-C12 alkanols and urea.
Preferred hydrotropes for use herein are sodium, potassium, calcium and
ammonium cumene sulfonate; sodium, potassium, calcium and ammonium xylene
sulfonate; sodium, potassium, calcium and ammonium toluene sulfonate and
mixtures
thereof. Most preferred are sodium cumene sulfonate and calcium xylene
sulfonate and
mixtures thereof. These preferred hydrotrope materials can be present in the
composition
to the extent of from about 0.5% to 8% by weight.
The composition will preferably contain at least about 0.1%, more preferably
at
least about 0.2%, even more preferably still, at least about 0.5% by weight of
the
composition of hydrotrope. The composition will also preferably contain no
more than
about 15%, more preferably no more than about 10%, even more preferably, no
more
than about 8% by weight of the composition of hydrotrope.
Bleaching Compounds
Bleaching Agents and Bleach Activators The detergent compositions herein may
further
contain a bleach and/or a bleach activators. Bleaches agents will typically,
when present,
be at levels of from about 1% to about 30%, more typically from about 5% to
about 20%,
of the detergent composition, especially for fabric laundering. If present,
the amount of
bleach activators will typically be from about 0.1 % to about 60%, more
typically from
about 0.5% to about 40% of the composition comprising the bleaching agent-plus-
bleach
activator.
The bleaches used herein can be any of the bleaches useful for detergent
compositions in textile cleaning, hard surface cleaning, or other cleaning
purposes that
66
CA 02372892 2004-07-20
are now known or become known. These include oxygen bleaches as well as other
bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or
tetra-
hydrate) can be used herein.
Another category of bleaches that can be used without restriction encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of
this class of
agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt
of
metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaches are disclosed in U.S. Patent
4,483,781,
Hartman, issued November 20, 1984, U.S. Patent No. 4,634,551, Burns et al,
European Patent Application 0,133,354, Banks et al, published February
20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
Highly
preferred bleaches also include 6-nonylamino-6-oxoperoxycaproic acid as
described in
U.S. Patent 4,634,551, issued January 6, 1987 to Bums et al.
Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds
include sodium carbonate peroxyhydrate and equivalent 'percarbonate"
bleaches, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate
TM
bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000
micrometers, not
more than about 10% by weight of said particles being smaller than about 200
micrometers and not more than about 10% by weight of said particles being
larger than
about 1,250 micrometers. Optionally, the percarbonate can be coated with
silicate,
borate or water-soluble surfactants. Percarbonate is available from various
commercial
sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaches can also be used.
Peroxygen bleaches, the perborates, the percarbonates, etc., are preferably
combined with bleach activators, which lead to the in situ production in
aqueous solution
(i.e., during the washing process) of the peroxy acid corresponding to the
bleach
activator. Various nonlimiting examples of activators are disclosed in U.S.
Patent
4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The
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nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED)
activators are typical, and mixtures thereof can also be used. See also U.S.
4,634,551 for
other typical bleaches and activators useful herein.
Bleach Activators
Bleach activators useful herein include amides, imides, esters and anhydrides.
Commonly at least one substituted or unsubstituted acyl moiety is present,
covalently
connected to a leaving group as in the structure R-C(O)-L. In one preferred
mode of use,
bleach activators are combined with a source of hydrogen peroxide, such as the
perborates or percarbonates, in a single product. Conveniently, the single
product leads
to in situ production in aqueous solution (i.e., during the washing process)
of the
percarboxylic acid corresponding to the bleach activator. The product itself
can be
hydrous, for example a powder, provided that water is controlled in amount and
mobility
such that storage stability is acceptable. Alternately, the product can be an
anhydrous
solid or liquid. In another mode, the bleach activator or oxygen bleach is
incorporated in
a pretreatment product, such as a stain stick; soiled, pretreated substrates
can then be
exposed to further treatments, for example of a hydrogen peroxide source. With
respect
to the above bleach activator structure RC(O)L, the atom in the leaving group
connecting
to the peracid-forming acyl moiety R(C)O- is most typically 0 or N. Bleach
activators
can have non-charged, positively or negatively charged peracid-forming
moieties and/or
noncharged, positively or negatively charged leaving groups. One or more
peracid-
forming moieties or leaving-groups can be present. See, for example, U.S.
5,595,967,
U.S. 5,561,235, U.S. 5,560,862 or the bis-(peroxy-carbonic) system of U.S.
5,534,179.
Mixtures of suitable bleach activators can also be used. Bleach activators can
be
substituted with electron-donating or electron-releasing moieties either in
the leaving-
group or in the peracid-forming moiety or moieties, changing their reactivity
and making
them more or less suited to particular pH or wash conditions. For example,
electron-
withdrawing groups such as NO2 improve the efficacy of bleach activators
intended for
use in mild-pH (e.g., from about 7.5- to about 9.5) wash conditions.
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An extensive and exhaustive disclosure of suitable bleach activators and
suitable
leaving groups, as well as how to determine suitable activators, can be found
in US
Patents 5,686,014 and 5,622,646.
Cationic bleach activators include quaternary carbamate-, quaternary carbonate-
,
quaternary ester- and quatemary amide- types, delivering a range of cationic
peroxyimidic, peroxycarbonic or peroxycarboxylic acids to the wash. An
analogous but
non-cationic palette of bleach activators is available when quaternary
derivatives are not
desired. In more detail, cationic activators include quatemary ammonium-
substituted
activators of WO 96-06915, U.S. 4,751,015 and 4,397,757, EP-A-284292, EP-A-
331,229
and EP-A-03520. Also useful are cationic nitriles as disclosed in EP-A-303,520
and in
European Patent Specification 458,396 and 464,880. Other nitrile types have
electron-
withdrawing substituents as described in U.S. 5,591,378.
Other bleach activator disclosures include GB 836,988; 864,798; 907,356;
1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132;
EP-
A-0120591; U.S. Pat. Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and
4,675,393,
and the phenol sulfonate ester of alkanoyl aminoacids disclosed in U.S.
5,523,434.
Suitable bleach activators include any acetylated diamine types, whether
hydrophilic or
hydrophobic in character.
Of the above classes of bleach precursors, preferred classes include the
esters,
including acyl phenol sulfonates, acyl alkyl phenol sulfonates or acyl
oxybenzenesulfonates (OBS leaving-group); the acyl-amides; and the quaternary
ammonium substituted peroxyacid precursors including the cationic nitriles.
Preferred bleach activators include N,N,N'N'-tetraacetyl ethylene diamine
(TAED)
or any of its close relatives including the triacetyl or other unsymmetrical
derivatives.
TAED and the acetylated carbohydrates such as glucose pentaacetate and
tetraacetyl
xylose are preferred hydrophilic bleach activators. Depending on the
application, acetyl
triethyl citrate, a liquid, also has some utility, as does phenyl benzoate.
Preferred hydrophobic bleach activators include sodium nonanoyloxybenzene
sulfonate (NOBS or SNOBS), N-(alkanoyl)aminoalkanoyloxy benzene sulfonates,
such
as 4- [N-(nonanoyl)aminohexanoyloxy] -benzene sulfonate or (NACA-OBS) as
described
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CA 02372892 2004-07-20
in US Patent 5,534,642 and in EPA 0 355 384 Al, substituted amide types
described in
detail hereinafter, such as activators related to NAPAA, and activators
related to certain
imidoperacid bleaches, for example as described in U.S. Patent 5,061,807,
issued
October 29, 1991 and assigned to Hoechst Aktiengesellschaft of Frankfurt,
Germany and
Japanese Laid-Open Patent Application (Kokai) No. 4-28799.
Another group of peracids and bleach activators herein are those derivable
from
acyclic imidoperoxycarboxylic acids and salts thereof, See US Patent 5415796,
and
cyclic imidoperoxycarboxylic acids and salts thereof, see US patents
5,061,807,
5,132,431, 5,6542,69, 5,246,620, 5,419,864 and 5,438,147.
Another class of useful bleach activators comprises the benzoxazin-type
activators
disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990.
Still another class of useful bleach activators includes the acyl lactam
activators.
See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, which
discloses acyl
caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Other suitable bleach activators include sodium-4-benzoyloxy benzene sulfonate
(SBOBS); sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-
benzoyloxy benzoate (SPCC); trimethyl ammonium toluvloxy-benzene sulfonate; or
sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS).
Bleach activators may be used in an amount of up to 20%, preferably from 0.1-
10%
by weight, of the composition, though higher levels, 40% or more, are
acceptable, for
example in highly concentrated bleach additive product forms or forms intended
for
appliance automated dosing.
Highly preferred bleach activators useful herein are amide-substituted and an
extensive and exhaustive disclosure of these activators can be found in US
Patents
5,686,014 and 5,622,646.
Other useful activators, disclosed in U.S. 4,966,723, are benzoxazin-type,
such as a
C6H4 ring to which is fused in the 1,2-positions a moiety --C(O)OC(Rl)=N-. A
highly
preferred activator of the benzoxazin-type is:
CA 02372892 2004-07-20
0
li~O
c
N
Depending on the activator and precise application, good bleaching results can
be
obtained from bleaching systems having with in-use pH of from about 6 to about
13,
preferably from about 9.0 to about 10.5. Typically, for example, activators
with electron-
withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
Alkalis and
buffering agents can be used to secure such pH.
Acyl lactam activators are very useful herein, especially the acyl
caprolactams (see
for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639). See
also
U.S. 4,545,784 which discloses acyl caprolactams, including benzoyl
caprolactam
adsorbed into sodium perborate. In certain preferred embodiments of the
invention,
NOBS, lactam activators, imide activators or amide-functional activators,
especially the
more hydrophobic derivatives, are desirably combined with hydrophilic
activators such as
TAED, typically at weight ratios of hydrophobic activator : TAED in the range
of 1:5 to
5:1, preferably about 1:1. Other suitable lactam activators are alpha-
modified, see WO
96-22350 Al, July 25, 1996. Lactam activators, especially the more hydrophobic
types,
are desirably used in combination with TAED, typically at weight ratios of
amido-derived
or caprolactam activators : TAED in the range of 1:5 to 5:1, preferably about
1:1. See
also the bleach activators having cyclic amidine leaving-group disclosed in
U.S.
5,552,556.
Nonlimiting examples of additional activators useful herein are to be found in
U.S. 4,915,854, U.S. 4,412,934 and 4,634,551. The hydrophobic activator
nonanoyloxybenzene sulfonate (NOBS) and the hydrophilic tetraacetyl ethylene
diamine
(TAED) activator are typical, and mixtures thereof can also be used.
Additional activators useful herein include those of U.S. 5,545,349.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching
agents and salts thereof. Suitable examples of this class of agents include
magnesium
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monoperoxyphthalate hexahydrate, the magnesium salt of inetachloro perbenzoic
acid, 4-
nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such
bleaching
agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20,
1984;
European Patent Application EP-A-133,354, Banks et al., Published February 20,
1985;
and U.S. Patent 4,412,934, Chung et al., Issued November 1, 1983. Highly
preferred
bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as
described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
Various non-limiting examples of activators are disclosed in U.S. Patent
4,915,854,
Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November
1, 1983
to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl
ethylene
diamine (TAED) activators are typical. Mixtures thereof can also be used. See
also the
hereinbefore referenced U.S. 4,634,551 for other typical bleaches and
activators useful
herein.
Bleaches other than oxygen bleaching agents are also known in the art and can
be
utilized herein. One type of non-oxygen bleaching agent of particular interest
includes
photoactivated bleaches such as the sulfonated zinc and/or aluminum
phthalocyanines.
See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used,
detergent
compositions will typically contain from about 0.025% to about 1.25%, by
weight, of
such bleaches, especially sulfonate zinc phthalocyanine.
Bleach Catalysts
The present invention compositions may optionally utilize metal-containing
bleach catalysts that are effective for use in cleaning compositions.
Preferred are
manganese and cobalt-containing bleach catalysts.
For examples of suitable bleach catalysts see U.S. Pat. Nos. 4,246,612,
5,804542,
5,798,326, 5,246,621, 4,430,243, 5,244,594, 5,597,936, 5,705,464, 4,810,410,
4,601,845,
5,194,416, 5,703,030, 4,728,455, 4,711,748, 4,626,373, 4,119,557, 5,114,606,
5,599,781,
5,703,034, 5,114,611, 4,430,243, 4,728,455, and 5,227,084; EP Pat. Nos.
408,131,
549,271, 384,503, 549,272, 224,952, and 306,089; DE Pat. No. 2,054,019; CA Pat
No.
866,191.
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well known in the art and include, for example,
the
manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S.
Pat. 5,194,416; U.S. Pat. 5,114,606; European Pat. App. Pub. Nos. 549,271A1,
72
CA 02372892 2004-07-20
549,272A1, 544,440A2, 544,490A1; and CA 2,282,466; CA 2,282,477; CA 2,283,163;
and
CA 2,282,406.
Preferred examples of these catalysts include MnN2(u-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(PF6)2, MnII12(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(CI04)2, MnN4(u-O)6(1,4,7-triazacyclononane)4(C104)4, MnIII-
MnIV4(u-O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3,
MnIV(1,4,7-
trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other
metal-
based bleach catalysts include those disclosed in U.S. Patents 4,430,243,
5,114,611
5,622,646 and 5,686,014. The use of manganese with various complex ligands to
enhance bleaching is also reported in the following United States Patents:
4,728,455;
5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and
5,227,084.
Compositions herein may also suitably include as a bleach catalyst the class
of
transition metal complexes of a niacropolycyclic rigid ligand. The phrase
"macropolycyclic rigid ligand" is sometimes abbreviated as "MRL". One useful
MRL is
[MnByclamC12], where "Bcyclam" is (5,12-dimethyl-1,5,8,12-tetraaza-
bicyclo[6.6.2]hexadecane). See CA 2,282,466; CA 2,282,477;
CA 2,283,163; and CA 2,282,406. The amount used is a
catalytically effective amount, suitably about 1 ppb or more, for
example up to about 99.9%, more typically about 0.001 ppm or more, preferably
from
about 0.05 ppm to about 500 ppm (wherein "ppb" denotes parts per billion by
weight and
"ppm" denotes parts per million by weight).
One type of preferred bleach catalysts are the cobalt (IIl) catalysts having
the
formula:
Co[(NH3)nM'mB'bT'tQqPp] I'y
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5
(preferably 4 or 5;
most preferably 5); M' represents a monodentate ligand; m is an integer from 0
to 5
(preferably I or 2; most preferably 1); B' represents a bidentate ligand; b is
an integer
from 0 to 2; T' represents a tridentate ligand; t is 0 or 1; Q is a
tetradentate ligand; q is 0
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WO 00/71652 PCT/US00/14564
or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p =
6; Y is one
or more appropriately selected counteranions present in a number y, where y is
an integer
from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a-1 charged
anion), to obtain
a charge-balanced salt, preferred Y are selected from the group consisting of
chloride,
iodide, I3-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate,
carbonate, bromide,
PF6-, BF4-, B(Ph)4-, phosphate, phosphite, silicate, tosylate,
methanesulfonate, and
combinations thereof [optionally, Y can be protonated if more than one anionic
group
exists in Y, e.g., HP042-, HCO3-, H2P04-, etc., and further, Y may be selected
from the
group consisting of non-traditional inorganic anions such as anionic
surfactants, e.g.,
linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS),
alkylethoxysulfonates (AES),
etc., and/or anionic polymers, e.g., polyacrylates, polymethacrylates, etc.];
and wherein
further at least one of the coordination sites attached to the cobalt is
labile under
automatic dishwashing use conditions and the remaining coordination sites
stabilize the
cobalt under automatic dishwashing conditions such that the reduction
potential for
cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4
volts (preferably
less than about 0.2 volts) versus a normal hydrogen electrode.
Preferred cobalt catalysts of this type have the formula:
[Co(NH3)n(M')m] Yy
wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M'
is a
labile coordinating moiety, preferably selected from the group consisting of
chlorine,
bromine, hydroxide, water, and (when m is greater than 1) combinations
thereof; m is an
integer from 1 to 3 (preferably 1 or 2; most preferably 1); m+n = 6; and Y is
an
appropriately selected counteranion present in a number y, which is an integer
from 1 to
3 (preferably 2 to 3; most preferably 2 when Y is a-1 charged anion), to
obtain a charge-
balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride salts having the formula [Co(NH3)5C1] Yy, and especially
[Co(NH3)5C1]C12.
More preferred are the present invention compositions which utilize cobalt
(III)
bleach catalysts having the formula:
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WO 00/71652 PCT/US00/14564
[Co(NH3)n(M)m(B)b] Ty
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or more
ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1);
B is a ligand
coordinated to the cobalt by two sites; b is 0 or 1(preferably 0), and when
b=0, then m+n
= 6, and when b=1, then m=0 and n=4; and T is one or more appropriately
selected
counteranions present in a number y, where y is an integer to obtain a charge-
balanced
salt (preferably y is 1 to 3; most preferably 2 when T is a-1 charged anion);
and wherein
further said catalyst has a base hydrolysis rate constant of less than 0.23 M-
1 s-1 (25 C).
The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate
salts having the formula [Co(NH3)5OAc] Ty, wherein OAc represents an acetate
moiety,
and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]C12; as well
as
[CO(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2; [Co(NH3)5OAc](SO4); [Co-
(NH3)5OAc] (BF4)2; and [Co(NH3)5OAc] (NO3)2.
As a practical matter, and not by way of limitation, the cleaning compositions
and
cleaning processes herein can be adjusted to provide on the order of at least
one part per
hundred million of the active bleach catalyst species in the aqueous washing
medium,
and will preferably provide from about 0.01 ppm to about 25 ppm, more
preferably from
about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to
about 5
ppm, of the bleach catalyst species in the wash liquor. In order to obtain
such levels in
the wash liquor of an automatic dishwashing process, typical automatic
dishwashing
compositions herein will comprise from about 0.0005% to about 0.2%, more
preferably
from about 0.004% to about 0.08%, of bleach catalyst by weight of the cleaning
compositions.
Chelating Agents - The detergent compositions herein may also optionally
contain a
chelating agent which serves to chelate metal ions, e.g., iron and/or
manganese, within
the non-aqueous detergent compositions herein. Such chelating agents thus
serve to form
complexes with metal impurities in the composition which would otherwise tend
to
deactivate composition components such as the peroxygen bleaching agent.
Useful
chelating agents can include amino carboxylates, phosphonates, amino
phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
CA 02372892 2004-07-20
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates,
nitrilotriacetates, ethylene-diamine tetrapropionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, ethylenediaminedisuccinates and ethanol
diglycines.
The alkali metal salts of these materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of this invention when at least low levels of total phosphorus
are permitted
in detergent compositions, and include ethylenediaminetetrakis (methylene-
phosphonates) as DEQUEST. Preferably, these ainino phosphonates do not contain
alkyl
or alkenyl groups with more than about 6 carbon atoms.
Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP),
diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid
(EDDS)
and dipicolinic acid (DPA) and salts thereof. The chelating agent may, of
course, also act
as a detergent builder during use of the compositions herein for fabric
laundering/bleaching. The chelating agent, if employed, can comprise from
about 0.1%
to 4% by weight of the compositions herein. More preferably, the chelating
agent will
comprise from about 0.2% to 2% by weight of the detergent compositions herein.
Thickening, Viscosity Control and/or Dispersing Agents
The detergent compositions herein may also optionally contain a polymeric
material
which serves to enhance the ability of the composition to maintain its solid
particulate
components in suspension. Such materials may thus act as thickeners, viscosity
control
agents andlor dispersing agents. Such materials are frequently polymeric
polycarboxylates but can include other polymeric materials such as
polyvinylpyrrolidone
(PVP) or polyamide resins.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, maleic acid (or maleic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid.
The presence in the polymeric polycarboxylates herein of monomeric segments,
containing no carboxylate radicals such as vinylmethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight of
the polymer.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble
salts of
polymerized acrylic acid. The average molecular weight of such polymers in the
acid
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form preferably ranges from about 2,000 to 100,000, more preferably from about
2,000 to
10,000, even more preferably from about 4,000 to 7,000, and most preferably
from about
4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include,
for
example, the alkali metal, salts. Soluble polymers of this type are known
materials. Use
of polyacrylates of this type in detergent compositions has been disclosed,
for example,
Diehl, U.S. Patent 3,308,067, issued March 7, 1967. Such materials may also
perform a
builder function.
If utilized, the optional thickening, viscosity control and/or dispersing
agents should
be present in the compositions herein to the extent of from about 0.1% to 4%
by weight.
More preferably, such materials can comprise from about 0.5% to 2% by weight
of the
detergents compositions herein.
Clay Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water-
soluble
ethoxylated amines having clay soil removal and anti-redeposition properties.
If used,
soil materials can contain from about 0.01% to about 5% by weight of the
compositions
herein.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay soil
removal-anti-redeposition agents are the cationic compounds disclosed in
European
Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other
clay soil
removal/anti-redeposition agents which can be used include the ethoxylated
amine
polymers disclosed in European Patent Application 111,984, Gosselink,
published June
27, 1984; the zwitterionic polymers disclosed in European Patent Application
112,592,
Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
Patent
4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or
anti-
redeposition agents known in the art can also be utilized in the compositions
herein.
Another type of preferred anti-redeposition agent includes the carboxy methyl
cellulose
(CMC) materials. These materials are well known in the art.
Polymeric Soil Release Agent
Any polymeric soil release agent known to those skilled in the art can
optionally be
employed in the compositions and processes of this invention. Polymeric soil
release
agents are characterized by having both hydrophilic segments, to hydrophilize
the surface
of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments,
to deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles and, thus, serve as an anchor for the hydrophilic segments.
This can enable
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CA 02372892 2004-07-20
stains occurring subsequent to treatment with the soil release agent to be
more easily
cleaned in later washing procedures.
Examples of polymeric soil release agents useful herein include U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink; U.S. Patent 4,000,093, issued
December 28, 1976 to Nicol, et al.; European Patent Application 0 219 048,
published
April 22, 1987 by Kud, et al.; U.S. Patent 4,702,857, issued October 27, 1987
to
Gosselink; U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel.
TM
Commercially available soil release agents include the SOKALAN type of
material, e.g.,
SOKALAN HP-22, available from BASF (West Germany). Also see U.S. Patent
3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur
issued
July 8, 1975. Examples of this polymer include the commercially available
material
1'M 'CM
ZELCON 5126 (from Dupont) and MILEASE T (from ICI). Other suitable polymeric
soil release agents include the terephthalate polyesters of U.S. Patent
4,711,730, issued
December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters
of U.S.
Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block
polyester
oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to
Gosselink.
Preferred polymeric soil release agents also include the soil release agents
of U.S. Patent
4,877,896, issued October 31, 1989 to Maldonado et al.
If utilized, soil release agents will generally comprise from about 0.01% to
about
10.0%, by weight, of the detergent compositions herein, typically from about
0.1% to
about 5%, preferably from about 0.2% to about 3.0%.
Dye Transfer Inhibiting Agents
The compositions of the present invention may also include one or more
materials
effective for inhibiting the transfer of dyes from one fabric to another
during the cleaning
process. Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone
polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
If used,
these agents typically comprise from about 0.01% to about 10% by weight of the
composition, preferably from about 0.01% to about 5%, and more preferably from
about
0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain
units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit
to which an N-O group can be attached or the N-O group can form part of the
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polymerizable unit or the N-O group can be attached to both units; A is one of
the
following structures: -NC(O)-, -C(O)O-, -S-, -0-, -N=; x is 0 or 1; and R is
aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination
thereof to which the nitrogen of the N-0 group can be attached or the N-0
group is part
of these groups. Preferred polyamine N-oxides are those wherein R is a
heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives thereof.
The N-0 group can be represented by the following general structures:
0 0
1 1
(RI)x i -(R2)y; =N-(Rt)x
(R3)Z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of the
polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric
backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide,
polyimides,
polyacrylates and mixtures thereof. These polymers include random or block
copolymers
where one monomer type is an amine N-oxide and the other monomer type is an N-
oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-
oxide of 10:1
to 1:1,000,000. However, the number of amine oxide groups present in the
polyamine
oxide polymer can be varied by appropriate copolymerization or by an
appropriate degree
of N-oxidation. The polyamine oxides can be obtained in almost any degree of
polymerization. Typically, the average molecular weight is within the range of
500 to
1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
This
preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions
herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000
and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a
class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has
an average
molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to
200,000,
and most preferably from 10,000 to 20,000. (The average molecular weight range
is
determined by light scattering as described in Barth, et al., Chemical
Analysis, Vol 113.
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CA 02372892 2004-07-20
"Modern Methods of Polymer Characterization".) The
PVPVI copolymers typically have a molar ratio of
N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from
0.8:1 to
0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or
branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP' ) having an average molecular weight of from about 5,000 to about
400,000,
preferably from about 5,000 to about 200,000, and more preferably from about
5,000 to
about 50,000. PVP's are known to persons skilled in the detergent field; see,
for example,
EP-A-262,897 and EP-A-256,696. Compositions containing PVP
can also contain polyethylene glycol ("PEG") having an average
molecular weight from about 500 to about 100,000, preferably from about 1,000
to about
10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash
solutions
is from about 2:1 to about 50:1, and more preferably from about 3:1 to about
10:1.
The detergent compositions herein may also optionally contain from about
0.005%
to 5% by weight of certain types of hydrophilic optical brighteners which also
provide a
dye transfer inhibition action. If used, the compositions herein will
preferably comprise
from about 0.0 1% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having
the structural formula:
R, R2
N H H N
N
N~>-N O C=C ~ N'--(P~,
v H H R2 SO3M 8O3M Rr
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis((4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradeinark Tinopal-UNPA-
GX by
Ciba-Geigy Corporation. Tinopal-LTNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
CA 02372892 2004-07-20
When in the above formula, RI is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
trademark Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such
as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially
marketed under the trademark Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for usc in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used in
combination with the selected polymeric dye transfer inhibiting agents
hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO
and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal
5BM-
GX and/or Tinopal AMS-GX) provides significantly better dye transfer
inhibition in
aqueous wash solutions than does either of these two detergent composition
components
when used alone. Without being bound by theory, it is believed that such
brighteners
work this way because they have high affinity for fabrics in the wash solution
and
therefore deposit relatively quick on these fabrics. The extent to which
brighteners
deposit on fabrics in the wash solution can be defined by a parameter called
the
"exhaustion coefficient". The exhaustion coefficient is in general as the
ratio of a) the
brightener material deposited on fabric to b) the initial brightener
concentration in the
wash liquor. Brighteners with relatively high exhaustion coefficients are the
most
suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types of
compounds can optionally be used in the present compositions to provide
conventional
fabric "brightness" benefits, rather than a true dye transfer inhibiting
effect. Such usage
is conventional and well-known to detergent formulations.
Form Of the com osp ition - The compositions of the present invention may be
of any
useful form. That is the compositions may be in the form of a granule, liquid,
bar, gel,
liqui-gel, paste, microemulsion, aerosol, powdes, solid, and the like. The
form of the
composition will be selected depending upon the desired properties of the
formulation
and the intended use of the composition.
Specific Form Application Compositions
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It is more preferred that the selection of the carrier and other adjuncts
ingredients be
based on the end use and form of the composition. For example when the
detergent
composition is in the form of a nonaqueous liquid laundry detergent
composition the carrier
and other adjuncts ingredients used would be those appropriate to those
laundry detergent
compositions.
The detergent compositions of the present invention typically, but are not
limited to,
include personal cleansing compositions, liquid and non-liquid hard surface
cleaning
compositions, aqueous and nonaqueous liquid laundry detergents, laundry bars,
shampoos,
hand soap, syndet bars, shampoos, antidandruff shampoos, liquid laundry
compositions,
automatic dishwashing compositions, fabric softening compositions, rinse aid
compositions
and mixtures thereof.
The compositions can be in the form of granules, tablets, liquids, Iiqui-gels,
gels,
microemulsions, thixatropic liquids, bars, pastes, powders and mixtures
thereof.
When the compositions of the present invention is a personal cleansing
composition, such as body washes, facial scrubs, styling mousse, hair gel,
shampoos,
conditioners, etc, the composition typically includes a conventional personal
cleansing
additive, more preferably selected from the group consisting of conditioning
agents,
preferably selected from nonvolatile hydrocarbon conditioning agents,
nonvolatile silicone
conditioning agents and mixtures thereof; deposition polymer; conventional
personal care
polymer; antidandruff agent; surfactant; dispersed phase polymer; and mixtures
thereof.
When the personal cleansing compositions include a conditioning agent they
must also
contain a suspending agent. Furthermore, when the compositions of the present
invention is
a personal cleansing composition, such as a shampoo, conditioner, styling gel
or mousse,
they may also optionally contain a water insoluble hair styling polymer, a
volatile water
insoluble solvent, and optionally, a cationic spreading agent.
When the compositions of the present invention is an antidandruff shampoo the
composition typically includes an antidandruff agent.
When the compositions of the present invention is a hard surface cleaning
composition (HSC) the composition typically includes a conventional surface
cleansing
additive, more preferably selected from the group consisting of surfactant;
and mixtures
thereof. HSC compositions preferably are in the form of a liquid, powder,
paste, gel, liquid-
gel, microemulsion or granule.
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When the compositions of the present invention is a nonaqueous heavy
dutyliquid
laundry detergent (HDL) composition the composition typically is in the form
of a stable
suspension of solid, substantially insoluble particulate material dispersed
throughout a
structured, surfactant-containing liquid phase, wherein the nonaqueous,
liquid, heavy-duty
detergent composition further comprises:
from about 55% to 98.9% by weight of the composition of a structured,
surfactant-
containing liquid phase formed by combining:
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i) from about 1% to 80% by weight of said liquid phase of one or more
nonaqueous organic diluents; and
ii) from about 20% to 99%, preferably from about 35% to 70%, more
preferably from about 50% to 65% by weight of said liquid phase of a
surfactant system comprising surfactants selected from the group
consisting of anionic, nonionic, cationic surfactants and combinations
thereof;
optionally, but preferably, wherein the detergent composition further
comprises
from at least about 0.1% by weight of the composition of a bleach activator
selected from the group consisting of nonanoyloxybenzene sulfonate, amido-
derived bleach activators of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
and mixtures thereof;
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl,
aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is a
suitable leaving group.
It is also prefered that when the composition is a nonaqueous, liquid, heavy-
duty
detergent it further comprises from about 0.1 to about 8% of an alkyl
polyhydroxy fatty
acid amide.
The surfactant-containing, non-aqueous liquid phase of the present invention
will
generally comprise from about 52% to about 98.9% by weight of the detergent
compositions herein. More preferably, this liquid phase is surfactant-
structured and will
comprise from about 55% to 98% by weight of the compositions. Most preferably,
this
non-aqueous liquid phase will comprise from about 55% to 70% by weight of the
compositions herein. Such a surfactant-containing liquid phase will frequently
have a
density of from about 0.6 to 1.4 g/cc, more preferably from about 0.9 to 1.3
g/cc. The
liquid phase of the nonaqueous HDL detergent compositions herein is preferably
formed
from one or more non-aqueous organic diluents into which is mixed a surfactant
structuring agent which is preferably a specific type of anionic surfactant-
containing
powder.
It is also prefered that when the composition is a nonaqueous, liquid, heavy-
duty
detergent that the particulate material comprises from about 0.01% to 50% by
weight of
the composition, said particulate material ranging in size from about 0.1 to
1500 microns,
and is preferably selected from the group consisting of peroxygen bleaching
agents,
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bleach activators, colored speckles, organic detergent builders, inorganic
alkalinity
sources and mixtures thereof.
It is also prefered that when the composition is a nonaqueous, liquid, heavy-
duty
detergent that the nonaqueous, liquid, heavy-duty detergent further comprises
from about
0.1 to about 8%, by weight of an alkyl dimethyl amine oxide and from about
0.05 to
about 2%, by weight of magnesium ions.
When the compositons of the present invention is a an aqueous based heavy-duty
liquid detergent composition then the an aqueous based heavy-duty liquid
detergent
composition typically further comprises:
A) from about 5% to about 70%, by weight of composition, of a surfactant
system;
B) from about 0.1 to about 8% of a co-surfactant composition selected from the
group consisting of alkyl polyhydroxy fatty acid amide, alkyl amidopropyl
dimethyl amine and mixtures thereof; and
C) from about 30% to about 95%, of an aqueous liquid carrier.
It is also prefered that when the composition is an aqueous based heavy-duty
liquid detergent composition that the composition further comprises
conventional
detergent additives selected from the group consisting of builders; bleaching
compounds,
such as bleach activators, preferably selected from (6-octanamido-caproyl)
oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-
caproyl) oxybenzenesulfonate and mixtures thereof., bleach, bleach catalysts,
etc.;
polymeric dispersing agents; anti-redeposition agents polymeric soil release
agents;
enzymes; additional surfactants; and mixture thereof.
It is also prefered that when the composition is an aqueous based heavy-duty
liquid detergent composition that the composition further comprises 6-
nonylamino-6-
oxoperoxycaproic acid.
It is also prefered that when the composition is an aqueous based heavy-duty
liquid
detergent composition that the the surfactant system comprises at least one
amine based
surfactant of the general formula:
, R3
RI-X-(CH2)õ-N,
R4
wherein R1 is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging group
which can be absent; when X is present X is selected from NH, CONH, COO, and
0; R3
and R4 are individually selected from H, C1-C4 alkyl and CH2-CH2-O(R5) wherein
R5
is H or methyl.
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CA 02372892 2004-07-20
Non-Aqueous HDL compositions
Non-aqueous Organic Diluents - When the compositions of the present invention
are
non-aqueous HDL detergent compositions, the major component of the liquid
phase of
the non-aqueous HDL detergent compositions herein comprises one or more non-
aqueous
organic diluents. The non-aqueous organic diluents used in this invention may
be either
surface active, i.e., surfactant, liquids or non-aqueous, non-surfactant
liquids referred to
herein as non-aqueous solvents. The term solvent' is used herein- to
connote the non-
surfactant, non-aqueous liquid portion of the compositions herein. While some
of the
essential and/or optional components of the compositions herein may actually
dissolve in
the "solvent"-containing liquid phase, other components will be present as
particulate
material dispersed within the "solvent"-containing liquid phase. Thus the term
"solvent"
is not meant to require that the solvent material be capable of actually
dissolving all of
the detergent composition components added thereto.
The non-aqueous liquid diluent component will generally comprise from about
50%
to 100%, more preferably from about 50% to 80%, most preferably from about 55%
to
75%, of a structured, surfactant-containing liquid phase. Preferably the
liquid phase of
the compositions herein, i.e., the non-aqueous liquid diluent component, will
comprise
both non-aqueous liquid surfactants and non-surfactant non-aqueous solvents.
i) Non-aqueous Surfactant Liquids
Suitable types of non-aqueous surfactant liquids which can be used to for.m
the
liquid phase of the non-aqueous HDL detergent compositions herein include the
alkoxylated alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers,
polyhydroxy fatty acid amides, alkylpolysaccharides, and the like. Such
normally liquid
surfactants are those having an H]LB ranging from 10 to 16. Most preferred of
the
surfactant liquids are the alcohol alkoxylate nonionic surfactants.
The amount of total liquid surfactant in the preferred surfactant-structured,
non-
aqueous liquid phase herein will be determined by the type and amounts of
other
composition components and by the desired composition properties. Generally,
the
liquid surfactant can comprise from about 35% to 70% of the non-aqueous liquid
phase
of the compositions herein. More preferably, the liquid surfactant will
comprise from
about 50% to 65% of a non-aqueous structured liquid phase. This corresponds to
a non-
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aqueous liquid surfactant concentration in the total composition of from about
15% to
70% by weight, more preferably from about 20% to 50% by weight, of the
composition.
ii) Non-surfactant Non-aqueous Organic Solvents
The liquid phase of the non-aqueous HDL detergent compositions herein may
also comprise one or more non-surfactant, non-aqueous organic solvents. Such
non-
surfactant non-aqueous liquids are preferably those of low polarity. For
purposes of this
invention, "low-polarity" liquids are those which have little, if any,
tendency to dissolve
one of the preferred types of particulate material used in the compositions
herein, i.e., the
peroxygen bleaching agents, sodium perborate or sodium percarbonate. Thus
relatively
polar solvents such as ethanol are preferably not utilized. Suitable types of
low-polarity
solvents useful in the non-aqueous liquid detergent compositions herein do
include non-
vicinal C4-C8 alkylene glycols, alkylene glycol mono lower alkyl ethers, lower
molecular
weight polyethylene glycols, lower molecular weight methyl esters and amides,
and the
like. For example, suitable low-polarity solvents include hexylene glycol, (4-
methyl-2,4-
pentanediol), 1,6-hexanediol, 1,3-butylene glycol, 1,4-butylene glycol,
diethylene glycol
monobutyl ether, tetraethylene glycol monobutyl ether, lower molecular weight
polyethylene glycols (PEGs), dipropolyene glycol monoethyl ether, and
dipropylene
glycol monobutyl ether. Diethylene glycol monobutyl ether, hexylene glycol,
dipropylene glycol monobutyl ether and butoxy-propoxy-propanol (BPP) are
especially
preferred
The non-aqueous, generally low-polarity, non-surfactant organic solvent(s)
employed should, of course, be compatible and non-reactive with other
composition
components, e.g., bleach and/or activators, used in the liquid detergent
compositions
herein. Such a solvent component is preferably utilized in an amount of from
about 1% to
70% by weight of the liquid phase. More preferably, a non-aqueous, low-
polarity, non-
surfactant solvent will comprise from about 10% to 60% by weight of a
structured liquid
phase, most preferably from about 20% to 50% by weight, of a structured liquid
phase of
the composition. Utilization of non-surfactant solvent in these concentrations
in the
liquid phase corresponds to a non-surfactant solvent concentration in the
total
composition of from about 1% to 50% by weight, more preferably from about 5%
to 40%
by weight, and most preferably from about 10% to 30% by weight, of the
composition.
Surfactant Structurant - The non-aqueous liquid phase of the non-aqueous HDL
detergent
compositions of this invention is prepared by combining with the non-aqueous
organic
liquid diluents hereinbefore described a surfactant which is generally, but
not necessarily,
selected to add structure to the non-aqueous liquid phase of the detergent
compositions
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CA 02372892 2004-07-20
herein. Structuring surfactants can be of the anionic, nonionic, cationic,
and/or
amphoteric types, such as thoses herein before described.
Preferred structuring surfactants are the anionic surfactants such as the
alkyl
sulfates (primary or secondary), such as the C8-C18 paraffin sulfonates and
the C8-C18
olefin sulfonates, the alkyl polyalkoxylate sulfates (also known as
alkoxylated alkyl
sulfates or alkyl ether sulfates), C 10-C 18 alkyl alkoxy carboxylates
(especially the EO I
to 5 ethoxycarboxylates) and the C 10-C 18 sarcosinates, especially oleoyl
sarcosinate and
the linear alkyl benzene sulfonates(LAS), with LAS being the most preferred.
sulfonated
anionic surfactants.
Additional suitable surfactants for use in the present invention included
nonionic
surfactants, specifically, polyhydroxy fatty acid amides.
If utilized, alkyl sulfates will generally comprise from about 1% to 30% by
weight
of the composition, more preferably from about 5% to 25% by weight of the
composition. Non-aqueous liquid detergent compositions containing alkyl
sulfates,
peroxygen bleaching agents, and bleach activators are described in greater
detail in Kong-
Chan et al.; WO 96/10073; Publiched April 4, 1996.
If utilized, alkyl polyalkoxylate sulfates can also generally comprise from
about 1%
to 30% by weight of the composition, more preferably from about 5% to 25% by
weight
of the composition. Non-aqueous liquid detergent compositions containing alkyl
polyalkoxylate sulfates, in combination with polyhydroxy fatty acid amides,
are described
in greater detail in CA 2,216,937.
Preferred surfactants for use in the non-aqueous HDL detergent compositions
described herein are amine based surfactants of the general formula:
'R3
RI-X-(CH2)n-N,
Ra
wherein RI is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging group
which is selected from NH, CONH, COO, or 0 or X can be absent; and R3 and R4
are
individually selected from H, CI-C4 alkyl, or (CH2-CH2-O(R5)) wherein R5 is H
or
methyl. Especially preferred amines based surfactants include the following:
R1-(CH2)2-NH2,
R1-O-(CH2)3-NH2
R1-C(O)-NH-(CH2)3-N(CH3)2
(R5CH(OH)CHZ)2NRI
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wherein Rl is a C6-C12 alkyl group and R5 is H or CH3. Particularly preferred
amines
for use in the surfactants defined above include those selected from the group
consisting
of octyl amine, hexyl amine, decyl amine, dodecyl amine, C8-C12
bis(hydroxyethyl)amine, Cg-C12 bis(hydroxyisopropyl)amine, C8-C12 amido-propyl
dimethyl amine, or mixtures thereof.
In a highly preferred embodiment, the amine based surfactant is described by
the
formula:
R1-C(O)-NH-(CH2)3-N(CH3)2
wherein R1 is C8-C12 alkyl.
Solid Particulate Materials - The non-aqueous HDL detergent compositions
herein
preferably comprise from about 0.01% to 50% by weight, more preferably from
about
0.2% to 30% by weight, of solid phase particulate material which is dispersed
and
suspended within the liquid phase. Generally such particulate material will
range in size
from about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns.
Most
preferably, such material will range in size from about 5 to 200 microns.
The particulate material utilized herein can comprise one or more types of
detergent
composition components which in particulate form are substantially insoluble
in the non-
aqueous liquid phase of the composition. The types of particulate materials
which can be
utilized are described in detail as follows:
Peroxygen Bleaching Agent With Optional Bleach Activators - The most preferred
type
of particulate material useful in the non-aqueous HDL detergent compositions
herein
comprises particles of a peroxygen bleaching agent. Such peroxygen bleaching
agents
may be organic or inorganic in nature. Inorganic peroxygen bleaching agents
are
frequently utilized in combination with a bleach activator. Suitable peroxygen
bleaching
agents for use as particulate material in the non-aqueous HDL detergent
compositions are
hereinbefore described.
Especially suitable for then non-aqueous HDL detergent compositions herein are
the amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an
alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or
alkaryl
containing from about 1 to about 10 carbon atoms, and L is any suitable
leaving group,
for example, oxybenzene sulfonate, -OOH, -OOM. A leaving group is any group
that is
displaced from the bleach activator as a consequence of the nucleophilic
attack on the
bleach activator by the perhydrolysis anion. A preferred leaving group is
phenol
sulfonate.
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CA 02372892 2004-07-20
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)
oxybenzenesulfonate,
(6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof . described in
U.S. Patent 4,634,551. Such mixtures are characterized herein as
(6-C8-C10 alkamido-caproyl)oxybenzenesulfonate.
If peroxygen bleaching agents are used as all or part of the particulate
material, they
will generally comprise from about 0.1% to 30% by weight of the composition.
More
preferably, peroxygen bleaching agent will comprise from about 1% to 20% by
weight of
the composition. Most preferably, peroxygen bleaching agent will be present to
the
extent of from about 5% to 20% by weight of the composition. If utilized,
bleach
activators can comprise from about 0.5% to 20%, more preferably from about 3%
to
10%, by weight of the composition. Frequently, activators are employed such
that the
molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1,
more preferably
from about 1.5:1 to 5:1.
In addition, it has been found that bleach activators, when agglomerated with
certain
acids such as citric acid, are more chemically stable.
Organic Builder Material - Another possible type of particulate material which
can be
suspended in the non-aqueous liquid detergent compositions herein comprises an
organic
detergent builder material which serves to counteract the effects of calcium,
or other ion,
water hardness encountered during laundering/bleaching use of the compositions
herein.
Examples of such materials include the alkali metal, citrates, succinates,
malonates, fatty
acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl
carboxvlates. Specific examples include sodium, potassium and lithium salts of
oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric
acid. Other
examples of organic phosphonate type sequestering agents such as those which
have been
sold by Monsanto under the Dequest trademark and alkanehydroxy phosphonates.
Citrate salts are highly preferred.
If utilized as all or part of the particulate material, insoluble organic
detergent
builders can generally comprise from about 2% to 20% by weight of the
compositions
herein. More preferably, such builder material can comprise from about 4% to
10% by
weight of the composition. Suitable builders for use as particulate material
in the non-
aqueous HDL detergent compositions are hereinbefore described.
Inorganic Alkalinitv Sources - Another possible type of particulate material
which can be
suspended in the non-aqueous liquid detergent compositions herein can comprise
a
material which serves to render aqueous washing solutions formed from such
compositions generally alkaline in nature. Such materials may or may not also
act as
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detergent builders, i.e., as materials which counteract the adverse effect of
water hardness
on detergency performance.
Examples of suitable alkalinity sources include water-soluble alkali metal
carbonates, bicarbonates, borates, silicates and metasilicates. Although not
preferred for
ecological reasons, water-soluble phosphate salts may also be utilized as
alkalinity
sources. These include alkali metal pyrophosphates, orthophosphates,
polyphosphates
and phosphonates. Of all of these alkalinity sources, alkali metal carbonates
such as
sodium carbonate are the most preferred.
If utilized as all or part of the particulate material component, the
alkalinity source
will generally comprise from about 1% to 25% by weight of the compositions
herein.
More preferably, the alkalinity source can comprise from about 2% to 15% by
weight of
the composition. Such materials, while water-soluble, will generally be
insoluble in the
non-aqueous detergent compositions herein. Thus such materials will generally
be
dispersed in the non-aqueous liquid phase in the form of discrete particles.
Suitable
builders for use as particulate material in the non-aqueous HDL detergent
compositions
are hereinbefore described.
Colored Speckles - The non-aqueous HDL detergent compositions herein may also
optionally contain from about 0.05% to 2%, more preferably 0.1% to 1%, of the
composition of colored speckles. Such colored speckles themselves are
combinations of
a conventional dye or pigment material with a certain kind of carrier material
that imparts
specific characteristics to the speckles. For purposes of this invention,
"colored" speckles
are those which have a color that is visibly distinct from the color of the
liquid detergent
composition in which they are dispersed.
Aqueous-HDL compositions
Surfactants - The present invention also comprises aqueous based HDL detergent
compositions. The aqueous HDL detergent compositions preferably comprise from
about
10% to about 98%, preferably from about 30% to about 95%, by weight of an
aqueous
liquid carrier which is preferably water. Additionally, the aqueous HDL
detergent
compositions of the present invention comprise a surfactant system which
preferably
contains one or more detersive surfactants. The surfactants can be selected
from
nonionic detersive surfactant, anionic detersive surfactant, zwitterionic
detersive
surfactant, amine oxide detersive surfactant, and mixtures thereof. The
surfactant system
typically comprises from about 5% to about 70%, preferably from about 15% to
about
30%, by weight of the detergent composition. Suitable surfactants for use in
the aqueous
HDL detergent compositions are hereinbefore described.
Builders
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The aqueous HDL detergent compositions herein also optionally, but preferably,
contain up to about 50%, more preferably from about 1% to about 40%, even more
preferably from about 5% to about 30%, by weight of a detergent builder
material. Lower
or higher levels of builder, however, are not meant to be excluded. Suitable
biuilders for
use in the aqueous HDL detergent compositions are hereinbefore described.
Structure Elasticizing Agents
Both the non-aqueous and aqueous HDL detergent compositions herein can also
contain from about 0.1 % to 5%, preferably from about 0.1 % to 2% by weight of
a finely
divided, solid particulate material which can include silica, e.g., fumed
silica, titanium
dioxide, insoluble carbonates, finely divided carbon or combinations of these
materials.
Fine particulate material of this type functions as a structure elasticizing
agent in the
products of this invention. Such material has an average particle size ranging
from about
7 to 40 nanometers, more preferably from about 7 to 15 nanometers. Such
material also
has a specific surface area which ranges from about 40 to 400m2/g.
The finely divided elasticizing agent material can improve the shipping
stability of
the non-aqueous liquid detergent products herein by increasing the elasticity
of the
surfactant-structured liquid phase without increasing product viscosity. This
permits
such products to withstand high frequency vibration which may be encountered
during
shipping without undergoing undesirable structure breakdown which could lead
to
sedimentation in the product.
In the case of titanium dioxide, the use of this material also imparts
whiteness to the
suspension of particulate material within the detergent compositions herein.
This effect
improves the overall appearance of the product.
Other Optional HDL Compositional Components
In addition to the liquid and solid phase components as hereinbefore
described, the
aqueous and non-aqueous based HDL detergent compositions can, and preferably
will,
contain various other optional components. Such optional components may be in
either
liquid or solid form. The optional components may either dissolve in the
liquid phase or
may be dispersed within the liquid phase in the form of fine particles or
droplets. Some
of the other materials which may optionally be utilized in the compositions
herein
include, but is not limited to, enzymes, inorganic builders, chelants,
thickening, viscosity
control and/or dispersing agents, clay soil removal/anti-redeposition agents,
liquid bleach
activators, bleach catalysts, perfume, brignteners, polymeric soil release
agents and
mixtures thereof.
Hard Surface Cleaning (HSC) compositions
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When the compositions of the present invention are hard surface cleaner
composition of the present invention they may additionally contain a
conventional
surface cleansing additive. The conventional surface cleansing additive are
present from
about 0.001% to about 99.9% by weight. Preferably, conventional surface
cleansing
additive will be present from at least about 0.5%, more preferably, at least
about 1%,
even more preferably at least about 2%, by weight. Additionally, the
conventional
surface cleansing additives can also be present at least about 5%, at least
about 8% and
at least about 10%, by weight but it is more preferable that the conventional
surface
cleansing additive be present in at least about 2% by weight. Furthermore, the
conventional surface cleansing additive will be preferably present in the hard
surface
composition at preferably at less than about 45%, more preferably less than
about 40%,
even more preferably less than about 35%, even more preferably less than about
30%,
even more preferably less than about 20%, by weight. This conventional surface
cleansing additive is selected from the group comprising, liquid carrier;
surfactant;
builder; solvent; polymeric additive; pH adjusting material; hydrotropes; and
mixtures
thereof.
The polymeric additives, useful in the HSC compositions of the present
invention
can be further selected from the group comprising
1) polyalkoxylene glycol;
2) PVP homopolymers or copolymers thereof;
3) polycarboxylate;
4) sulfonated polystyrene polymer; and
5) mixtures thereof.
Liquid Carrier - The balance of the HSC compositions can be water and non-
aqueous
polar solvents with only minimal cleaning action like methanol, ethanol,
isopropanol,
ethylene glycol, glycol ethers having a hydrogen bonding parameter of greater
than 7.7,
propylene glycol, and mixtures thereof, preferably isopropanol. The level of
non-
aqueous polar solvent is usually greater when more concentrated formulas are
prepared.
Typically, the level of non-aqueous polar solvent is from about 0.5% to about
40%,
preferably from about 1% to about 10%, more preferably from about 2% to about
8%
(especially for "dilute" compositions) and the level of aqueous liquid carrier
is from
about 50% to about 99%, preferably from about 75% to about 95%.
Surfactant - The hard surface cleaning compositions according to the present
invention
contains at least one surfactants, preferably selected from: anionic
surfactants, cationic
surfactants; nonionic surfactants; amphoteric surfactants; zwiterionic
surfactants and
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mixtures thereof. Surfactants suitable for use in HSC compositions according
to the
present invention have been herein before described.
The hard surface cleaning compositions of the present invention will
preferably
comprise from about 0.001 % to about 20%, preferably from about 0.1 % to about
10%, by
weight of surfactants.
Builders - The level of builder can vary widely depending upon the end use of
the
composition and its desired physical form. When present, the HSC compositions
will
preferably comprise from about 0.001% to about 10%, more preferably 0.01% to
about
7%, even more preferably 0.1% to about 5% by weight of the composition of a
builder.
Builders suitable for use in HSC compositions according to the present
invention have
been herein before described.
Co-Solvents - Optionally, the HSC compositions of the present invention
further
comprise one or more co-solvents. The level of co-solvent, when present in the
composition, is typically from about 0.001% to about 30%, preferably from
about 0.01%
to about 10%, more preferably from about 1% to about 5%. Co-solvents are
broadly
defined as compounds that are liquid at temperatures of 20 C-25 C and which
are not
considered to be surfactants. One of the distinguishing features is that co-
solvents tend
to exist as discrete entities rather than as broad mixtures of compounds. Some
co-
solvents which are useful in the hard surface cleaning compositions of the
present
invention contain from about 1 carbon atom to about 35 carbon atoms, and
contain
contiguous linear, branched or cyclic hydrocarbon moieties of no more than
about 8
carbon atoms. Examples of suitable co-solvents for the present invention
include,
methanol, ethanol, propanol, isopropanol, 2-methyl pyrrolidinone, benzyl
alcohol and
morpholine n-oxide. Preferred among these co-solvents are methanol and
isopropanol.
The HSC compositions herein may additionally contain an alcohol having a
hydrocarbon chain comprising 8 to 18 carbon atoms, preferably 12 to 16. The
hydrocarbon chain can be branched or linear, and can be mono, di or
polyalcohols.
The co-solvents which can be used herein include all those known to the those
skilled in the art of hard-surfaces cleaner compositions. Suitable co-solvents
for use
herein include ethers and diethers having from 4 to 14 carbon atoms,
preferably from 6 to
12 carbon atoms, and more preferably from 8 to 10 carbon atoms, glycols or
alkoxylated
glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched
alcohols,
alkoxylated aliphatic branched alcohols, alkoxylated linear Cl-C5 alcohols,
linear C1-C5
alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-
C16
glycol ethers and mixtures thereof.
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Polymeri c additives - The hard surface cleaning compositions of the present
invention
may comprise from about 0.001% to about 20%, preferably from about 0.01% to
about
10%, more preferably from about 0.1% to about 5%, and even more preferably
from
about 0.1% to about 3% of a polymeric additive. Suitable polymeric additives
include:
1) polyalkoxylene glycol;
2) PVP homopolymers or copolymers thereof;
3) polycarboxylate;
4) sulfonated polystyrene polymer; and
5) mixtures thereof.
1) Polyalkoxylene Glycol - The HSC compositions according to the present
invention
may contain an antiresoiling agent selected from the group consisting of
polyalkoxylene
glycol, mono- and dicapped polyalkoxylene glycol and a mixture thereof. The
compositions of the present invention may comprise from 0.001% to 20% by
weight of
the total composition of said antiresoiling agent or a mixture thereof,
preferably from
0.01% to 10%, more preferably from 0.1% to 5% and most preferably from 0.2% to
2%
by weight, when such an agent is present in the hard surface cleaning
composition.
2) PVP homopolymers or copolymers thereof - The hard surface cleaning
compositions
according to the present invention may contain a vinylpyrrolidone homopolymer
or
copolymer or a mixture thereof. The compositions of the present invention
comprise
from 0.001% to 20% by weight of the total composition of a vinylpyrrolidone
homopolymer or copolymer or a mixture thereof, preferably from 0.01% to 10%,
more
preferably from 0.1% to 5% and most preferably from 0.2% to 2%, when PVP
homopolymers or copolymers are present.
Suitable vinylpyrrolidone homopolymers which can be used herein is an
homopolymer
of N-vinylpyrrolidone having the following repeating monomer:
H
I
C-CHZ
N
HZ C~ C=O
H2 C- CH2
n
wherein n (degree of polymerization) is an integer of from 10 to 1,000,000,
preferably
from 20 to 100,000, and more preferably from 20 to 10,000.
Accordingly, suitable vinylpyrrolidone homopolymers ("PVP") which can be used
herein have an average molecular weight of from 1,000 to 100,000,000,
preferably from
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2,000 to 10,000,000, more preferably from 5,000 to 1,000,000, and most
preferably from
50,000 to 500,000.
Suitable vinylpyrrolidone homopolymers are commercially available from ISP
Corporation, New York, NY and Montreal, Canada under the product names PVP K-
15
(viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of
40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90
(average
molecular weight of 360,000). Other suitable vinylpyrrolidone homopolymers
which are
commercially available from BASF Cooperation include Sokalan HP 165 and
Sokalan
HP 12 ; vinylpyrrolidone homopolymers known to persons skilled in the
detergent field
(see for example EP-A-262,897 and EP-A-256,696).
Suitable copolymers of vinylpyrrolidone which can be used herein include
copolymers
of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures
thereof.
3) Pol ca~box ylate - The hard surface cleaning composition of the present
invention may
optionally contain a polycarboxylate polymer. When present the polycarboxylate
polymer will be preferably from about 0.001% to about 10% , more preferably
from
about 0.01% to about 5%, even more preferably about 0.1% to 2.5%, by weight of
composition.
Polycarboxylate polymers can be those formed by polymerization of monomers, at
least some of which contain carboxylic functionality. Common monomers include
acrylic acid, maleic acid, ethylene, vinyl pyrrollidone, methacrylic acid,
methacryloylethylbetaine, etc. In general, the polymers should have molecular
weights
of more than 10,000, preferably more than about 20,000, more preferably more
than
about 300,000, and even more preferably more than about 400,000. It has also
been
found that higher molecular weight polymers, e.g., those having molecular
weights of
more than about 3,000,000, are extremely difficult to formulate and are less
effective in
providing anti-spotting benefits than lower molecular weight polymers.
Accordingly, the
molecular weight should normally be, especially for polyacrylates, from about
20,000 to
about 3,000,000; preferably from about 20,000 to about 2,500,000; more
preferably from
about 300,000 to about 2,000,000; and even more preferably from about 400,000
to
about 1,500,000.
4) Sulfonated Polystyrene Polymer - Another suitable materials which can be
included in
to the hard surface cleaning composition of the invention are high molecular
weight
sulfonated polymers such as sulfonated polystyrene. A typical formula is as
follows.
-[CH(C6H4SO3Na) - CH21n CH(C6H5) - CH2 -
wherein n is a number to give the appropriate molecular weight as disclosed
below.
CA 02372892 2004-07-20
Typical molecular weights are from about 10,000 to about 1,000,000, preferably
from about 200,000 to about 700,00.
Examples of suitable materials for use herein include poly(vinyl
pyrrolidone/acrylic acid) sold under the name 'Acrylidone"O by ISP and
poly(acrylic
acid) sold under the name "Accumer"O by Rohm & Haas. Other suitable materials
include sulfonated polystyrene polymers sold under the name Versaflex0 sold by
National Starch and Chemical Company, especially Versaflex 7000.
The level of polymer should normally be, when polymer is present in the hard
surface cleaning composition, from about 0.01% to about 10%, preferably from
about
0.05% to about 0.5%, more preferably from about 0.1% to about 0.3%.
Optional Components
The hard surface cleaning compositions of the present invention may further
comprise one or more optional components known for use in hard surface
cleaning
compositions provided that the optional components are physically and
chemically
compatible with the essential component described herein, or do not otherwise
unduly
impair product stability, aesthetics or performance. Concentrations of such
optional
components typically range from about 0.001% to about 30% by weight of the
hard
surface cleaning compositions, when present.
Optional components include, but not limited to, chelants, bleaches (including
oxygen, chlorine and redox), dyes, perfumes, and mixtures thereof. This list
of optional
components is not meant to be exclusive, and other optional components can be
used.
Personal Cleansing compositions
The compositions of the present invention may also be a personal cleansing
composition. That is a composition for direct application to a persons, skin,
hair etc.
Examples of personal cleansing compositions includes, but is not limited to,
body
washes, facial scrubs, shampoos, conditions, medicated shampoos, anti-dandruff
shampoos, so-called 2-in- shampoo and conditiones, toilet bars, hand soap
(including
liquid or bar), deoderant soap, and the like.
The conventional personal cleansing composition of the present invention
additionally contains a conventional personal cleansing additive. The
conventional
personal cleansing additive are present from about 0.001% to about 49.9% by
weight.
Preferably, the conventional personal cleansing additive will be present from
at least
about 0.5%, more preferably, at least about 1%, even more preferably at least
about 2%,
by weight. Additionaly, the conventional personal cleansing additives can also
be
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present at least about 5%, at least about 8% and at least about 10%, by weight
but it is
more preferable that the conventional personal cleansning additive be present
in at least
about 2% by weight. Furthermore, the conventional personal cleansing additive
will be
preferably present in the personal cleansing composition at preferably at less
than about
45%, more preferably less than about 40%, even more preferably less than about
35%,
even more preferably less than about 30%, even more preferably less than about
20%, by
weight. This conventional personal cleansing additive is selected from the
group
comprising;
a) conditioning agent
b) conventional personal care polymer;
c) antidandruff agent
d) cosurfactant; and
e) mixtures thereof.
These conventional personal cleansing additives are just some of the possible
ingredients which can be conventionally added to personal cleansing
compositions.
The conditioning agents, (a), useful in the present invention can be further
selected from the group comprising
1) non-volatile hydrocarbons conditioning agents;
2) silicone conditioning agents; and
3) mixtures thereof.
The conventional personal care polymers, (b), useful in the present invention
can
be further selected from the group comprising
i) deposition polymers;
ii) styling polymers and solvent;
iii) dispersed phase polymers; and
iv) mixtures thereof
a) Conditioning Agent
The personal cleansing compositions of the present invention comprise from
about 0.005% to about 20%, preferably from about 0.01% to about 10%, more
preferably
from about 0.1% to about 5%, and even more preferably from about 0.5% to about
3% of
dispersed particles of a nonvolatile hair or skin conditioning agent. Suitable
hair or skin
conditioning agents include nonvolatile silicone conditioning agents,
nonvolatile
hydrocarbon conditioning agents, and mixtures thereof.
As used herein, average particle size of the conditioning agent particles may
be
measured within the personal cleansing compositions by light scattering
methods well
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CA 02372892 2004-07-20
known in the art for detennining average particle size for emulsified liquids.
One such
method involves the use of a Horiba LA-910 particle size analyzer.
For more information and additional examples of conditioning agents see
WO 98/16189 and WO 98/18433. See also U.S. Patent No. 4,741,855.
1) Nonvolatile Silicone Conditioning Agents Preferred conditioning agents
useful herein
include nonvolatile, dispersed silicone conditioning agents. By nonvolatile is
meant that
the silicone conditioning agent exhibits very low or no significant vapor
pressure at
ambient conditions, e.g., I atmosphere at 25 C. The nonvolatile silicone
conditioning
agent preferably has a boiling point at ambient pressure of above about 250 C,
preferably
of above about 260 C, and more preferably of above about 275 C. By dispersed
is meant
that the conditioning agent forms a separate, discontinuous phase from the
aqueous
carrier such as in the fonn of an emulsion or a suspension of droplets.
The nonvolatile silicone hair conditioning agents suitable for use herein
preferably
have a viscosity of from about 1,000 to about 2,000,000 centistokes at 250C,
more
preferably from about 10,000 to about 1,800,000, and even more preferably from
about
100,000 to about 1,500,000. The viscosity can be measured by means of a glass
capillary
viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20,
1970. Suitable silicone fluids include polyalkyl
siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether
siloxane copolymers, and mixtures thereof. Other nonvolatile silicones having
hair
conditioning properties can also be used.
The silicones herein also include polyalkyl or polyaryl siloxanes with the
following
structure:
R R R
A-Si--O Si-O Si-A
I I I
R R xR
wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000.
"A"
represents groups which block the ends of the silicone chains. The alkyl or
aryl groups
substituted on the siloxane chain (R) or at the ends of the siloxane chains
(A) can have
any structure as long as the resulting silicone remains fluid at room
temperature, is
dispersible, is neither irritating, toxic nor otherwise harmful when applied
to the hair, is
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CA 02372892 2004-07-20
compatible with the other components of the composition, is chemically stable
under
normal use and storage conditions, and is capable of being deposited on and
conditions
the hair. Suitable A groups include hydroxy, methyl, methoxy, ethoxy, propoxy,
and
aryloxy. The two R groups on the silicon atom may represent the same group or
different groups. Preferably, the two R groups represent the same group.
Suitable R
groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl.
The
preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and
polymethylphenylsiloxane. Polydimethylsiloxane, which is also known as
dimethicone,
is especially preferred. The polyalkylsiloxanes that can be used include, for
example,
polydimethylsiloxanes. These siliconcs are available, for example, from the
General
Eleetric Company in their ViscasilR and SF 96 series, and from Dow Coming in
their
Dow Coming 200 series.
Polyalkylaryl siloxane fluids can also be used and include, for example,
polymethylphenylsiloxanes. These siloxanes are available, for example, from
the
General Electric Company as SF 1075 methyl phenyl fluid or from Dow Coming as
556
Cosmetic Grade Fluid.
Especially preferred, for enhancing the shine characteristics of hair, are
highly
arylated silicones, such as highly phenylated polyethyl silicone having
refractive indices
of about 1.46 or higher, especially about 1.52 or higher. When these high
refractive
index silicones are used, they should be mixed with a spreading agent, such as
a
surfactant or a silicone resin, as described below to decrease the surface
tension and
enhance the film forming ability of the material.
The silicones that can be used include, for example, a polypropylene oxide
modified polydimethylsiloxane although ethylene oxide or mixtures of ethylene
oxide
and propylene oxide can also be used. The ethylene oxide and polypropylene
oxide level
should be sufficiently low so as not to interfere with the dispersibility
characteristics of
the silicone. These material are also known as dimethicone copolyols.
Other silicones include amino substituted materials. Suitable alkylamino
substituted silicones include those represented by the following structure
(II)
CH3 OH
HO l i l i-O H
I H3 iCH2)3
x NH
(CH2}2
NH2
y
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wherein x and y are integers which depend on the molecular weight, the average
molecular weight being approximately between 5,000 and 10,000. This polymer is
also
known as "amodimethicone".
Suitable cationic silicone fluids include those represented by the formula
(III)
(R1)aG3-a-Si-(-OSiG2)n-(-OSiGb(Rl)2-b)m-O-SiG3-a(R1)a in which G is chosen
from
the group consisting of hydrogen, phenyl, OH, C1-C8 alkyl and preferably
methyl; a
denotes 0 or an integer from 1 to 3, and preferably equals 0; b denotes 0 or 1
and
preferably equals 1; the sum n+m is a number from I to 2,000 and preferably
from 50 to
150, n being able to denote a number from 0 to 1,999 and preferably from 49 to
149 and
m being able to denote an integer from 1 to 2,000 and preferably from 1 to 10;
Rl is a
monovalent radical of formula CqH2qL in which q is an integer from 2 to 8 and
L is
chosen from the groups
-N(R2)CH2-CH2-N(R2)2
-N(R2)2
-N(R2)3A
-N(R2)CH2-CH2-NR2H2A
in which R2 is chosen from the group consisting of hydrogen, phenyl, benzyl, a
saturated
hydrocarbon radical, preferably an alkyl radical containing from 1 to 20
carbon atoms,
and A denotes a halide ion.
An especially preferred cationic silicone corresponding to formula (III) is
the
polymer known as "trimethylsilylamodimethicone", of formula (IV):
IH IH3
(CH3)3Si O- i i O- i i OSi(CH3)3
L CH (CH2)
n I
NH
I
(CHz),
I
NH2
m
In this formula n and nl are selected depending on the exact molecular weight
of
the compound desired.
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Other silicone cationic polymers which can be used in the personal cleansing
compositions are represented by the formula (V):
RaCH2-CHOH-CH2-N+(R3)3Q
R3
I
(R3)3S1--O ~ I--O i I-O SI-O-SI(R3)3
R3 R3
r
where R3 denotes a monovalent hydrocarbon radical having from 1 to 18 carbon
atoms,
preferably an alkyl or alkenyl radical such as methyl; R4 denotes a
hydrocarbon radical,
preferably a C 1-C 1 g alkylene radical or a C 1-C 1 g, and more preferably C
1-Cg,
alkyleneoxy radical; Q is a halide ion, preferably chloride; r denotes an
average
statistical value from 2 to 20, preferably from 2 to 8; s denotes an average
statistical
value from 20 to 200, and preferably from 20 to 50. A preferred polymer of
this class is
available from Union Carbide under the trademark "UCAR SILICONE ALE 56."
References disclosing suitable silicones include U.S. Patent No. 2,826,551, to
Geen; U.S. Patent No. 3,964,500, to Drakoff, issued June 22, 1976; U.S. Patent
No.
4,364,837, to Pader; British Patent No. 849,433, to Woolston, and "Silicon
Compounds"
distributed by Petrarch Systems, Inc., 1984. This reference provides an
extensive, though
not exclusive, listing of suitable silicones.
Another silicone hair conditioning material that can be especially useful is a
silicone gum. The term "silicone gum", as used herein, means a
polyorganosiloxane
material having a viscosity at 25 C of greater than or equal to 1,000,000
centistokes. It
is recognized that the silicone gums described herein can also have some
overlap with
the above-disclosed silicones. This overlap is not intended as a limitation on
any of
these materials. Silicone gums are described by Petrarch, Id., and others
including U.S.
Patent No. 4,152,416, to Spitzer et al., issued May 1, 1979 and Noll, Walter,
Chemistry
and Technology of Silicones, New York: Academic Press 1968. Also describing
silicone
gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE
54 and
SE 76. The "silicone gums" will typically have a mass molecular weight in
excess
of about 200,000, generally between about 200,000 and about 1,000,000.
Specific
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examples include polydimethylsiloxane, (polydimethylsiloxane)
(methylvinylsiloxane)
copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane)
copolymer
and mixtures thereof.
Also useful are silicone resins, which are highly crosslinked polymeric
siloxane
systems. The crosslinking is introduced through the incorporation of
trifunctional and
tetrafunctional silanes with monofunctional or difunctional, or both, silanes
during
manufacture of the silicone resin. As is well understood in the art, the
degree of
cross]inking that is required in order to result in a silicone resin will vary
according to
the specific silane units incorporated into the silicone resin. In general,
silicone
materials which have a sufficient level of trifunctional and tetrafunctional
siloxane
monomer units, and hence, a sufficient level of crosslinking, such that they
dry down to a
rigid, or hard, film are considered to be silicone resins. The ratio of oxygen
atoms to
silicon atoms is indicative of the level of crosslinking in a particular
silicone material.
Silicone materials which have at least about 1.1 oxygen atoms per silicon atom
will
generally be silicone resins herein. Preferably, the ratio of oxygen:silicon
atoms is at
least about 1.2:1Ø Silanes used in the manufacture of silicone resins
include
monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-,
monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the
methy]-substituted silanes being most commonly utilized. Preferred resins are
offered by
General Electric as GE SS4230 and SS4267. Commercially available silicone
resins will
generally be supplied in a dissolved form in a low viscosity volatile or
nonvolatile
silicone fluid. The silicone resins for use herein should be supplied and
incorporated
into the present compositions in such dissolved form, as will be readily
apparent to those
skilled in the art. Without being limited by theory, it is believed that the
silicone resins
can enhance deposition of other silicones on the hair and can enhance the
glossiness of
hair with high refractive index volumes.
Other useful silicone resins are silicone resin powders such as the material
given
the CTFA designation polymethylsilsequioxane, which is commercially available
as
TospearlTM from Toshiba Silicones.
Background material on silicones, including sections discussing silicone
fluids,
gums, and resins, as well as the manufacture of silicones, can be found in
Encyclopedia
of Polymer Science and Engineering, Volume 15, Second Edition, pp 204-308,
John
Wiley & Sons, Inc., 1989.
Siliconematerials and silicone resins in particular, can conveniently be
identified
according to a shorthand nomenclature system well known to those skilled in
the art as
the "MDTQ" nomenclature. Under this system, the silicone is described
according to the
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WO 00/71652 PCT/US00/14564
presence of various siloxane monomer units which make up the silicone.
Briefly, the
symbol M denotes the monofunctional unit (CH3)3SiO0.5; D denotes the
difunctional
unit (CH3)2SiO; T denotes the trifunctional unit (CH3)Si01.5; and Q denotes
the
quadri- or tetra-functional unit Si02. Primes of the unit symbols, e.g., M',
D', T', and Q'
denote substituents other than methyl, and must be specifically defined for
each
occurrence. Typical alternate substituents include groups such as vinyl,
phenyl, amino,
hydroxyl, etc. The molar ratios of the various units, either in terms of
subscripts to the
symbols indicating the total number of each type of unit in the silicone, or
an average
thereof, or as specifically indicated ratios in combination with molecular
weight,
complete the description of the silicone material under the MDTQ system.
Higher
relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or or M' in a
silicone resin
is indicative of higher levels of crosslinking. As discussed before, however,
the overall
level of crosslinking can also be indicated by the oxygen to silicon ratio.
The silicone resins for use herein which are preferred are MQ, MT, MTQ, MQ
and MDTQ resins. Thus, the preferred silicone substituent is methyl.
Especially
preferred are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about
1.5:1.0 and
the average molecular weight of the resin is from about 1000 to about 10,000.
2)Nonvolatile Hydrocarbon Conditioning Agents Other suitable hair conditioning
agents
suitable for use in the personal cleansing composition include nonvolatile
organic
conditioning agents. Suitable nonvolatile organic conditioning agents for use
in the
composition are those conditioning agents that are known or otherwise
effective for use
as hair or skin conditioning agent.
The nonvolatile hydrocarbons for use in the personal cleansing composition may
be saturated or unsaturated, and may be straight, cyclic or branched chain. By
nonvolatile is meant that the hydrocarbon conditioning agent exhibits very low
or no
significant vapor pressure at ambient conditions, e.g., 1 atmosphere at 250C.
The
nonvolatile hydrocarbon agent preferably has a boiling point at ambient
pressure of
above about 2500C, preferably above about 2600C, and more preferably of above
about
2750C. The nonvolatile hydrocarbons preferably have from about 12 to about 40
carbon
atoms, more preferably from about 12 to about 30 carbon atoms, and most
preferably
from about 12 to about 22 carbon atoms. Also encompassed herein are polymeric
hydrocarbons of alkenyl monomers, such as polymers of C2-C 12 alkenyl
monomers,
including 1-alkenyl monomers such as polyalphaolefin monomers. These polymers
can
be straight or branched chain polymers. The straight chain polymers will
typically be
relatively short in length, having a total number of carbon atoms as described
above in
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this paragraph. The branched chain polymers can have substantially higher
chain
lengths. Also useful herein are the various grades of mineral oils. Mineral
oils are liquid
mixtures of hydrocarbons that are obtained from petroleum.
Specific examples of suitable nonvolatile hydrocarbons include, but are not
limited to, paraffin oil, mineral oil, dodecane, isododecane, hexadecane,
isohexadecane,
eicosene, isoeicosene, tridecane, triglyceride oils, tetradecane, polyoctene,
polydecene,
polydodecene, products of polymerization of mixtures of C2-12 monomers, for
example
the polymer produced by the polymerization of polyoctene, polydecene and
polydodecene, and mixtures thereof. Tsododecane, isohexadeance, and
isoeicosene are
rM
commercially available as Permethyl 99A, Permethyl IOIA, and Permethyl 1082,
from
Presperse, South Plainfield, NJ. TryA copolymer of isobutene and normal butene
is
commercially available as Indopol H-100 from Amoco Chemicals. Preferred among
these hydrocarbons are mineral oil, isododecane, isohexadecane, polybutene,
polyisobutene, and mixtures thereof.
Oational Suspending Agent The personal cleansing compositions of the present
invention may further comprise a suspending agent at concentrations effective
for
suspending the optional conditioning agent, or other water-insoluble material,
in
dispersed form in the personal cleansing compositions. Such concentrations
range from
about 0.1% to about 10%, preferably from about 0.5% to about 5.0%, by weight
of the
personal cleansing compositions.
Optional suspending agents include crystalline suspending agents that can be
categorized as acyl derivatives, long chain amine oxides, or combinations
thereof,
concentrations of which range from about 0.3% to about 5.0%, preferably from
about
0.5% to about 3.0%, by weight of the personal cleansing compositions. When
used in
the personal cleansing compositions, these suspending agents are present in
crystalline
form. These suspending agents are described in U.S.
Patent 4,741,855. These preferred suspending agents
include ethylene glycol esters of fatty acids preferably having from about 16
to about 22
carbon atoms. More preferred are the ethylene glycol stearates, both mono and
distearate, but particularly the distearate containing less than about 7% of
the mono
stearate. Other suitable suspending agents include alkanol amides of fatty
acids,
preferably having from about 16 to about 22 carbon atoms, more preferably
about 16 to
18 carbon atoms, preferred examples of which include stearic monoethanolamide,
stearic
diethanolaniide, stearic monoisopropanolamide and stearic monoethanolamide
stearate.
Other long chain acyl derivatives include long chain esters of long chain
fatty acids (e.g.,
stearyl stearate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl
distearate) and long
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chain esters of long chain alkanol amides (e.g., stearamide diethanolamide
distearate,
stearamide monoethanolamide stearate). Long chain acyl derivatives, ethylene
glycol
esters of long chain carboxylic acids, long chain amine oxides, and alkanol
amides of
long chain carboxylic acids in addition to the preferred materials listed
above may be
used as suspending agents. For example, it is contemplated that suspending
agents with
long chain hydrocarbyls having C8-C22 chains may be used.
Other long chain acyl derivatives suitable for use as suspending agents
include
N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na, K),
particularly N,N-di(hydrogenated) C16, C18 and tallow amido benzoic acid
species of
this family, which are conunercially available from Stepan Company
(Northfield,
Illinois, USA).
Examples of suitable long chain amine oxides for use as suspending agents
include alkyl (C16-C22) dimethyl amine oxides, e.g., stearyl dimethyl amine
oxide
Other suitable suspending agents include xanthan gum at concentrations ranging
from about 0.3% to about 3%, preferably from about 0.4% to about 1.2%, by
weight of
the personal cleansing compositions. The use of xanthan gum as a suspending
agent in
silicone containing personal cleansing compositions is described, for example,
in U.S.
Patent 4,788,006. Combinations of long chain acyl
derivatives and xanthan gum may also be used as a suspending agent
in the personal cleansing compositions. Such combinations are described in
U.S. Patent
4,704,272.
Other suitable suspending agents include carboxyvinyl polymers. Preferred
among these polymers are the copolymers of acrylic acid crosslinked with
polyallylsucrose as described in U.S. Patent 2,798,053. Examples of these
polymers
include CarbopolTM 934, 940, 941, and 956, available from B.F. Goodrich
Company.
Other suitable suspending agents include primary amines having a fatty alkyl
moiety having at least about 16 carbon atoms, examples of which include
palmitamine or
stearamine, and secondary amines having two fatty alkyl moieties each having
at least
about 12 carbon atoms, examples of which include dipalmitoylamine or
di(hydrogenated
tallow)amine. Still other suitable suspending agents include di(hydrogenated
tallow)phthalic acid amide, and crosslinked maleic anhydride-methyl vinyl
ether
copolymer.
Other suitable suspending agents may be used in the personal cleansing
compositions, including those that can impart a gel-like viscosity to the
composition,
such as water soluble or colloidally water soluble polymers like cellulose
ethers (e.g.,
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methylcellulose, hydroxybutyl methylcellulose, liyroxypropylcellulose,
hydroxypropyl
methylcellulose, hydroxyethyl ethylcellulose and hydorxethylcellulose), guar
gum,
polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and
starch
derivatives, and other thickeners, viscosity modifiers, gelling agents, etc.
Mixtures of
these materials can also be used.
b) Conventional Personal Care Polymer:
The personal cleansing compositions of the present invention comprise from
about 0.01 % to about 20%, preferably from about 0.05% to about 10%, more
preferably
from about 0.1% to about 5%, and even more preferably from about 0.1% to about
3% of
a conventional personal care polymer. Suitable conventional personal care
polymers
include:
i) deposition polymers;
ii) styling polymers and solvent;
iii) dispersed phase polymers; and
iv) mixtures thereof
i) Deposition Polymer
The personal cleansing compositions of the present invention can additionally
comprise an organic deposition polymer as a deposition aid. It can be present
at levels of
from about 0.01 to about 5%, preferably from about 0.05 to about 1%, more
preferably
from about 0.08% to about 0.5% by weight. The polymer may be a homopolymer or
be
formed from two or more types of monomers. The molecular weight of the polymer
will
generally be between about 25,000 and about 10,000,000, preferably between
about
100,000 and about 5,000,000, more preferably in the range between about
300,000 to
about 3,000,000 and most preferably from about 500,000 to about 2,000,000.
Preferably
the deposition polymer is a cationic polymer and preferably will have cationic
nitrogen
containing groups such as quaternary ammonium or protonated amino groups, or a
mixture thereof. It is preferred that when the deposition polymer is present
there is
additionally present in the composition a hair conditioning agent,
antidandruff agent,
styling polymer or mixtures thereof, all of which are defined hereafter.
Alternatively the
deposition polymer can be used independantly, that is on its own, in the
personal
cleansing composition.
See WO 99/05243 for exemplification of deposition polymers.
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The cationic charge density has been found to need to be at least 0.1 meq/g,
preferably above 0.5 and most preferably above 0.8 or higher. The cationic
charge
density should not exceed 5 meq/g, it is preferably less than 3 and more
preferably less
than 2 meq/g. The charge density can be measured using the Kjeldahl method and
should be within the above limits at the desired pH of use, which will in
general be from
about 3 to 9 and preferably between 4 and 8.
The concentration of the deposition polymer in the personal cleansing when it
is a
cationic polymer is preferably from about 0.025% to about 3%, more preferably
from
about 0.05% to about 2%, even more preferably from about 0.1 % to about 1%, by
weight
of the personal cleansing composition.
Any anionic counterions can be use in association with the cationic polymers
so
long as the polymers remain soluble in water, in the personal cleansing
composition, or
in a coacervate phase of the personal cleansing composition, and so long as
the
counterions are physically and chemically compatible with the essential
components of
the personal cleansing composition or do not otherwise unduly impair product
perfomlance, stability or aesthetics. Non limiting examples of such
counterions include
halides (e.g., chlorine, fluorine, bromine, iodine), sulfate and
methylsulfate.
The cationic nitrogen-containing moiety of the cationic polymer is generally
present as a substituent on all, or more typically on some, of the monomer
units thereof.
Thus, the cationic polymer for use in the personal cleansing composition
includes
homopolymers, copolymers, terpolymers, and so forth, of quaternary ammonium or
cationic amine-substituted monomer units, optionally in combination with non-
cationic
monomers referred to herein as spacer monomers. Non limiting examples of such
polymers are described in the CTFA Cosmetic Ingredient Dictionary, 3rd
edition, edited
by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance
Association, Inc.,
Washington, D.C. (1982)).
Suitable cationic polymers include, for example, copolymers of vinyl monomers
having cationic amine or quaternary ammonium functionalities with water
soluble spacer
monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl
(meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and
dialkyl
substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-C3
alkyl
groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic
anhydride,
propylene glycol and ethylene glycol.
The cationic amines can be primary, secondary or tertiary amines, depending
upon the particular species and the pH of the personal cleansing. In general
secondary
and tertiary amines, especially tertiary, are preferred.
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Anlines substituted vinyl monomers and amines can be polymerized in the amine
form and then converted to ammonium by quaternization.
Suitable cationic amino and quatemary arnmonium monomers include, for
example, vinyl compounds substituted with dialkyl aminoalkyl acrylate,
dialkylamino
alkylmethacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl
methacrylate,
trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium
sale, diallyl
quaternary ammonium salts, and vinyl quaternary ammonium monomers having
cyclic
cationic nitrogen-containing rings such as pyridinium, imidazolium, and
quatemized
pyrrolidine, e.g., alkyl vinyl imidazolium, and quaternized pyrrolidine, e.g.,
alkyl vinyl
imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidine salts. The alkyl
portions of
these monomers are preferably lower alkyls such as the Cl-C3 alkyls, more
preferably
C1 and C2 alkyls.
Suitable amine-substituted vinyl monomers for use herein include
dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl
acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are
preferably C1-C7 hydrocarbyls, more preferably C1-C3 alkyls.
The cationic polymers hereof can comprise mixtures of monomer units derived
from amine-and/or quaternary ammonium-substituted monomer and/or compatible
spacer monomers.
Suitable cationic deposition polymers include, for example: copolymers of 1-
vinyl-2-pyrrolidine and 1-vinyI-3-methyl-imidazolium salt (e.g., Chloride
salt) (referred
to in the industry by the Cosmetic, Toiletry, and Fragrance Association,
"CTFA" as
Polyquaternium-16) such as those commercially available from BASF Wyandotte
Corp.
(Parsippany, NJ, USA) under the LUVIQUAT trademark (e.g., LUVIQUAT FC 370);
copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate
(referred to in
the industry by CTFA and Polyquatemium- 11) such as those commercially from
ISP
Corporation (Wayne, NJ, USA) under the GAFQUAT trademark (e.g., GAFQUAT 755N);
cationic diallyl quatemary ammonium-containing polymers including, for
example,
dimethyldiallyammonium chloride homopolymer and copolymers of acrylamide and
dimethyldiallyammonium chloride, referred to in the industry (CTFA) as
Polyquaternium
6 and Polyquaternium 7, respectively; and mineral acid salts of amino-alkyl
esters of
homo-and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon
atoms,
as described in U.S. Patent 4,009,256.
Other cationic polymers that can be used include polysaccharide polymers, such
as cationic cellulose derivatives and cationic starch derivatives. Cationic
polysaccharide
polymer materials suitable for use herein include those of the fornlula:
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Ri
A---O--(R-i+-R3X)
R
wherein: A is an anhydroglucose residual group, such as starch or cellulose
anhydroglucose residual, R is an alkylene oxyalklene, polyoxyalkylene, or
hydroxyalkylene group, or combination thereof, R1, R2 and R3 independently are
alkyl,
aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group
containing up to
about 18 carbon atoms, and the total number of carbon atoms for each cationic
moiety
(i.e., the sum of carbon atoms in Rl, R2 and R3) preferably being about 20 or
less, and X
is an anionic counterion, as previously described.
Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in their
Polymer JR (trademark) and LR (trade mark) series of polymers, as salts of
hydroxyethyl
cellulose reacted with trimethyl ammonium substituted epoxide, referred to in
the
industry (CTFA) as Polyquatemium 10. Another type of cationic cellulose
includes the
polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with
lauryl
dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as
Polyquaternium 24. These materials are available from Amerchol Corp. (Edison,
NJ,
USA) under the -trademark Polymer LM-200.
Other cationic polymers that can be used include cationic guar gum
derivatives,
such as guar hydroxypropyltrimonium chloride (commercially available from
Celanese
Corp. in their Jaguar trade mark series). Other materials include quatemary
nitrogen-
containing cellulose ethers (e.g., as described in U.S. Patent 3,962,418), and
copolymers of
etherified cellulose and starch (e.g., as described in U.S. Patent 3,958,581).
The deposition polymer does not have to be soluble in the personal cleansing
composition. Preferably, however, the cationic polymer is either soluble in
the personal
cleansing composition, or in a complex coacervate phase in the personal
cleansing
composition formed by the cationic polymer and anionic material. Complex
coacervates
of the cationic polymer can be formed with anionic surfactants or with anionic
polymers
that can optionally be added to the composition hereof (e.g., sodium
polystyrene
sulfonate).
Coacervate formation is dependent upon a variety of criteria such as molecular
weight, concentration, and ratio of interacting ionic materials, ionic
strength (including
modification of ionic strength, for example, by addition of salts), charge
density of the
cationic and anionic species, pH, and temperature. Coacervate systems and the
effect of
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CA 02372892 2004-07-20
these parameters have been described, for example, by J. Caelles, et al.,
"Anionic and
Cationic Compounds in Mixed Systems", Cosmetics & Toiletries, Vol. 106, April
1991,
pp 49-54, C. J. van Oss, "Coacervation, Complex-Coacervation and
Flocculation", J.
Dispersion Science and Technology, Vol. 9 (5,6), 1988-89, pp 561-573, and D.
J.
Burgess, "Practical Analysis of Complex Coacervate Systems", J of Colloid and
Interface Science, Vol. 140, No. 1, November 1990, pp 227-238.
It is believe to be particularly advantageous for the cationic polymer to be
present
in the personal cleansing in a coacervate phase, or to form a coacervate phase
upon
application or rinsing of the personal cleansing to or from the hair. Complex
coacervates
are believed to more readily deposit on the hair. Thus, in general, it is
preferred that the
cationic polymer exist in the personal cleansing as a coacervate phase or form
a
coacervate phase upon dilution. If not already a coacervate in the personal
cleansing, the
cationic polymer will preferably exist in a complex coacervate form in the
personal
cleansing upon dilution with water to a water:personal cleansing composition
rate ratio of
about 20:1, more preferably at about 10:1, even more preferably at about 8:1.
Techniques for analysis of formation of complex coacervates are known in the
art. For example, microscopic analyses of the personal cleansing compositions,
at any
chosen stage of dilution, can be utilized to identify whether a coacervate
phase has
formed. Such coacervate phase will be identifiable as an additional emulsified
phase in
the composition. The use of dyes can aid in distinguishing the coacervate
phase from
other insoluble phase dispersed in the composition.
Preferably the deposition polymer is selected from the group comprising
cationic
hydroxyalkyl cellulose ethers and cationic guar derivatives. Particularly
preferred
rM
deposition polymers are Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar C16 and
Jaguar C162. Other preferred cationic cellulose ethers include Polymer JR400,
JR30M
and JR125.
Surfactant soluble Conditioning Oil The shampoo compositions of the present
invention
may additionally comprise a low viscosity, surfactant soluble conditioning oil
which is
solubilized in the surfactant component as an additional hair conditioning
agent for use in
combination with the cationic hair conditioning polymer described
hereinbefore. The
concentration of the low viscosity, surfactant soluble oil ranges from about
0.05% to
about 3%, preferably from about 0.08% to about 1.5%, more preferably from
about 0.1%
to about I%, by weight of the shampoo composition.
The low viscosity, surfactant soluble, conditioning oils are water insoluble,
water
dispersible, liquids selected from the group consisting of hydrocarbon oils
and fatty
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esters, or combinations thereof , wherein the surfactant soluble conditioning
oil has a
viscosity of from about 1 to about 300 centipoise, preferably from about 1 Sto
about 150
centipoise, more preferably from about 2 to about 50 centipoise, as measured
at 40 C
according to ASTM D-445.
It has been found that these low viscosity surfactant soluble conditioning
oils
provide the shampoo composition with improved conditioning performance when
used in
combination with the deposition polymers described herein. These surfactant
soluble
conditioning oils are believed to be solubilized in the surfactant micelles of
the shampoo
composition. It is also believed that this solubilization into the surfactant
micelles
contributes to the improved hair conditioning performance of the shampoo
compositions
herein.
Suitable surfactant soluble conditioning oils for use in the shampoo
composition
include hydrocarbon oils having at least about 10 carbon atoms, such as cyclic
hydrocarbons, straight chain aliphatic hydrocarbons (saturated or
unsaturated), and
branched chain aliphatic hydrocarbons (saturated or unsaturated), including
polymers
thereof. Straight chain hydrocarbon oils preferably contain from about 12 to
about 19
carbon atoms. Branched chain hydrocarbon oils, including hydrocarbon polymers,
can
and typically will contain more than 19 carbon atoms. Specific non limiting
examples of
these hydrocarbon oils include paraffin oil, mineral oil, saturated and
unsaturated
dodecane, saturated and unsaturated tridecane, saturated and unsaturated
tetradecane,
saturated and unsaturated pentadecane, saturated and unsaturated hexadecane,
polybutene, polydecene, and combinations thereof. Branched-chain isomers of
these
compounds, as well as of higher chain length hydrocarbons, can also be used,
examples
of which include highly branched, saturated or unsaturated, alkanes such as
the
permethyl-substituted isomers, e.g., the permethyl-substituted isomers of
hexadecane and
eicosane, such as 2, 2, 4, 4, 6, 6, 8, 8-dimethyl-l0-methylundecane and 2, 2,
4, 4, 6, 6-
dimethyl-8-methylnonane, sold by Permethyl Corporation. Hydrocarbon polymers
such
as polybutene and polydecene, especially polybutene, can also be used.
Other surfactant soluble conditioning oils for use in the shampoo composition
include a liquid polyolefin such as a liquid polyalphaolefin or a hydrogenated
liquid
polyalphaolefin. Polyolefins suitable for use in the shampoo composition
herein are
prepared by polymerization of olefenic monomers containing from about 4 to
about 14
carbon atoms, preferably from about 6 to about 12 carbon atoms.
Polyalphaolefins are
preferred, and are prepared by polymerization of 1-alkene monomers having from
about
4 to about 14 carbon atoms, preferably from about 6 to about 12 carbon atoms.
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Non limiting examples of olefenic monomers for use in preparing the polyolefin
liquids herein include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-
octene, 1-
decene, 1-dodecene, 1-tetradecene, branched chain isomers such as 4-methyl-i-
pentene,
and combinations thereof. Also suitable for preparing the polyolefin liquids
are olefin-
containing refinery feedstocks or effluents. Preferred, however, are the
hydrogenated
alpha-olefin monomers having from about 4 to about 14 carbon atoms, or
combinations
thereof, examples of which include 1-hexene to 1-hexadecenes and combinations
thereof, and preferably are 1-octene to 1-tetradecene or combinations thereof.
(ii) Styling polymer
The personal cleansing compositions of the present invention may additionally
contain a water-insoluble hair styling polymer, concentrations of which range
from about
0.1 % to about 10%, preferably from about 0.3% to about 7%, more preferably
from about
0.5% to about 5%, by weight of the composition. These styling polymers provide
the
personal cleansing composition of the present invention with hair styling
performance by
providing a thin polymeric film on the hair after application from a personal
cleansing
composition. The polymeric film deposited on the hair has adhesive and
cohesive
strength, as is understood by those skilled in the art. It is essential that
when a styling
polymer is present in the personal cleansing compositions of the invention
that a solvent,
defined hereafter, is also present in the It is preferred that when a styling
polymer is
present a deposition polymer be also present. This combination improves
deposition and
retention of the styling polymer. Furthermore, it is preferd that when the
personal
cleansing composition contains a styling polymer it is preferred that a
cationic spreading
agent be present.
Many such polymers are known in the art, including water-insoluble organic
polymers and water-insoluble silicone-grafted polymers, all of which are
suitable for use
in the personal cleansing composition herein provided that they also have the
requisite
features or characteristics described hereinafter. Such polymers can be made
by
conventional or otherwise known polymerization techniques well known in the
art, an
example of which includes free radical polymerization.
See WO 98/18434 and WO 99/05243.
Examples of suitable organic and silicone grafted polymers for use in the
personal
cleansing composition of the present invention are described in greater detail
hereinafter.
Or anQ ic styling polymer The styling polymers suitable for use in the
personal cleansing
composition of the present invention include organic styling polymers well
known in the
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art. The organic styling polymers may be homopolymers, copolymers, terpolymers
or
other higher polymers, but must comprise one or more polymerizable hydrophobic
monomers to thus render the resulting styling polymer hydrophobic and water-
insoluble
as defined herein. The styling polymers may therefore further comprise other
water
soluble, hydrophilic monomers provided that the resulting styling polymers
have the
requisite hydrophobicity and water insolubility.
As used herein, the term "hydrophobic monomer" refers to polymerizable organic
monomers that can form with like monomers a water-insoluble homopolymer, and
the
term "hydrophilic monomer" refers to polymerizable organic monomers that can
form
with like monomers a water-soluble homopolymer.
The organic styling polymers preferably have a weight average molecular weight
of at least about 20,000, preferably greater than about 25,000, more
preferably greater
than about 30,000, most preferably greater than about 35,000. There is no
upper limit for
molecular weight except that which limits applicability of the invention for
practical
reasons, such as processing, aesthetic characteristics, formulateability, etc.
In general,
the weight average molecular weight will be less than about 10,000,000, more
generally
less than about 5,000,000, and typically less than about 2,000,000.
Preferably, the weight
average molecular weight will be between about 20,000 and about 2,000,000,
more
preferably between about 30,000 and about 1,000,000, and most preferably
between
about 40,000 and about 500,000.
The organic styling polymers also preferably have a glass transition
temperature
(Tg) or crystalline melting point (Tm) of at least about -20 C, preferably
from about 20
C to about 80 C, more preferably from about 20 C to about 60 C. Styling
polymers
having these Tg or Tm values form styling films on hair that are not unduly
sticky or
tacky to the touch. As used herein, the abbreviation "Tg" refers to the glass
transition
temperature of the backbone of the polymer, and the abbreviation "Tm" refers
to the
crystalline melting point of the backbone, if such a transition exists for a
given polymer.
Preferably, both the Tg and the Tm, if any, are within the ranges recited
hereinabove.
The organic styling polymers are carbon chains derived from polymerization of
hydrophobic monomers such as ethylenically unsaturated monomers, cellulosic
chains or
other carbohydrate-derived polymeric chains. The backbone may comprise ether
groups,
ester groups, amide groups, urethanes, combinations thereof, and the like.
The organic styling polymers may further comprise one or more hydrophilic
monomers in combination with the hydrophobic monomers described herein,
provided
that the resulting styling polymer has the requisite hydrophobic character and
water-
insolubility. Suitable hydrophilic monomers include, but are not limited to,
acrylic acid,
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methacrylic acid, N,N-dimethylacrylamide, dimethyl aminoethyl methacrylate,
quaternized dimethylaminoethyl methacrylate, methacrylamide, N-t-butyl
acrylamide,
maleic acid, maleic anhydride and its half esters, crotonic acid, itaconic
acid, acrylamide,
acrylate alcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium
chloride, vinyl
pyrrolidone, vinyl ethers (such as methyl vinyl ether), maleimides, vinyl
pyridine, vinyl
imidazole, other polar vinyl heterocyclics, styrene sulfonate, allyl alcohol,
vinyl alcohol
(such as that produced by the hydrolysis of vinyl acetate after
polymerization), salts of
any acids and amines listed above, and mixtures thereof. Preferred hydrophilic
monomers include acrylic acid, N,N-dimethyl acrylamide, dimethylaminoethyl
methacrylate, quaternized dimethyl aminoethyl methacrylate, vinyl pyrrolidone,
salts of
acids and amines listed above, and combinations thereof
Suitable hydrophobic monomers for use in the organic styling polymer include,
but are not limited to, acrylic or methacrylic acid esters of C 1-C 18
alcohols, such as
methanol, ethanol, methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-
methyl-l-
propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-l-butanol, 1-methyl-l-
butanol, 3-
methyl-l-butanol, 1-methyl-l-pentanol, 2-methyl-l-pentanol, 3-methyl-l-
pentanol, t-
butanol(2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethyl-l-butanol, 3-
heptanol,
benzyl alcohol, 2-octanol, 6-methyl-l-heptanol, 2-ethyl-l-hexanol, 3,5-
dimethyl-l-
hexanol, 3,5,5-tri methyl-l-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-
octa
decanol, and the like, the alcohols having from about 1 to about 18 carbon
atoms,
preferably from about 1 to about 12 carbon atoms; styrene; polystyrene
macromer; vinyl
acetate; vinyl chloride; vinylidene chloride; vinyl propionate; alpha-
methylstyrene; t-
butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene;
and
mixtures thereof. Preferred hydrophobic monomers include n-butyl methacrylate,
isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl
methacrylate,
methyl methacrylate, vinyl acetate, and mixtures thereof, more preferably t-
butyl acrylate,
t-butyl methacrylate, or combinations thereof.
The styling polymers for use in the personal cleansing composition preferably
comprise from about 20% to 100%, more preferably from about 50% to about 100%,
even more preferably from about 60% to about 100%, by weight of the
hydrophobic
monomers, and may further comprise from zero to about 80% by weight of
hydrophilic
monomers. The particular selection and combination of monomers for
incorporation into
the styling polymer will help determine its formulational properties. By
appropriate
selection and combination of, for example, hydrophilic and hydrophobic
monomers, the
styling polymer can be optimized for physical and chemical compatibility with
the
selected styling polymer solvent described hereinafter and other components of
the
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personal cleansing composition. The selected monomer composition of the
organic
styling polymer must, however, render the styling polymer water-insoluble but
may be
soluble in the selected solvent described hereinafter. In this context, the
organic styling
polymer is soluble in the solvent if the organic polymer is solubilized in the
solvent at 25
C at the polymer and solvent concentrations of the personal cleansing
formulation
selected. However, a solution of the organic styling polymer and solvent may
be heated
to speed up solubility of the styling polymer in the solvent. Such styling
polymer and
solvent formulation, including the selection of monomers for use in the
styling polymer,
to achieve the desired solubility is well within the skill of one in the art.
Examples of preferred organic styling polymers include t-butyl acrylate/2-
ethylhexyl acrylate copolymers having a weight/weight ratio of monomers of
about 95/5,
about 90/10, about 80/20, about 70/30, about 60/40, and about 50/50; t-butyl
acrylate/2-
ethylhexyl methacrylate copolymers having a weight/weight ratio of monomers of
about
95/5, about 90/10, about 80/20, about 70/30, about 60/40, and about 50/50; t-
butyl
methacrylate/2-ethvlhexyl acrylate copolymers having a weight/weight ratio of
monomers of about 95/5, about 90/10, about 80/20, about 70/30, about 60/40,
and about
50/50; t-butyl methacrylate/2-ethylhexyl methacrylate copolymers having a
weight/weight ratio of monomers of about 95/5, about 90/10, about 80/20, about
70/30,
about 60/40, and about 50/50; t-butyl ethacrylate/2-ethylhexyl methacrylate
copolymers
having a weight/weight ratio of monomers of about 95/5, about 90/10, about
80/20, about
70/30, about 60/40, and about 50/50; vinyl pyrrolidone/vinyl acetate
copolymers having a
weight/weight ratio of monomers of about 10/90, and about 5/95; and mixtures
thereof.
Especially preferred polymers are t-butyl acrylate/2-ethylhexyl methacrylate
copolymers having a weight/weight ratio of monomers of about 95/5, about
90/10, about
80/20, about 70/30, about 60/40, and about 50/50; t-butyl methacrylate/2-
ethylhexyl
methacrylate copolymers having a weight/weight ratio of monomers of about
95/5, about
90/10, about 80/20, about 70/30, about 60/40, and about 50/50; and mixtures
thereof.
Examples of other suitable styling polymers are described in U.S. Patent
5,120,531, to Wells et al., issued June 9, 1992; U.S. Patent 5,120,532, to
Wells et al.,
issued June 9, 1992; U.S. Patent 5,104,642, to Wells et al., issued April 14,
1992; U.S.
Patent 4,272,511, to Papantoniou et al., issued June 9, 1981; U.S. Patent
4,963,348, to
Bolich et al., issued October 16, 1990 and U.S. Patent 4,196,190, to Gehman et
al.,
issued April 1, 1980.
Silicone-grafted styling polymer Other suitable styling polymers for use in
the personal
cleansing composition of the present invention are silicone-grafted hair
styling resins.
These polymers may be used alone or in combination with the organic styling
polymers
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described hereinbefore. Many such polymers suitable for use in the personal
cleansing
composition herein are known in the art. These polymers are characterized by
polysiloxane moieties covalently bonded to and pendant from a polymeric carbon-
based
backbone.
The backbone of the silicone-grafted polymer is preferably a carbon chain
derived
from polymerization of ethylenically unsaturated monomers, but can also be
cellulosic
chains or other carbohydrate-derived polymeric chains to which polysiloxane
moieties
are pendant. The backbone can also include ether groups, ester groups, amide
groups,
urethane groups and the like. The polysiloxane moieties can be substituted on
the
polymer or can be made by co-polymerization of polysiloxane-containing
polymerizable
monomers (e.g. ethylenically unsaturated monomers, ethers, and/or epoxides)
with non-
polysiloxane-containing polymerizable monomers.
The silicone-grafted styling polymers for use in the personal cleansing
composition comprise "silicone-containing" (or "polysiloxane-containing")
monomers,
which form the silicone macromer pendant from the backbone, and non-silicone-
containing monomers, which form the organic backbone of the polymer. That is a
siloxane monomer grafted to the hair styling polymer.
Preferred silicone-grafted polymers comprise an organic backbone, preferably a
carbon backbone derived from ethylenically unsaturated monomers, such as a
vinyl
polymeric backbone, and a polysiloxane macromer (especially preferred are
polydialkylsiloxane, most preferably polydimethylsiloxane) grafted to the
backbone. The
polysiloxane macromer should have a weight average molecular weight of at
least about
500, preferably from about 1,000 to about 100,000, more preferably from about
2,000 to
about 50,000, most preferably about 5,000 to about 20,000. Organic backbones
contemplated include those that are derived from polymerizable, ethylenically
unsaturated monomers, including vinyl monomers, and other condensation
monomers
(e.g., those that polymerize to form polyamides and polyesters), ring-opening
monomers
(e.g., ethyl oxazoline and caprolactone), etc. Also contemplated are backbones
based on
cellulosic chains, ether-containing backbones, etc.
Preferred silicone grafted polymers for use in the personal cleansing
composition
comprise monomer units derived from: at least one free radically polymerizable
ethylenically unsaturated monomer or monomers and at least one free radically
polymerizable polysiloxane-containing ethylenically unsaturated monomer or
monomers.
The silicone grafted polymers suitable for use in the personal cleansing
composition generally comprise from about 1% to about 50%, by weight, of
polysiloxane-containing monomer units and from about 50% to about 99% by
weight, of
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non-polysiloxane-containing monomers. The non-polysiloxane-containing monomer
units can be derived from the hydrophilic and/or hydrophobic monomer units
described
hereinbefore.
The styling polymer for use in the personal cleansing composition can
therefore
comprise combinations of the hydrophobic and/or polysiloxane-containing
monomer
units described herein, with or without hydrophilic comonomers as described
herein,
provided that the resulting styling polymer has the requisite characteristics
as described
herein.
Suitable polymerizable polysiloxane-containing monomers include, but are not
limited to, those monomers that conform to the formula:
X(Y)nSl(R)3-mZm
wherein X is an ethylenically unsaturated group copolymerizable with the
hydrophobic
monomers described herein, such as a vinyl group; Y is a divalent linking
group; R is a
hydrogen, hydroxyl, lower alkyl (e.g. C 1-C4), aryl, alkaryl, alkoxy, or
alkylamino; Z is a
monovalent siloxane polymeric moiety having a number average molecular weight
of at
least about 500, which is essentially unreactive under copolymerization
conditions, and is
pendant from the vinyl polymeric backbone described above; n is 0 or 1; and m
is an
integer from 1 to 3. These polymerizable polysiloxane-containing monomers have
a
weight average molecular weight as described above.
A preferred polysiloxane-containing monomer conforms to the formula:
0
X-C-0-(CH2)q (O)p Si(R')3-mZm
wherein m is 1, 2 or 3 (preferably m = 1); p is 0 or 1; q is an integer from 2
to 6; R1 is
hydrogen, hydroxyl, lower alkyl, alkoxy, alkylamino, aryl, or alkaryl
(preferably R1 is
alkyl); X conforms to the formula
C H=C-
I I
R2 R3
wherein R2 is hydrogen or -COOH (preferably R2 is hydrogen); R3 is hydrogen,
methyl
or -CH2COOH (preferably R3 is methyl); Z conforms to the formula:
R5
R4 SiO
R6
r
wherein R4, R5, and R6 independently are lower alkyl, alkoxy, alkylamino,
aryl,
arylalkyl, hydrogen or hydroxyl (preferably R4, R5, and R6 are alkyls); and r
is an integer
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of about 5 or higher, preferably about 10 to about 1500 (most preferably r is
from about
100 to about 250). Most preferably, R4, R5, and R6 are methyl, p=O, and q=3.
Another preferred polysiloxane monomer conforms to either of the following
formulas
X (CH2)s-S'(Rl)3-m-Zm
(R2)n
or
X-C H2-(C H2 )S-S i (Rl)3-m-Zm
wherein: s is an integer from 0 to about 6, preferably 0, 1, or 2, more
preferably 0 or 1; m
is an integer from 1 to 3, preferably 1; R2 is Cl-C10 alkyl or C7-C10
alkylaryl,
preferably C 1-C6 alkyl or C7-C 10 alkylaryl, more preferably C 1-C2 alkyl; n
is an integer
from 0 to 4, preferably 0 or 1, more preferably 0.
The silicone grafted styling polymers suitable for use in the personal
cleansing
composition preferably comprise from about 50% to about 99%, more preferably
from
about 60% to about 98%, most preferably from about 75% to about 95%, by weight
of
the polymer, of non-silicone macromer-containing monomer units, e.g. the total
hydrophobic and hydrophilic monomer units described herein, and from about 1%
to
about 50%, preferably from about 2% to about 40%, more preferably from about
5% to
about 25%, of silicone macromer-containing monomer units, e.g. the
polysiloxane-
containing monomer units described herein. The level of hydrophilic monomer
units can
be from about 0% to about 70%, preferably from about 0% to about 50%, more
preferably from about 0% to about 30%, most preferably from about 0% to about
15%;
the level of hydrophobic monomer units, can be from 30% to about 99%,
preferably
from about 50% to about 98%, more preferably from about 70% to about 95%, most
preferably from about 85% to about 95%.
Examples of some suitable silicone grafted polymers for use in the personal
cleansing composition herein are listed below. Each listed polymer is followed
by its
monomer composition as weight part of monomer used in the synthesis:
(i) t-butylacrylatye/t-butyl-methacrylate/2-ethylhexyl-methacrylate/PDMS
macromer-20,000 molecular weight macromer 31/27/32/10
(ii) t-butylmethacrylate/2-ethylhexyl-methacrylate/PDMS macromer-15,000
molecular weight macromer 75/10/15
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(iii) t-butylmethacrylate/2-ethylhexyl-acrylate/PDMS macromer-10,000
molecular weight macromer 65/15/20
(iv) t-butylacrylate/2-ethylhexyl-acrylate/PDMS macromer-14,000 molecular
weight macromer 77/11/12
(v) t-butylacrylate/2-ethylhexyl-methacrylate/PDMS macromer-13,000
molecular weight macromer 81/9/10
Examples of other suitable silicone grafted polymers for use in the personal
cleansing composition of the present invention are described
in EPO Application 0 408 311 A2 on January 11, 1991, Hayama,
et al.; U.S. Patent 5,061,481, issued October 29, 1991, Suzuki et al.; U.S.
Patent
5,106,609, Bolich et al., issued April 21, 1992; U.S. Patent 5,100,658, Bolich
et al.,
issued March 31, 1992; U.S. Patent 5,100,657, Ansher-Jackson, et al., issued
March 31,
1992; U.S. Patent 5,104,646, Bolich et al., issued April 14, 1992; U.S. Patent
No. 5,658,557.
Solvent - The personal cleansing composition of the present invention must
additionally
comprise a volatile solvent for solubilizing the styling polymers, described
hereinbefore,
when such a styling polymer is present. The solvent helps disperse the styling
polymer
as water-insoluble fluid particles throughout the personal cleansing
composition, wherein
the dispersed particles comprise the styling polymer and the volatile solvent.
Solvents
suitable for this purpose include hydrocarbons, ethers, esters, amines, alkyl
alcohols,
volatile silicone derivatives and combinations thereof, many examples of which
are well
known in the art.
The volatile solvent must be water-insoluble or have a low water solubility.
The
selected styling polymer, however, must also be sufficiently soluble in the
selected
solvent to allow dispersion of the hair styling polymer and solvent
combination as a
separate, dispersed fluid phase in the personal cleansing composition.
The solvent suitable for use in the personal cleansing composition must also
be a
volatile material. In this context, the term volatile means that the solvent
has a boiling
point of less than about 300 C, preferably from about 90 C to about 260 C,
more
preferably from about 100 C to about 200 C (at about one atmosphere of
pressure).
The concentration of the volatile solvent in the personal cleansing
composition
must be sufficient to solubilize the hair styling polymer and disperse it as a
separate fluid
phase in the personal cleansing composition. Such concentrations generally
range from
about 0.10% to about 10%, preferably from about 0.5% to about 8%, most
preferably
from about 1% to about 6%, by weight of the personal cleansing composition,
wherein
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the weight ratio of styling polymer to solvent is preferably from about 10:90
to about
70:30, more preferably from about 20:80 to about 65:35, even more preferably
from
about 30:70 to about 60:40. If the weight ratio of styling polymer to solvent
is too low,
the lathering performance of the personal cleansing composition is negatively
affected. If
the ratio of polymer to solvent is too high, the composition becomes too
viscous and
causes difficulty in the dispersion of the styling polymer. The hair styling
agents should
have an average particle diameter in the final personal cleansing product of
from about
0.05 to about 100 microns, preferably from about 0.2 micron to about 25
microns.
Particle size can be measured according to methods known in the art,
including, for
example optical microscopy.
Preferred volatile solvents for use in the personal cleansing composition are
the
hydrocarbon solvents, especially branched chain hydrocarbon solvents. The
hydrocarbon
solvents may be linear or branched, saturated or unsaturated, hydrocarbons
having from
about 8 to about 18 carbon atoms, preferably from about 10 to about 16 carbon
atoms.
Saturated hydrocarbons are preferred, as are branched hydrocarbons.
Nonlimiting
examples of some suitable linear hydrocarbons include decane, dodecane,
decene,
tridecene, and combinations thereof. Suitable branched hydrocarbons include
isoparaffins, examples of which inMlude commercially available isoparaffins
from Exxon
Chemical Company such as Isopar I I and K (C 11-C 12 isoparaffins), and Isopar
L(C11-
C 13 isoparaffins). Preferred branched hydrocarbons are isohexadecane,
isododecane,
2,5-dimethyl decane, isotetradecane, and combinations thereof. Commercially
available
branched hydrocarbons include Perrnethyl 99A and IOlA (available from
Preperse, Inc.,
South Plainfield, NJ, USA).
Other suitable solvents include isopropanol, butyl alcohol, amyl alcohol,
phenyl
ethanol, benzyl alcohol, phenyl propanol, ethyl butyrate, isopropyl butyrate,
diethyl
phthalate, diethyl malonate, diethyl succinate, dimethyl malonate, dimethyl
succinate,
phenyl ethyl dimethyl carbinol, ethyl-6-acetoxyhexanoate, and methyl (2-
pentanyl-3-
oxy)cyclopentylacetate, and mixtures thereof. Preferred among such other
suitable
solvents are diethyl phthalate, diethyl malonate, diethyl succinate, dimethyl
malonate,
dimethyl succinate, phenylethyl dimethyl carbinol, ethyl-6-acetoxyhexanoate,
and
mixtures thereof.
Suitable ether solvents are the di(C5-C7) alkyl ethers and diethers,
especially the
di(C5-C6) alkyl ethers such as isoamyl ether, dipentyl ether and dihexyl
ether.
Other suitable solvents for use in the personal cleansing composition the
volatile
silicon derivatives such as cyclic or linear polydialkylsiloxane, linear
siloxy compounds
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or silane. The number of silicon atoms in the cyclic silicones is preferably
from about 3
to about 7, more preferably about 3 to about 5.
The general formula for such silicones is:
R2
I
Si O
R2
wherein R1 and R2 are independently selected from Cl to C8 alkyl, aryl or
alkylaryl and
wherein n=3-7. The linear polyorgano siloxanes have from about 2 to 7 silicon
atoms
and have the general formula:
RI R6
R2-Si-O Si-O Si-R7
R3 R5 jRs
n
wherein R1, R2, R3, R4, R5, R6, R7 and R8 can independently be saturated or
unsaturated C1 - C8 alkyl, aryl, alkylaryl, hydroxyalkyl, amino alkyl or alkyl
siloxy.
Linear siloxy compounds have the general formula:
Rz Rq
Rj-Si-O-R7-O-Si-R6
R3 R5
wherein R1, R2, R3, R4, R5, and R6 are independently selected from saturated
or
unsaturated Cl to C7 alkyl, aryl and alkyl aryl and R7 is Cl to C4 alkylene.
Silane compounds have the general formula:
RI
Ra-Si-R2
R3
wherein Rl, R2, R3, and R4 can independently be selected from Cl - C8 alkyl,
aryl,
alkylaryl, hydroxyalkyl and alkylsiloxy.
Silicones of the above type, both cyclic and linear, are offered by Dow Coming
TM
Corporation, Dow Corning 344, 345 and 200 fluids, Union Carbide, Silicone 7202
and
Silicone 7158, and Stauffer Chemical, SWS-03314.
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The linear volatile silicones generally have viscosities of less than about 5
centistokes at 25 C while the cyclic materials have viscosities less than
about 10
centistokes. Examples of volatile silicones are described in Todd and Byers,
"Volatile
Silicone Fluids for Cosmetics", Cosmetics and Toiletries, Vol. 91, January,
1976, pp. 27-
32, and also in Silicon Compounds, pages 253-295, distributed by Petrarch
Chemicals.
Cationic Spreading Agent The personal cleansing compositions of the present
invention
may additionally comprise select cationic materials which act for use as
spreading agents.
The spreading agents for use in the composition are select quaternary ammonium
or
protonated amino compounds defined in greater detail hereinafter. These select
spreading agents are useful to improve spreadability of the water=insoluble
styling
polymer on the body, for example on the hair. The concentration of the select
spreading
agents in the composition range from about 0.05% to about 5%, preferably from
about
0.1% to about 2%, more preferably from about 0.2% to about 1%, by weight of
the
personal cleansing composition.
It has been found that the select spreading agents will improve spreadability
of a
water-insoluble styling polymer when used in the personal cleansing
composition of the
present invention. ln particular, the improved insoluble solvent, water-
insoluble styling
polymer, and cationic deposition polymer, are especially effective at
improving styling
performance of the composition. The improved styling performance results from
the
improved spreading efficiency of water-insoluble styling polymer attributed to
the use of
the select spreading agent in the composition. onto hair. This improved
spreading results
in improved styling performance, or allows for formulation of the personal
cleansing
composition using reduced amounts of styling polymer or cationic deposition
polymer.
The select spreading agents are quatemary ammonium or amino compounds
having 2, 3 or 4 N-radicals which are substituted or unsubstituted hydrocarbon
chains
having from about 12 to about 30 carbon atoms, wherein the substituents
includes
nonionic hydrophilic moieties selected from alkoxy, polyoxalkylene,
alkylamido,
hydroxyalkyl, alkylester moieties, and mixtures thereof. Suitable hydrophile-
containing
radicals include, for example, compounds having nonionic hydrophile moieties
selected
from the group consisting of ethoxy, propoxy, polyoxyethylene,
polyoxypropylene,
ethylamido, propylamido, hydroxymethyl, hydroxyethyl, hydroxypropyl,
methylester,
ethylester, propylester, or mixtures thereof. The select spreading agents are
cationic and
must be positively charged at the pH of the personal cleansing compositions.
Generally,
the pH of the personal cleansing composition will be less than about 10,
typically from
about 3 to about 9, preferably from about 4 to about S.
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Select cationic spreading agents for use in the composition include those
corresponding to the to the formula:
R +
I'
R4-N-R2 X
R3
wherein R1, and R2 are independently a saturated or unsaturated, substituted
or
unsubstituted, linear or branched hydrocarbon chain having from about 12 to
about 30
carbon atoms, preferably from about 18 to about 22 carbon atoms, and wherein
the
hydrocarbon chain can contain one or more hydrophilic moieties selected from
the
alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, alkylester, and mixtures
thereof; R3
and R4 are independently a hydrogen, or a saturated or unsaturated,
substituted or
unsubstituted, linear or branched hydrocarbon chain having from about 1 to
about 30
carbon atoms, or a hydrocarbon having from about 1 to about 30 carbon atoms
containing
one or more aromatic, ester, ether, amido, amino moieties present as
substitutents or as
linkages in the chain, and wherein the hydrocarbon chain can contain one or
more
hydrophilic moieties selected from the alkoxy, polyoxyalkylene, alkylamido,
hydroxyalkyl, alkylester, and mixtures thereof; and X is a soluble salt
forming anion
preferably selected from halogen (especially chlorine), acetate, phosphate,
nitrate,
sulfonate, and alkylsulfate radicals.
An example of a select spreading agent for use in the composition include
those
corresponding to the formula:
CH3 +
I
CH3(CH2)n-CH2-N-(CH2)nCH3 X
CH3
wherein n is from 10-28, preferably 16, and X is a water soluble salt forming
anion (e.g.,
Cl, sulfate, etc.).
Other examples of select cationic spreading agents for use in the composition
include those corresponding to the formula:
+
0 Z1 0
R"-CNH(-CH2-)m-N -(-CH2 )n-NHCR' X
1
Z2
wherein Z1 and Z2 are independently saturated or unsaturated, substituted or
unsubstituted, linear or branched hydrocarbons, and preferably Z1 is an alkyl,
more
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CA 02372892 2004-07-20
preferably methyl, and Z2 is a short chain hydroxyalkyl, preferably
hydroxymethyl or
hydroxyethyl; n and m are independently integers from 1 to 4, inclusive,
preferably from
2 to 3, inclusive, more preferably 2; R' and R" are independently substituted
or
unsubstituted hydrocarbons, preferably C12-C20 alkyl or alkenyl; and X is a
soluble salt
forming anion (e.g., Cl, sulfate, etc.).
Nonlimiting examples of suitable cationic spreading agents include
ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methyl sulfate,
dihexadecyl dimethyl ammonium chloride, di-(hydrogenated tallow) dimethyl
ammonium chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl
ammonium chloride, didocosyl dimethyl ammonium chloride, di-(hydrogenated
tallow)
dimethyl ammonium acetate, dihexadecyl dimethyl ammonium acetate; ditallow
dipropyl
ammonium phosphate, ditallow dimethyl ammonium nitrate, di-(coconutalkyl)
dimethyl
ammonium chloride, ditallowamidoethyl hydroxypropylmonium methosulfate
TM
(commercially available as Varisoft 238), dihydrogenated tallowamidoethyl
hydroxyethylmonium methosulfate (commercially available as Varisoft 110),
ditallowamidoethyl hydroxyethylmonium methosulfate (commercially available as
Varisoft 222), and di(partially hardened soyoylethyl) hydroxyethylmonium
methosulfate
(commercially available as Armocare EQ-S). Ditallowdimethyl ammonium chloride,
ditallowamidoethyl hydroxypropylmonium methosulfate, dihydrogenated
tallowamidoethyl hydroxyethylmonium rnethosulfate, ditallowamidoethyl
hydroxyethylmonium methosulfate, and di(partially hardened soyoylethyl)
hydroxyethylmonium methosulfate are particularly preferred quatemary ammonium
cationic surfactants useful herein.
Other suitable quaternary ammonium cationic surfactants are described in M.C.
Publishing Co., McCutcheion's Detergents & Eniulsif ers, (North American
edition
1979); Schwartz, et al., Suiface Active Agents. Their Chemistry and
Technology, New
York: Interscience Publishers, 1949; U.S. Patent 3,155,591, to Hilfer, issued
Nov. 3,
1964; U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975; U.S.
Patent
3,959,461 to Bailey et al, issued May 25, 1976; and U.S. Patent 4,387,090 to
Bolich Jr.,
issued June 7, 1983.
iii) Dispersed Phase Polymers
Another optional component of the present invention is a dispersed phase
polymer. Suitable dispersed phase polymers include water soluble nonionic
polymers
and water soluble anionic polymers. Suitable nonionic polymers include
cellulose ethers
(e.g., hydroxybutyl methylcellulose, hydroxypropylcellulose, hydroxypropyl
methylcellulose, ethylhydroxy ethylcellulose and hydroxyethylcellulose),
propylene
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glycol alginates, polyacrylamide, poly(ethylene oxide), polyvinyl alcohol,
polyvinylpyrrolidone, hydroxypropyl guar gum, locust bean gum, amylose,
hydroxyethyl
amylose, starch and starch derivatives and mixtures thereof. Preferred
nonionic polymers
include hydroxyethyl cellulose, polyethylene oxide, polyvinyl pyrrolidone,
polyvinyl
alcohol, polyacrylamide, hydroxypropyl cellulose, ethylhydroxyethyl cellulose,
dextran,
polypropyleneoxide and hydroxypropyl guar or mixtures thereof.
Suitable anionic water-soluble polymers include carboxymethyl cellulose,
carrageenan, xanthum gum polystyrene sulfonate, gum agar, gum ghatti, gum
karaya,
pectins, alginate salts, as well as poly(acrylic acid) and acrylic or
methacrylic acid
derivatives such as the alkali metal and ammonium salts of acrylic acid,
methacrylic acid.
Mixtures of the above anionic water-soluble polymers may also be used:
These polymeric compositions may be homopolymers or they may be copolymers
or terpolymers with other copolymerizing monomers known in the art. Examples
of
copolymerizing monomers known in the art include but are not limited to
ethylene,
propylene, isobutylene, styrene, polystyrene, alphamethylstyrene, vinyl
acetate, vinyl
formate, alkyl ethers, acrylonitrile, methacrylonitrile, vinyl chloride,
vinylidene chloride,
the alkyl acrylates, the alkylmethacrylates, the alkyl fumarates, the alkyl
maleates, and
other olefinic monomers copolymerizable therewith as long as the resulting
polymers are
water soluble and phase separate in the compositions of this invention.
Copolymers of
anionic and nonionic monomers such as acrylic acid and methacrylic acid with
acrylamide, methacrylamide, the N-alkyl substituted amides, the N-
aminoalkylamides,
the corresponding N-alkylaminoalkyl substituted amides, the aminoalkyl
acrylates, the
aminoalkyl methacrylamides, and the N-alkyl substituted aminoalkyl esters of
either
acrylic or methacrylic acids.
Preferred anionic polymers include polyacrylic acid; sodium carboxy methyl
cellulose; polyacrylates; polymethyl acrylate; polysulphates such as polyvinyl
sulfate,
polystyrene sulfonate, polyphosphates, sodium dextran sulfate, alginate salts
and pectate
When combined with the aqueous surfactant system and phase separation
initiator, described below, the water-soluble nonionic or anionic polymer
separates to
form aqueous droplets suspended in a continuous aqueous phase. The number
average
particle size of the polymer droplets can be from 0.1 microns to about 10,000
microns,
preferably from about 1.0 micron to about 5000 microns, most preferably from
about 5
microns to about 1000 microns.
Most preferred for use in the present invention are ethyl hydroxyethyl
cellulose,
hydroxyethyl cellulose, hydroxypropyl guar and polystyrene sulfonate.
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The herein described polymers are preferably present at a concentration level
of
above about 0.1%, more preferably from about 0.15% to about 10%, most
preferably
from about 0.2% to about 2%. mixtures of the anionic and nonionic water-
soluble
polymers may also be used.
See also U.S. Patent No. 5,783,200.
The personal care compositions of the invention when a dispersed phase
polymers is present preferably contain a phase separation initiator, defined
herein after.
Phase Separation Initiators The compositions of the present invention may
additionally
contain a phase separation initiator. By the term "phase separation
initiators", as used
herein, means electrolytes, amphiphiles or mixtures thereof capable of
inducing phase
separation when combined with compositions comprising a surfactant system and
a
nonionic or anionic water-soluble polymer.
By the term "amphiphile" as used herein, means, generally, substances which
contain both hydrophilic and hydrophobic (lipophilic) groups. Amphiphiles
preferred for
use in the present invention are those which generally do not form micelles or
liquid
crystal phases and include, but are not limited to: amides of fatty acids;
fatty alcohols;
fatty esters, glycol mono- and di- esters of fatty acids; glyceryl esters.
Aniides, including alkanol amides, are the condensation products of fatty
acids
with primary and secondary amines or, alkanolamines to yield products of the
general
formula:
0
II /Ix
RC-N -,Y
wherein RCO is a fatty acid radical and R is C8-20; X is an alkyl, aromatic or
alkanol
(CHR'CH2OH wherein R' is H or C1-6 alkyl); Y is H, alkyl, alkanol or X.
Suitable
amides include, but are not limited to , cocamide, lauramide, oleamide and
stearamide.
Suitable alkanolamides include, but are not limited to, cocamide DEA, cocamide
MEA,
cocamide MIPA, isostearamide DEA, isostearamide MEA, isostearamide MIPA,
lanolinamide DEA, lauramide DEA, lauramide MEA, lauramide MIPA, linoleamide
DEA, linoleamide MEA, linoleamide MIPA, myristamide DEA, myristamide MEA,
myristamide MIPA, Oleamide DEA, Oleamide MEA, Oleamide MIPA, palmamide
DEA, palmamide MEA, palmamide MIPA, palmitamide DEA, palmitamide MEA, palm
kernelamide DEA, palm kemelamide MEA, palm kernelamide MIPA, peanutamide
MEA, peanutamide MIPA, soyamide DEA, stearamide DEA, stearamide MEA,
stearamide MIPA, tallamide DEA, tallowamide DEA, tallowamide MEA,
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undecylenamide DEA, undecylenamide MEA. The condensation reaction may be
carried
out with free fatty acids or with all types of esters of the fatty acids, such
as fats and oils,
and particularly methyl esters. The reaction conditions and the raw material
sources
determine the blend of materials in the end product and the nature of any
impurities.
Fatty alcohols are higher molecular weight, nonvolatile, primary alcohols
having
the general formula:
RCH 2OH
wherein R is a C8-20 alkyl. They can be produced from natural fats and oils by
reduction
of the fatty acid COOH- grouping to the hydroxyl function. Alternatively,
identical or
similarly structured fatty alcohols can be produced according to conventional
synthetic
methods known in the art. Suitable fatty alcohols include, but are not limited
to, behenyl
alcohol, C9-11 alcohols, C12-13 alcohols, C12-15 alcohols, C12-16 alcohols,
C14-15
alcohols, caprylic alcohol, cetearyl alcohol, coconut alcohol, decyl alcohol,
isocetyl
alcohol, isostearyl alcohol, lauryl alcohol, oleyl alcohol, palm kernel
alcohol, stearyl
alcohol, cetyl alcohol, tallow alcohol, tridecyl alcohol or myristyl alcohol.
Glyceryl esters comprise a subgroup of esters which are primarily fatty acid
mono- and di-glycerides or triglycerides modified by reaction with other
alcohols and the
like. Preferred glyceryl esters are mono and diglycerides. Suitable glyceryl
esters and
derivatives thereof include, but are not limited to, acetylated hydrogenated
tallow
glyceride, glyceryl behenate, glyceryl caprate, glyceryl caprylate, glyceryl
caprylate/caprate, glyceryl dilaurate, glyceryl dioleate, glyceryl erucate,
glyceryl
hydroxystearate, glyceryl isostearate, glyceryl lanolate, glyceryl laurate,
glyceryl
linoleate, glyceryl oleate, glyceryl stearate, glyceryl myristate, glyceryl
distearate and
mixtures thereof,
Also useful as amphiphiles in the present invention are long chain glycol
esters or
mixtures thereof. Included are ethylene glycol esters of fatty acids having
from about 8
to about 22 carbon atoms. Fatty esters of the formula RCO-OR' also act as
suitable
amphiphiles in the compositions of the present invention, where one of R and
R' is a C8-
22 alkyl and the other is a C 1-3 alkyl.
The amphiphiles of the present invention may also encompass a variety of
surface
active compounds such as nonionic and cationic. surfactants. If incorporated
into the
compositions of the present invention, these surface active compounds become
additional
surfactants used as amphilphiles for the purpose of initiating phase
separation and are
separate and apart from the surfactants of the surfactant system and the alkyl
glyceryl
sulfonate surfactant of the present invention.
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Amphiphiles preferred for use herein include cocamide MEA, cetyl alcohol and
stearyl alcohol.
The amphiphiles of the present invention are preferably present in the
personal
cleansing compositions at levels of from 0 to about 4%. preferably from about
0.5% to
about 2%.
Suitable electrolytes include mono-, di- and trivalent inorganic salts as well
as
organic salts. Surfactant salts themselves are not included in the present
electrolyte
definition but other salts are. Suitable salts include, but are not limited
to, phosphates,
sulfates, nitrates, citrates and halides. The counter ions of such salts can
be, but are not
limited to, sodium, potassium, ammonium, magnesium or other mono-, di and tri
valent
cation. Electrolytes most preferred for use in the compositions of the present
invention
include sodium chloride, ammonium chloride, sodium citrate, and magnesium
sulfate. It
is recognized that these salts may serve as thickening aids or buffering aids
in addition to
their role as a phase separation initiator. The amount of the electrolyte used
will
generally depend on the amount of the amphiphile incorporated, but may be used
at
concentration levels of from about 0.1% to about 4%, preferably from about
0.2% to
about 2%.
The amount of phase separation initiator comprising the electrolyte and/or the
amphiphile will vary with the type of surfactant and polymer, but is generally
present at a
level of from about 0.1% to about 5%, preferably from about 0.2% to about 3%.
In view of the essential nature and activity of the phase separation
initiators
described above, the compositions of the present invention are, preferably,
substantially
free of materials which would prevent the induction or formation of separate,
liquid
phases. The term "substantially free", as used here, means that the
compositions of the
present invention contain no more than about 0.5% of such materials,
preferably less than
0.25%, more preferably zero. Such materials typically include ethylene glycol,
propylene
glycol, ethyl alcohol and the like.
The compositions of the present invention are also preferably substantially
free of
other ingredients which unduly minimize the formation of separate and distinct
liquid
phases, especially ingredients which do not provide a significant benefit to
the present
invention.
c) Antidandruff agent
The personal cleansing compositions of the present invention can additionally
comprise a safe and effective amount of an antidandruff agent. The
antidandruff agent
provides the personal cleansing compositions with antidandruff activity. The
antidandruff agent is preferably a crystalline particulate that is insoluble
in, and dispersed
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throughout, the personal cleansing compositions. Effective concentrations of
such
antidandruff agents generally range from about 0.1% to about 5%, more
preferably from
about 0.3% to about 5%, by weight of the personal cleansing compositions.
See also U.S. Patent 4,948,576 to Verdicchio et al, and
WO 98/18434.
Suitable antidandruff agents includes, for example, platelet pyridinethione
salt
crystal, octopirox, selenium sulfide, ketoconazole and pyridinethione salts.
Selenium
sulfide is a preferred particulate antidandruff agent for use in the personal
cleansing
compositions, effective concentrations of which range from about 0.1% to about
5.0%,
preferably from about 0.3% to about 2.5%, more preferably from about 0.5% to
about
1.5%, by weight of the personal cleansing compositions. Selenium sulfide is
generally
regarded as a compound having one mole of selenium and two moles of sulfur,
although
it may also be a cyclic structure, SexSy, wherein x+ y = 8. Average particle
diameters
for the selenium sulfide (selenium disulfide) are less than 15um, preferably
less than 10
TM
um, as measured by forward laser light scattering device, e.g., Malvern 3600
instrument.
Selenium sulfide compounds are well known in the personal cleansing art, and
are
described, for example in U.S. Patent 2,694,668; U.S. Patent 3,152,046; U.S.
Patent
4,089,945; and U.S. Patent 4,885,107.
Pyridinethione aiitidandruff agents, especially 1 -hydroxy-2-pyridinethi one
salts,
are highly preferred particulate antidandruff agents for use in the personal
cleansing
compositions, concentrations of which range from about 0.1% to about 3%,
preferably
about 0.3% to about 2%, by weight of the personal cleansing compositions.
Preferred
pyridinethione salts are those formed from heavy metals such as zinc, tin,
cadmium,
magnesium, aluminum and zirconium. Zinc salts are most preferred, especially
the zinc
salt of 1-hydroxy-2-pyridinethione (zinc pyridinethione , ZPT). Other cations
such as
sodium may also be suitable.
Pyridinethione antidandruff agents are well known in the personal cleansing
art,
and are described, for example, in U.S. Patent 2,809,971; U.S. Patent
3,236,733; U.S.
Patent 3,753,196; U.S. Patent 3,761,418; U.S. Patent 4,345,080; U.S. Patent
4,323,683;
U.S. Patent 4,379,753; and U.S. Patent 4,470,982.
Sulfur may also be used as the particulate antidandruff agent in the personal
cleansing compositions herein. Effective concentrations of the particulate
sulfur are
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generally from about 1% to about 5%, more preferably from about 2% to about
5%, by
weight of the compositions.
Octopirox and related salts and derivatives may also be used as the
antidandruff
agent in the personal cleansing compositions. Such antidandruff agents are
soluble in the
personal cleansing composition and, therefore, do not disperse throughout the
composition as crystalline particulates as do the other antidandruff agents
described
hereinbefore. Other antidandruff agents such as azoles may also be used.
Examples of
azole antidandruff agents are: ketoconazole, itraconazole, fluconazole,
miconazole,
econazole.
Water soluble non-particulate antidandruff substances whose deposition and
retention is enhanced by the water-soluble nitrogen containing polymers
described herein
include (i.e. deposition polymers)
(a) 1-hydroxy-2-pryidoner of the formula
R3
Rz R4
RI N 0
OH
wherein Rl is hydrogen, alkyl of I to 17 carbon atoms, cycloalkyl-alkyl of 1
to 4 alkyl
carbon atoms, the cycloalkyl groups being optionally substituted by alkyl
groups of 1 to 4
carbon atoms, aryl, aralkylof I to 4 alkyl carbon atoms, aryl-alkcnyl of 2 to
4 alkenyl
carbon atoms, aryloxy-alkyl or arylthio-alkyl of 1 to 4 alkyl carbon atoms,
benzhydyl,
phenylsulfonyl-alky of 1 to 4 alkyl carbon atoms, furyl or furyl-alkenyl of 2
to 4 alkenyl
carbon atoms, the aryl groups being optionally substituted by alkyl of I to 4
carbon
atoms, by alkoxyl of 1 to 4 carbon atoms, by nitrogen, or cyano halogen atoms.
R2 is
hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl or alkinyl of 2 to 4 carbon
atoms, halogen
atoms or benzyl. R3 is hydrogen, alkyl of I to 4 carbon atoms or phenyl. R4 is
hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms,
methoxy-methyl,
halogen or benzyl andlor salts thereof.
These compounds are disclosed and more fully described in U.S. Patent No.
4,185,106 and such compounds are available commercially from Hoechst
Aktiengesellschaft under the trade mark Octopirox.
(b) magnesium sulfate adducts of 2,2'-dithiobis(pyridine-l-oxide) of the
formula
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MgSO4
+ i
O O
These compounds are available from Olin corporation under the trade mark:
Omadine MDS.
It is preferred that an antidandruff agent be used in combination with a
deposition
polymer, where such a combination would result in improved deposition and
retention of
the antidandruff agent.
Additionally, the antidandruff agent can be a heavy metal magnesium or
aluminium salts of 1-hydroxy-2-pyridinethione which has the following
structural
formula in tautomeric form, the sulfur being attached to the No. 2 position in
the pyridine
ring:
0
OH (SH
The metal salts represent substitution of the metal cation for the hydrogen of
one
of the tautomeric forms. Depending, of course, on the valence of the metal
involved
there may be more than one of the pyridinethione rings in the compound.
Suitable heavy
metals include zinc, tin, cadmium and zirconium.
The personal cleansing compositions of the invention can optionally contain a
antidandruff agent which is a platelet pyridinethione salt crystal. When
present, platelet
pyridinethione salt crystals are predominantly flat platelets which have a
mean sphericity
less than about 0.65, preferably between about 0.20 and about 0.65 and a
median size of
at least about 2 diameter, expressed as the median equivalent diameter of a
sphere of
equal volume. It is preferred that the mean particle size be not greater than
15 ,
measured on the same basis. The median diameters are on a mass basis with 50%
of the
mass of particles falling on either side of the value given.
The diameter of a sphere of equivalent volume for a particle can be detennined
by
a varieties of sedimentation techniques which are based on Stokes' Law for the
settling
velocity of a partivle in a fluid. Such techniques are described in Stockham,
J.D. and
Fochtman, E.G., Particle Size Analysis, Ann Arbour Science, 1978.
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The sphericity of a particle is also described by Stockham and Fochtman at
page
113 as
y1= (dv/ds)2
where dv is the diameter of a sphere of equivalent volume, supra, and ds is
the diameter
of a sphere of equivalent area. In the present invention
the mean sphericity = (-dv/-ds)2 or
surface areas of spheres having equivalent volume distribution divided by the
actual
surface area of particles as measured. See U.S. Patent No. 4,379,753 to
Bolich, Jr.
Co-surfactants.
The surfactant system of the personal cleansing compositions of the present
invention can comprise, one or more detersive co-surfactants selected from the
group
consisting of anionic co-surfactant, nonionic co-surfactant, cationic co-
surfactant,
amphoteric co-surfactant, zwitterionic co-surfactants, and mixtures thereof.
The total
amount of surfactant present in the personal cleansing composition is
preferably at least
about 5%, more preferably still at least about 8%, even more preferably at
least about
10%, by weight. Furthermore, the total amount of surfactant (i.e., the mid-
chain
branched surfactant plus co-surfactant) present in the personal cleansing
composition will
be present at preferably less than about 45%, more preferably less than about
35%, even
more preferably less than about 30%, even more preferably less than about 25%,
even
more preferably less than about 20%, most preferably less than about 15%, by
weight.
Anionic Co-surfactant
The personal cleansing compositions preferably comprise an anionic co-
surfactant, and preferably at concentrations of at least about 0.5%, more
preferably, at
least about 1%, even more preferably at least about 2%, even more preferably
still at least
about 5%, even more preferably still at least about 8%, most preferably at
least about
10%, by weight. Furthermore, amount of anionic co-surfactant present in the
personal
cleansing composition will be present at preferably less than about 35%, more
preferably
less than about 30%, even more preferably less than about 25%, by weight of
the
composition. It is preferred that the total amount of anionic surfactant (i.e.
anionic mid-
chain branched plus anionic co-surfactant) present in the personal cleansing
composition
is preferably about 5% or greater, more preferrably 8% or greater, even more
preferably
about 10% or greater, even more preferably still about 12% or greater, by
weight of the
composition.
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Anionic co-surfactants for use in the personal cleansing compositions include
alkyl and alkyl ether sulfates. These materials have the respective formulae
ROSO3M
and RO(C2H40)xSO3M, wherein R is alkyl or alkenyl of from about 8 to about 30
carbon atoms, x is 1 to 10, and M is a cation such as ammonium, alkanolamines,
such as
triethanolamine, monovalent metals, such as sodium and potassium, and
polyvalent metal
cations, such as magnesium, and calcium. The cation M, of the anionic co-
surfactant
should be chosen such that the anionic co-surfactant component is water
soluble.
Solubility will depend upon the particular anionic co-surfactants and cations
chosen.
Preferably, R has from about 12 to about 18 carbon atoms in both the alkyl and
alkyl ether sulfates. The alkyl ether sulfates are typically made as
condensation products
of ethylene oxide and monohydric alcohols having from about 8 to - about 24
carbon
atoms. The alcohols can be derived from fats, e.g., coconut oil or tallow, or
can be
synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil
are
preferred herein. Such alcohols are reacted with between about 0 and about 10,
and
especially about 3, molar proportions of ethylene oxide and the resulting
mixture of
molecular species having, for example, an average of 3 moles of ethylene oxide
per mole
of alcohol, is sulfated and neutralized.
Specific examples of alkyl ether sulfates which may be used in the personal
cleansing compositions of the present invention are sodium and ammonium salts
of
coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene
glycol ether sulfate,
and tallow alkyl hexaoxyethylene sulfate. Highly preferred alkyl ether
sulfates are those
comprising a mixture of individual compounds, said mixture having an average
alkyl
chain length of from about 10 to about 16 carbon atoms and an average degree
of ethoxy-
lation of from about 1 to about 4 moles of ethylene oxide.
Other suitable anionic co-surfactants are the water-soluble salts of organic,
sulfuric acid reaction products of the general formula [ R1-S03-M ] where Rl
is selected
from the group consisting of a straight or branched chain, saturated aliphatic
hydrocarbon
radical having from about 8 to about 24, preferably about 10 to about 18,
carbon atoms;
and M is a cation, as previously described, subject to the same limitations
regarding
polyvalent metal cations as previously discussed. Examples of such co-
surfactants are
the salts of an organic sulfuric acid reaction product of a hydrocarbon of the
methane
series, including iso-, neo-, and n-paraffins, having about 8 to about 24
carbon atoms,
preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g.,
SO3, H2SO4,
obtained according to known sulfonation methods, including bleaching and
hydrolysis.
Preferred are alkali metal and ammonium sulfonated C10-18 n-paraffins.
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Still other suitable anionic co-surfactants are the reaction products of fatty
acids
esterified with isethionic acid and neutralized with sodium hydroxide where,
for
example, the fatty acids are derived from coconut oil; sodium or potassium
salts of fatty
acid amides of methyl tauride in which the fatty acids, for example, are
derived from
coconut oil. Other similar anionic co-surfactants are described in U.S.
Patents 2,486,921;
2,486,922; and 2,396,278.
Other anionic co-surfactants suitable for use in the personal cleansing
compositions are the succinnates, examples of which include disodium
N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl
sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate;
diamyl
ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic
acid; dioctyl
esters of sodium sulfosuccinic acid.
Other suitable anionic co-surfactants include olefin sulfonates having about
10 to
about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean
compounds
which can be produced by the sulfonation of alpha-olefins by means of
uncomplexed
sulfur trioxide, followed by neutralization of the acid reaction mixture in
conditions such
that any sulfones which have been formed in the reaction are hydrolyzed to
give the
corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be liquid or
gaseous,
and is usually, but not necessarily, diluted by inert diluents, for example by
liquid SO2,
chlorinated hydrocarbons, etc., when used in the liquid form, or by air,
nitrogen, gaseous
SO2, etc., when used in the gaseous for.m.
The alpha-olefins from which the olefin sulfonates are derived are mono-
olefins
having about 12 to about 24 carbon atoms, preferably about 14 to about 16
carbon atoms.
Preferably, they are straight chain olefins.
In addition to the true alkene sulfonates and a proportion of
hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of
other
materials, such as alkene disulfonates depending upon the reaction conditions,
proportion
of reactants, the nature of the starting olefins and impurities in the olefin
stock and side
reactions during the sulfonation process.
A specific alpha-olefin sulfonate mixture of the above type is described more
fully in the U.S. Patent 3,332,880.
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Another class of anionic co-surfactants suitable for use in the personal
cleansing
compositions are the beta-alkyloxy alkane sulfonates. These compounds have the
following formula:
OR2 H
R~ SO,M
H H
where R1 is a straight chain alkyl group having from about 6 to about 20
carbon atoms,
R2 is a lower alkyl group having from about 1(preferred) to about 3 carbon
atoms, and
M is a water-soluble cation as hereinbefore described.
Many other anionic co-surfactants suitable for use in the personal cleansing
compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989
Annual,
published by M. C. Publishing Co., and in U.S. Patent 3,929,678.
Preferred anionic co-surfactants for use in the personal cleansing
compositions
include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine
lauryl sulfate,
triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine
laureth
sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate,
diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric
monoglyceride
sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium
lauryl sulfate,
potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl
sarcosinate, Iauryl
sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl
sulfate,
sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,
potassium lauryl
sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,
monoethanolamine
cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene
sulfonate, and
sodium dodecyl benzene sulfonate.
Amphoteric and zwitterionic co-surfactants
The detersive co-surfactant of the personal cleansing compositions may
comprise
an amphoteric and/or zwitterionic co-surfactant. Concentrations of such co-
surfactants
will generally range from about 0.5% to about 20%, preferably from about 1 /
to about
10%, by weight of the personal cleansing compositions.
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Amphoteric co-surfactants for use in the personal cleansing compositions
include
the derivatives of aliphatic secondary and tertiary amines in which the
aliphatic radical is
straight or branched and one of the aliphatic substituents contains from about
8 to about
18 carbon atoms and one contains an anionic water solubilizing group, e.g.,
carboxy,
sulfonate, sulfate, phosphate, or phosphonate.
Suitable amphoteric co-surfactants for use in the personal cleansing
compositions
include long chain tertiary amine oxides of the formula [ R1R2R3N -a O] where
Rl
contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to
about 18
carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about
1 glyceryl
moiety, and R2 and R3 contain from about 1 to about 3 carbon atoms and from 0
to about
1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl
radicals.
Suitable amphoteric co-surfactants for use in the personal cleansing
compositions
include long chain tertiary phosphine oxides of the formula [RR'R"P -> 0]
where R
contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to
about 18
carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and
from 0 to
about 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl
groups
containing from about 1 to about 3 carbon atoms.
Suitable amphoteric co-surfactants for use in the personal cleansing
compositions
include long chain dialkyl sulfoxides containing one short chain alkyl or
hydroxy alkyl
radical of from about 1 to about 3 carbon atoms (usually methyl) and one long
hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl
radicals
containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene
oxide
moieties and from 0 to about 1 glyceryl moiety.
Zwitterionic co-surfactants for use in the personal cleansing compositions
include
the derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium
compounds, in which the aliphatic radicals are straight or branched, and
wherein one of
the aliphatic substituents contains from about 8 to about 18 carbon atoms and
one
contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or
phosphonate.
A general formula for these compounds is:
(R3)x
R2-Y CH2-R4-Z
where R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8
to about
18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to
about 1
glyceryl moiety; Y is selected from the group consisting of nitrogen,
phosphorus, and
sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing about 1 to
about 3
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carbon atoms; X is I when Y is a sulfur atom, and 2 when Y is a nitrogen or
phosphorus atom; R4 is an alkylene or hydroxyalkylene of from about 1 to about
4
carbon atoms and Z is a radical selected from the group consisting of
carboxylate,
sulfonate, sulfate, phosphonate, and phosphate groups.
Examples of amphoteric and zwitterionic co-surfactants also include sultaines
and amidosultaines. Sultaines and amidosultaines can be used as foam enhancing
co-
surfactants that are mild to the eye in partial replacement of anionic co-
surfactants.
Sultaines, including amidosultaines, include for example,
cocodimethylpropylsultaine, stearyldimethylpropylsultaine,
lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the
amidosultaines such
as cocoamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine,
laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like. Preferred are
amidohydroxysultaines such as the C12-C 1 g hydrocarbyl amidopropyl hydroxy-
sultaines, especially C12-C14 hydrocarbyl amido propyl hydroxysultaines, e.g.,
laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other
sul-
taines are described in U.S. Patent 3,950,417.
Other suitable amphoteric co-surfactants are the aminoalkanoates of the
formula R-NH(CH2)nCOOM, the iminodialkanoates of the formula
R-N[(CH2)mCOOM]2
and mixtures thereof; wherein n and m are numbers from 1 to 4, R is C8 - C22
alkyl
or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, anunonium
or
alkanolammonium.
Examples of suitable aminoalkanoates include n-alkylamino-propionates and
n-alkyliminodipropionates, specific examples of which include N-lauryl-beta-
amino
propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid or
salts
thereof, and mixtures thereof.
Other suitable amphoteric co-surfactants include those represented by the
formula :
R3
Rl CON-(CHZ)ri N CH2Z
R4 R2
wherein Rl is C8 - C22 alkyl or alkenyl, preferably C12-C16, R2 is hydrogen or
CH2CO2M, R3 is CH2CH2OH or CH2CH2OCH2CH2COOM, R4 is hydrogen,
CH2CH2OH, or CH2CH2OCH2CH2COOM, Z is CO2M or CH2CO2M, n is 2 or 3,
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preferably 2, M is hydrogen or a cation, such as alkali metal (e.g., lithium,
sodium,
potassium), alkaline earth metal (beryllium, magnesium, calcium, strontium,
barium),
or ammonium. This type of co-surfactant is sometimes classified as an
imidazoline-type amphoteric co-surfactant, although it should be recognized
that it
does not necessarily have to be derived, directly or indirectly, through an
imidazoline
intennediate.
Suitable materials of this type are marketed under the trade mark MIRANOL
and are understood to comprise a complex mixture of species, and can exist in
protonated and non-protonated species depending upon pH with respect to
species
that can have a hydrogen at R2. All such variations and species are meant to
be
encompassed by the above formula.
Examples of co-surfactants of the above formula are monocarboxylates and
dicarboxylates. Examples of these materials include
cocoamphocarboxypropionate,
cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately
referred
to as cocoamphodiacetate), and cocoamphoacetate.
Commercial amphoteric co-surfactants include those sold under the trade
marks; MH~ANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P., MIRANOL
C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril
Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38,
MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical
Group); and SCHERCOTERIC MS-2 (Scher Chemicals).
Betaine co-surfactants (zwitterionic) suitable for use in the personal
cleansing
compositions are those represented by the formula:
O R4 R2
RS NI -(CHZ -N+-Y-Rl
I
R3
n
wherein:
Rl is a member selected from the group consisting of
COOM and CH(OH)-CH2SO3M
R2 is lower alkyl or hydroxyalkyl;
R3 is lower alkyl or hydroxyalkyl;
R4 is a member selected from the group consisting of hydrogen and lower alkyl;
R5 is higher alkyl or alkenyl;
Y is lower alkyl, preferably methyl;
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m is an integer from 2 to 7, preferably from 2 to 3;
n is the integer 1 or 0;
M is hydrogen or a cation, as previously described, such as an alkali metal,
alkaline
earth metal, or ammonium.
The term "lower alkyl" or "hydroxyalkyl" means straight or branch chained,
saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals
having
from one to about three carbon atoms such as, for example, methyl, ethyl,
propyl, iso-
propyl, hydroxypropyl, hydroxyethyl, and the like. The term "higher alkyl or
alkenyl"
means straight or branch chained saturated (i.e., "higher alkyl") and
unsaturated (i.e.,
"higher alkenyl") aliphatic hydrocarbon radicals having from about eight to
about 20
carbon atoms such as, for example, lauryl, cetyl, stearyl, oleyl, and the
like. It should
be understood that the term "higher alkyl or alkenyl" includes mixtures of
radicals
which may contain one or more intermediate linkages such as ether or polyether
linkages or non-functional substitutents such as hydroxyl or halogen radicals
wherein
the radical remains of hydrophobic character.
Examples of co-surfactant betaines of the above formula wherein n is zero
which are useful herein include the alkylbetaines such as
cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryl
dimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine,
lauryl-bis-(2-hydroxyethyl)carboxymethylbetaine, stearyl-bis-(2-hy-
droxypropyl)carboxymethylbetaine, oleyldimethyl-gamma-carboxypropylbetaine,
lauryl-bis-(2-hydroxypropyl)alpha-carboxyethylbetaine, etc. The sulfobetaines
may
be represented by cocodimethylsulfopropylbetaine,
stearyldimethylsulfopropylbetaine,
lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine, and the like.
Specific examples of amido betaines and amidosulfo betaines useful in the
personal cleansing compositions include the amidocarboxybetaines, such as
cocoamidodimethylcarboxymethylbetaine, laurylamidodi-
methylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine,
laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine,
cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc. The amido
sulfobetaines
may be represented by cocoamidodimethylsulfopropylbetaine,
stearylamidodimethylsulfopropylbetaine, lauryl-
amido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.
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Nonionic co-surfactant
The personal cleansing compositions of the present invention may comprise a
nonionic co-surfactant as the detersive co-surfactant component therein.
Nonionic co-
surfactants include those compounds produced by condensation of alkylene oxide
groups
(hydrophilic in nature) with an organic hydrophobic compound, which may be
aliphatic
or alkyl aromatic in nature.
Concentrations of such co-surfactants will generally range from about 0.01% to
about 20%, preferably from about 1% to about 10%, by weight of the personal
cleansing
compositions.
Preferred nonionic co-surfactants for use in the personal cleansing
compositions
include the following:
(1) polyethylene oxide condensates of alkyl phenols, e.g., the condensation
products of alkyl phenols having an alkyl group containing from about 6 to
about 20
carbon atoms in either a straight chain or branched chain configuration, with
ethylene
oxide, the said ethylene oxide being present in amounts equal to from about 10
to about
60 moles of ethylene oxide per mole of alkyl phenol;
(2) those derived from the condensation of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylene diamine products;
(3) condensation products of aliphatic alcohols having from about 8 to about
18
carbon atoms, in either straight chain or branched chain configuration, with
ethylene
oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 10
to about
30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol
fraction
having from about 10 to about 14 carbon atoms;
(4) alkyl polysaccharide (APS) co-surfactants (e.g. alkyl polyglycosides),
examples of which are described in U.S. Patent
4,565,647, and which discloses APS co-surfactants having a
hydrophobic group with about 6 to about 30 carbon atoms and polysaccharide
(e.g.,
polyglycoside) as the hydrophilic group; optionally, there can be a
polyalkylene-oxide
group joining the hydrophobic and hydrophilic moieties; and the alkyl group
(i.e., the
hydrophobic moiety) can be saturated or unsaturated, branched or unbranched,
and
unsubstituted or substituted (e.g., with hydroxy or cyclic rings); and
(5) polyethylene glycol (PEG) glyceryl fatty esters, such as those of the
formula
R(O)OCH2 CH(OH)CH2 (OCH CHZ)nOH wherein n is from about 5 to about 200,
preferably from about 20 to about 100, and R is an aliphatic hydrocarbyl
having from
about 8 to about 20 carbon atoms.
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Cationic Co-surfactants
Optional cationic co-surfactants for use as conditioning agents in the
personal
cleansing compositions will typically contain quatemary nitrogen moieties.
Examples of
suitable cationic co-surfactants are described in
following documents: M.C. Publishing Co., McCutcheon's,
Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al.,
Surface
Active Agents, Their Chemistry and Technology, New York: Interscience
Publishers,
1949; U.S. Patent 3,155,591; U. S. Patent 3,929,678; U. S. Patent 3,959,461
and U. S.
Patent 4,387,090.
Concentrations of such co-surfactants will generally range from about 0.01% to
about 20%, preferably from about 1% to about 10%, by weight of the personal
cleansing
compositions.
Examples of suitable cationic co-surfactants are those corresponding to the
general formula:
+
R,*"~R3
R2/ R4
wherein R1, R2, R3, and R4 are independently selected from an aliphatic group
of from 1
to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido,
hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and
X is a salt-
forming anion such as those selected from halogen, (e.g. chloride, bromide),
acetate,
citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate
radicals. The
aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether
linkages,
and other groups such as amino groups. The longer chain aliphatic groups,
e.g., those of
about 12 carbons, or higher, can be saturated or unsaturated. Preferred is
when R1, R2,
R3, and R4 are independently selected from C 1 to about C22 alkyl. Especially
preferred
are cationic materials containing two long alkyl chains and two short alkyl
chains or
those containing one long alkyl chain and three short alkyl chains. The long
alkyl chains
in the compounds described in the previous sentence have from about 12 to
about 22
carbon atoms, preferably from about 16 to about 22 carbon atoms, and the short
alkyl
chains in the compounds described in the previous sentence have from 1 to
about 3
carbon atoms, preferably from 1 to about 2 carbon atoms.
Aqueous Liquid Carrier
The personal cleansing compositions herein further contain from about 50% to
99.899%, preferably from about 60% to about 95%, more preferably from about
70% to
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about 85%, by weight of an aqueous liquid carrier in which the other essential
and
optional compositions components are dissolved, dispersed or suspended.
One essential component of the aqueous liquid carrier is, of course, water.
The
aqueous liquid carrier, however, may contain other materials which are liquid,
or which
dissolve in the liquid carrier, at room temperature and which may also serve
some other
function besides that of a simple filler. Such materials can include, for
example,
hydrotropes and co-solvents.
a) Hydrotropes
The aqueous liquid carrier may comprise one or more materials which are
hydrotropes. Hydrotropes suitable for use in the compositions herein include
the C1-C3
alkyl aryl sulfonates, C6-C12 alkanols, C1-C6 carboxylic sulfates and
sulfonates, urea,
Cl-C6 hydrocarboxylates, Cl-C4 carboxylates, C2-C4 organic diacids and
mixtures of
these hydrotrope materials.
Suitable C1-C3 alkyl aryl sulfonates include sodium, potassium, calcium and
ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluene
sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; and
sodium,
potassium, calcium and ammonium substituted or unsubstituted naphthalene
sulfonates
and mixtures thereof.
Suitable C 1-Cg carboxylic sulfate or sulfonate salts are any water soluble
salts or
organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent
groups),
which are substituted with sulfate or sulfonate and have at least one
carboxylic group.
The substituted organic compound may be cyclic, acylic or aromatic, i.e.
benzene
derivatives. Preferred alkyl compounds have from 1 to 4 carbon atoms
substituted with
sulfate or sulfonate and have from 1 to 2 carboxylic groups. Examples of this
type of
hydrotrope include sulfosuccinate salts, sulfophthalic salts, sulfoacetic
salts, m-
sulfobenzoic acid salts and diester sulfosuccinates, preferably the sodium or
potassium
salts as disclosed in U.S. 3,915,903.
Suitable C 1-C4 hydrocarboxylates and C 1-C4 carboxylates for use herein
include
acetates and propionates and citrates. Suitable C2-C4 diacids for use herein
include
succinic, glutaric and adipic acids.
Other compounds which deliver hydrotropic effects suitable for use herein as a
hydrotrope include C6-C12 alkanols and urea.
Preferred hydrotropes for use herein are sodium, potassium, calcium and
ammonium cumene sulfonate; sodium, potassium, calcium and ammonium xylene
sulfonate; sodium, potassium, calcium and ammonium toluene sulfonate and
mixtures
thereof. Most preferred are sodium cumene sulfonate and sodium xylene
sulfonate and
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mixtures thereof. These preferred hydrotrope materials can be present in the
composition
to the extent of from about 0.1 /o to 8% by weight.
b) Co-Solvents
A variety of water-miscible liquids such as lower alkanols, diols, other
polyols,
ethers, amines, and the like may be used as part of the aqueous liquid
carrier.
Particularly preferred are the Cl-C4 alkanols. Such co-solvents can be present
in the
compositions herein to the extent of up to about 8%. These co-solvents are
different to
the solvents used in combination with styling polymers as the co-solvents
dissolved,
dispersed or suspended any or all of the components of the personal cleansing
compositions. Whereas, the solvent is concerned with only dispersing, and
preferably
dissolving, the styling polymer.
Optional Components
The personal cleansing compositions of the present invention may further
comprise one or more optional components known for use in shampoo,
conditioning and
other personal cleansing compositions, provided that the optional components
are
physically and chemically compatible with the essential component described
herein, or
do not otherwise unduly impair product stability, aesthetics or performance.
Concentrations of such optional components typically range from about 0.001 %
to about
30% by weight of the personal cleansing compositions, when present.
Optional components include anti static agents, dyes, diluents, emollient oils
(such as polyisobutylene, mineral oil, petrolatum and isocetyl stearyl
stearate),
pearlescent aids, foam boosters, pediculocides, pH adjusting agents, perfumes,
preservatives, proteins, antioxidants; chelators and sequestrants; and
aesthetic
components such as fragrances, colorings, essential oils, skin sensates,
astringents, skin
soothing agents, skin healing agents and the like, nonlimiting examples of
these aesthetic
components include panthenol and derivatives (e.g. ethyl panthenol),
pantothenic acid
and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol,
menthyl lactate,
witch hazel distillate, allantoin, bisabalol, dipotassium glycyrrhizinate and
the like,
sunscreens, thickeners, vitamins and derivatives thereof (e.g., ascorbic acid,
vitamin E,
tocopheryl acetate, retinoic acid, retinol, retinoids, and the like), and
viscosity adjusting
agents. This list of optional components is not meant to be exclusive, and
other optional
components can be used.
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Laundry Bars
The compositions of the present invention may also be in the form of Laundry
bars. That is, the compositions are designed for use in hand washing of
fabrics and is in
the form of a bar.
Detergent surfactant - Laundry bars of the present invention typically
comprise 10% to
about 60%, preferably about 15% to about 40% of an anionic surfactant. A
preferred
anionic surfactant for use is an alkyl sulfate (AS) having an alkyl chain of
from 10 to 20
carbon atoms, a branched-chain alkylbenzene sulfonate (ABS) having an alkyl
chain of
from 10 to 22 carbon atoms, a linear-chain alkylbenzene sulfonate (LAS) having
an alkyl
chain of from 10 to 22 carbon atoms, and mixtures thereof.
The alkyl portion of said ABS or LAS surfactant preferably contains from 10 to
16 carbon atoms, more preferably from 10 to 14 carbon atoms. Most preferably,
the
alkylbenzene sulfonate surfactant is LAS.
The alkyl portion of the AS surfactant preferably contains from 10 to 18
carbon
atoms, more preferably from 12 to 16 carbon atoms. The AS surfactant can
comprise a
mixture of a longer-chain AS, such as one having 16 to 18 carbons, and a
shorter-chain
alkyl such as one having 11-13 carbons. Preferred AS surfactants include
coconut alkyl
sulfate, tallow alkylsulfate, and mixtures thereof; most preferably, coconut
alkyl sulfate.
A preferred anionic surfactant comprises a mixture of AS and alkylbenzene
sulfonate.
Also preferred are mixtures of AS and LAS surfacants at a ratio of AS:LAS of
about
0:100 to 100:0.
The cation for the ABS, LAS and the AS is preferably sodium, although other
useful cations include triethanolamine, potassium, ammonium, magnesium, and
calcium,
or mixtures thereof.
Other optional surfactants include zwitterionic, nonionic, amphoteric
surfactants
alone or in conjuction with anionic surfactants.
Detergent Builder - The laundry bars of the present invention comprise from
about 5% to
about 60% by weight detergent builder. Preferred laundry bars comprise from
about 5%
to about 30% builder, more preferably from about 7% to about 20%, by weight of
the
bar. These detergent builders can be, for example, water-soluble alkali-metal
salts of
phosphates, pyrophosphates, orthophosphates, tripolyphosphates, higher
polyphosphates,
and mixtures thereof. A preferred builder is a water-soluble alkali-metal salt
of
tripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate. The
builder can
also be a non-phosphate detergent builder. Specific examples of a non-
phosphorous,
inorganic detergency builder include water-soluble inorganic carbonate and
bicarbonate
salts. The alkali metal (e.g., sodium and potassium) carbonates, bicarbonates,
and
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silicates are particularly useful herein. Specific preferred examples of
builders include
sodium tripolyphosphates (STPP) and sodium pyrophosphates (TSPP), and mixtures
thereof. Other specifically preferred examples of builders include zeolite and
polycarboxylates.
Sodium carbonate is a particularly preferred ingredient in laundry bars, since
in
addition to its use as a builder, it can also provide alkalinity to the
laundry bar for
improved detergency, and also can serve as a neutralizing agent for acidic
components
added in the bar processing. Sodium carbonate is particularly preferred as a
neutralizing
inorganic salt for an acid precursor of an anionic surfactant used in such
laundry bars,
such as the alkyl sulfurie acid and alkyl benzene sulfonic acid.
Co-polymers of acrylic acid and maleic acid are preferred as auxiliary
builders,
since it has been observed that their use in combination with the fabric
softening clay and
the clay flocculating agent further stabilizes and improves the clay
deposition and fabric
softening performance.
Optional Laundry Bar componet
Auxiliary Surfactants - The detergent bars of the present invention can
contain up to
about 70% by weight of optional ingredients commonly used in detergent
products. A
typical listing of the classes and species optional surfactants, optional
builders and other
ingredients useful herein appears in U.S. Pat. No. 3,664,961, issued to Norris
on May 23,
1972, and EP 550,652, published on April 16, 1992.
The following are representative of such materials, but are not intended to be
limiting.
In addition to the auxiliary surfactants mentioned above, a hydrotrope, or
mixture
of hydrotropes, can be present in the laundry detergent bar. Preferred
hydrotropes
include the alkali metal, preferably sodium, salts of tolune sulfonate, xylene
sulfonate,
cumene sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the
hydrotrope, in
either the acid form or the salt form, and being substantially anhydrous, is
added to the
linear alkyl benzene sulfonic acid prior to its neutralization. The hydrotrope
will
preferably be present at from about 0.5% to about 5% of the laundry detergent
bar.
Fabric Softening Clay - The fabric softening clay is preferably a smectite-
type clay. The
smectite-type clays can be described as expandable, three-layer clays; i.e.,
alumino-
silicates and magnesium silicates, having an ion exchange capacity of at least
about 50
meq/100 g. of clay. Preferably the clay particles are of a size that they can
not be
perceived tactilely, so as not to have a gritty feel on the treated fabric of
the clothes. The
fabric softening clay can be added to the bar to provide about 1% to about 30%
by
weight of the bar, more preferably from about 5% to about 20%, and most
preferably
about 8% to 14%.
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While any of the smectite-type clays described herein are useful in the
present
TM
invention, certain clays are preferred. For example, Gelwhite GP is an
extremely white
form of smectite-type clay and is therefore preferred when formulating white
granular
detergent compositions. Volclay BC, which is a smectite-type clay mineral
containing at
least 3% iron (expressed as Fe203) in the crystal lattice, and which has a
very high ion
exchange capacity, is one of the most efficient and effective clays for use in
the instant
compositions from the standpoint of product performance. On the other hand,
certain
smectite-type clays are sufficiently contaminated by other silicate minerals
that their ion
exchange capacities fall below the requisite range; such clays are of no use
in the instant
compositions.
Clay Flocculating Agent - It has been found that the use of a clay
flocculating agent in a
laundry bar containing softening clay provides surprisingly improved softening
clay
deposition onto the clothes and clothes softening performance, compared to
that of
laundry bars comprising softening clay alone. The polymeric clay flocculating
agent is
selected to provide improved deposition of the fabric softening clay.
Typically such
materials have a high molecular weight, greater than about 100,000. Examples
of such
materials can include long chain polymers and copolymers derived from monomers
such
as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate,
vinyl
alcohol, vinyl pyrrolidone, and ethylene imine. Gums, like guar gums, are
suitable as
well. The preferred clay flocculating agent is a poly(ethylene oxide) polymer.
Other Optional Inizredients - A particularly preferred optional component of
the present
invention is a detergent chelant. Such chelants are able to sequester and
chelate alkali
cations (such as sodium, lithium and potassium), alkali metal earth cations
(such as
magnesium and calcium), and most preferably, heavy metal cations such as iron,
manganese, zinc and aluminum. Preferred cations include sodium, magnesium,
zinc, and
mixtures thereof. The detergent chelant is particularly beneficial for
maintaining good
cleaning performance and improved surfactant mileage, despite the presence of
the
softening clay and the clay flocculating agent.
The detergent chelant is preferably a phosphonate chelant, particular one
selected
from the group consisting of diethylenetriamine penta(methylene phosphonic
acid),
ethylene diamine tetra(methylene phosphonic acid), and mixtures and salts and
complexes thereof, and an acetate chelant, particularly one selected from the
group
consisting of diethylenetriamine penta(acetic acid), ethylene diamine
tetra(acetic acid),
and mixtures and salts and complexes thereof. Particularly preferred are
sodium, zinc,
magnesium, and aluminum salts and complexes of diethylenetriamine
penta(methylene
phosphonate) diethylenetriamine penta (acetate), and mixtures thereof.
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Preferably such salts or complexes have a molar ratio of metal ion to chelant
molecule of at least 1:1, preferably at least 2:1.
The detergent chelant can be included in the laundry bar at a level up to
about
5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to
about
2%, most preferably from about 0.5% to about 1.0%. Such detergent chelant
component
can be used beneficially to improve the surfactant mileage of the present
laundry bar,
meaning that for a given level of anionic surfactant and level of detergent
chelant,
equivalent sudsing and cleaning performance can be achieved compared to a
similar bar
containing a higher level of the anionic surfactant but without the detergent
chelant.
Another preferred additional component of the laundry bar is fatty alcohol
having
an alkyl chain of 8 to 22 carbon atoms, more preferably from 12 to 18 carbon
atoms.
Fatty alcohol is effective at reducing the bar wear rate and smear (mushiness)
of the
present laundry bars. A preferred fatty alcohol has an alkyl chain
predominantly
containing from 16 to 18 carbon atoms, so-called "high-cut fatty alcohol,"
which can
exhibit less base odor of fatty alcohol relative to broad cut fatty alcohols.
Typically fatty
alcohol is contained in the laundry bar at up to a level of 10%, more
preferably from
about 0.75% to about 6%, most preferably from about 2% to about 5%. The fatty
alcohol
is generally added to the formulation of the present invention as free fatty
alcohol.
However, low levels of fatty alcohol can be introduced into the bars as
impurities or as
unreacted starting material. For example, laundry bars based on coconut fatty
alkyl
sulfate can contain, as unreacted starting material, from 0.1% to 3.5%, more
typically
from 2% to 3%, by weight of free coconut fatty alcohol on a coconut fatty
alkyl sulfate
basis.
Another preferred optional component in the laundry bar is a dye transfer
inhibiting (DTI) ingredient to prevent diminishing of color fidelity and
intensity in
fabrics. A preferred DTI ingredient can include polymeric DTI materials
capable of
binding fugitives dyes to prevent them from depositing on the fabrics, and
decolorization
DTI materials capable of decolorizing the fugitives dye by oxidation. An
example of a
decolorization DTI is hydrogen peroxide or a source of hydrogen peroxide, such
as
percarbonate or perborate. Non-limiting examples of polymeric DTI materials
include
polyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole
copolymer, and mixtures thereof. Copolymers of N-vinylpyrrolidone and N-
vinylimidazole polymers (referred to as "PVPI") are also preferred for use
herein.
Another preferred optional component in the laundry bar is a secondary fabric
softener component in addition to the softening clay. Such materials can be
used at
levels of about 0.1% to 5%, more preferably from 0.3% to 3%, and can include:
amines
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of the fonnuia R4R5R6N, wherein R4 is C5 to C22 hydrocarbyl, R5 and R6 are
independently CI to CIO hydrocarbyl. One preferred amine is ditallowmethyl
amine;
complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is
C9 to
C22 hydrocarbyl, as disclosed in EP No. 0,133,804; complexes of such amines
with
phosphate esters of the formula R80-P(O)(OH)-OR9 and HO-P(O)(OH)-OR9, wherein
R8 and R9 are independently CI to C20 alkyl of alkyl ethoxylate of the formula
-alkyl-
(OCH2CH2); cyclic amines such as imidazolines of the general formula 1 -
(higher alkyl)
amido (lower alkyl)-2-(higher alkyl)imidazoline, where higher alkyl is from 12
to 22
carbons and lower alkyl is from I to 4 carbons, such as described in UK Patent
Application GB 2,173,827; and quatemary amrnonium compounds of the formula
R10R11R12R13N+X-, wherein RIO is alkyl having 8 to 20 carbons, Rl l is alkyl
having
I to 10 carbons, R12 and R13 are alkyl having 1 to 4 carbons, preferably
methyl, and X
is an anion, preferablyCl- or Br-, such as C 12-13 alkyl trimethyl ammonium
chloride.
Yet another optional component in the laundry bar is a bleach component. The
bleaching component can be a source of -OOH group, such as sodium perborate
monohydrate, sodium perborate tetrahydrate and sodium percarbonate. Sodium
percarbonate (2Na2CO3-3H2O2) is preferred since it has a dual function of both
a source
of HOOH and a source of sodium carbonate.
Another optional bleaching component is a peracid per se, such as a formula:
CH3(CH2)w-NH-C(O)-(CH2)zCO3H
wherein z is from 2 to 4 and w is from 4 to 10. (The compound of the latter
formula
where z is 4 and w is 8 is hereinafter referred to as NAPAA.) The bleaching
component
can contain, as a bleaching component stabilizer, a chelating agent of
polyaminocarboxylic acids, polyaminocarboxylates such as
ethylenediaminotetraacetic
acid, diethylenetriaminopentaacetic acid, and ethylenediaminodisuccinic acid,
and their
salts with water-soluble alkali metals. The bleach components can be added to
the bar at
a level up to 20%, preferably from about 1% to about 10%, more preferably from
about
2% to about 6%.
Sodium sulfate is a well-known filler that is compatible with the compositions
of
this invention. It can be a by-product of the surfactant sulfation and
sulfonation
processes, or it can be added separately.
TM
Calcium carbonate (also known as Calcarb) is also a well known and often used
component of laundry bars. Such materials are typically used at levels up to
40%,
preferably from about 5% to about 25%.
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Binding agents for holding the bar together in a cohesive, soluble form can
also
be used, and include natural and synthetic starches, gums, thickeners, and
mixtures
thereof.
Soil suspending agents can be used. In the present invention, their use is
balanced with the fabric softening clay/clay flocculating agent combination to
provide
optimum cleaning and fabric softening performance. Soil suspending agents can
also
include water-soluble salts of carboxymethylcellulose and carboxyhydroxy-
methylcellulose. A preferred soil suspending agent is an acrylic/maleic
copolymer,
commercially available as Sokolan , from BASF Corp. Other soil suspending
agents
include polyethylene glycols having a molecular weight of about 400 to 10,000,
and
ethoxylated mono- and polyamines, and quaternary salts thereof.
Optical brighteners are also preferred optional ingredients in laundry bars of
the
present invention. Preferred optical brighteners are diamino stilbene,
distyrilbiphenyl-
type optical brighteners. Preferred as examples of such brighteners are 4,4'-
bis{[4-
anilino-6-bis(2-hydoxyethyl) amino-1,3,5-trizin-2-yl]amino} stilbene-2,2'-
disulfonic acid
disodium salt, 4-4'-bis(2-sulfostyryl) biphenyl and 4,4'-bis[(4-anilino-6-
morpholino-
1,3,5-triazin-2-yl) amino] stilbene-2,2'-disulfonic acid disodium salt. Such
optical
brighteners, or mixtures thereof, can be used at levels in the bar of from
about 0.05% -
1.0%.
Dyes, pigments, germicides, and perfumes can also be added to the bar
composition.
Processes For preparing the compositions
The compositions of the present invention can be prepared in any conventional
manner appropriate to the desired form and application of the composition.
Such as
mixing, spray drying, plodding etc.
Processing of Laundry Bars- The detergent laundry bars of the present
invention can be
processed in conventional soap or detergent bar making equipment with some or
all of
the following key equipment: blender/mixer, mill or refining plodder, two-
stage vacuum
plodder, logo printer/cutter, cooling tunnel and wrapper.
In a typical process, the raw materials are mixed in the blender. Alkylbenzene
sulfonic acid (when used) is added into a mixture of alkaline inorganic salts
(preferably
which includes sodium carbonate) and the resulting partially neutralized
mixture is
mechanically worked to effect homogeneity and complete neutralization of the
mixture.
Once the neutralization reaction is completed, the alkyl sulfate surfactant is
added,
followed by the remaining other ingredient materials. The mixing can take from
1
minute to 1 hour, with the usual mixing time being from 2 to 20 minutes. The
blender
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mix is discharged to a surge tank. The product is conveyed from the surge tank
to the
mill or refining plodder via a multi-worn transfer conveyor.
The alkyl benzene sulfonic acid (HLAS) can be made by well-known processes,
such as with S03 or oleum. It can be preferably to include excess inorganic
sulfuric acid
(H2SO4) in the stock of HLAS, which, upon neutralization, helps to increase
the
temperature of the product due to the heat of neutralization of the inorganic
sulfuric acid.
After milling or preliminary plodding, the product is then conveyed to a
double
stage vacuum plodder, operating at a high vacuum, e.g. 600 to 740 millimeters
of
mercury vacuum, so that entrapped air is removed. The product is extruded and
cut to
the desired bar length, and printed with the product brand name. The printed
bar can be
cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent
to storage.
Examples of compositions of the present invention are listed hereafter by way
of
exemplification, and not by way of limitation.
EXAMPLES
The following examples illustrate the preparation and performance advantages
of
the suds boosting polymers containing compositions of the instant invention.
Such
examples, however, are not necessarily meant to limit or otherwise define the
scope of
the invention herein. All parts, percentages and ratios used herein are
expressed as
percent weight unless otherwise specified. In the following Examples, the
abbreviations
for the various ingredients used for the compositions have the following
meanings.
ABBREVIATIONS
LAS Sodium linear alkyl benzene sulfonate
MLAS Modified Alkyl Benzene sulfonate
MBASx Mid-chain branched primary alkyl (average total carbons =
x) sulfate
MBAEXSz Mid-chain branched primary alkyl (average total carbons =
z) ethoxylate (average EO = x) sulfate, sodium salt
MBAEx Mid-chain branched primary alkyl (average total
carbons = x) ethoxylate (average EO = 5)
Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by
NOVO Industries A/S
MEA Monoethanolamine
PG Propanediol
BPP Butoxy - propoxy - propanol
EtOH Ethanol
NaOH Solution of sodium hydroxide
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NaTS Sodium toluene sulfonate
Citric acid Anhydrous citric acid
CxyFA C 1 x-C 1 y fatty acid
CxyEz A C 1 x-1 y branched primary alcohol condensed with an
average of z moles of ethylene oxide
Carbonate Anhydrous sodium carbonate with a particle size
between 200 m and 900 m
Citrate Tri-sodium citrate dihydrate of activity 86.4% with a
particle size distribution between 425 m and 850 m
TFAA C 16-18 alkyl N-methyl glucamide
LMFAA C12-14 alkyl N-methyl glucamide
APA C8-C10 amido propyl dimethyl amine
Fatty Acid (C 12/ 14) C 12-C 14 fatty acid
Fatty Acid (TPK) Topped palm kernel fatty acid
Fatty Acid (RPS) Rapeseed fatty acid
Borax Na tetraborate decahydrate
PAA Polyacrylic Acid (mw = 4500)
PEG Polyethylene glycol (mw=4600)
MES Alkyl methyl ester sulfonate
SAS Secondary alkyl sulfate
NaPS Sodium paraffin sulfonate
C45AS Sodium C14-C15 linear alkyl sulfate
CxyAS Sodium Clx-Cly alkyl sulfate (or other salt if specified)
CxyEzS Sodium C 1 x-C 1 y alkyl sulfate condensed with z moles of
ethylene oxide (or other salt if specified)
CxyEz A Clx-ly branched primary alcohol condensed with an
average of z moles of ethylene oxide
AQA R2.N+(CH3)x((C2H4O)yH)z with R2 = C8 - C18 x+z = 3,
x = 0 to 3, z = 0 to 3, y = 1 to 15.
STPP Anhydrous sodium tripolyphosphate
Zeolite A Hydrated Sodium Aluminosilicate of formula
Na12(A102SiO2)12. 27H20 having a primary particle size
in the range from 0.1 to 10 micrometers
NaSKS-6 Crystalline layered silicate of formula 8-Na2Si2O5
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Carbonate Anhydrous sodium carbonate with a particle size between
200 m and 900 m
Bicarbonate Anhydrous sodium bicarbonate with a particle size
distribution between 400 m and 1200 m
Silicate Amorphous Sodium Silicate (Si02:Na2O; 2.0 ratio)
Sulfate Anhydrous sodium sulfate
PAE ethoxylated (15-18) tetraethylene pentamine
PIE ethoxylated polyethylene imine
PAEC methyl quaternized ethoxylated dihexylene triamine
MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular
weight about 70,000.
CMC Sodium carboxymethyl cellulose
Protease Proteolytic enzyme of activity 4KNPU/g sold by NOVO
Industries A/S under the trademark Savinase
Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO
Industries A/S under the trademark Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by NOVO
Industries A/S under the trademark Termamy160T
Lipase Lipolytic enzyme of activity 100kLU/g sold by NOVO
Industries A/S under the tradeinark Lipolase
PB1 Anhydrous sodium perborate bleach of nominal formula
NaBO2.H202
Percarbonate Sodium Percarbonate of nominal formula
2Na2CO3.3H2O2
NaDCC Sodium dichloroisocyanurate
NOBS Nonanoyloxybenzene sulfonate, sodium salt
TAED Tetraacetylethylenediamine
DTPMP Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under Trade mark Dequest 2060
Photoactivated bleach Sulfonated Zinc Phthalocyanine
bleach encapsulated in dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-
yl)amino) stilbene-2:2'-disulfonate.
HEDP 1, 1 -hydroxyethane diphosphonic acid
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SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and
terephthaloyl backbone
SRP 2 sulfonated ethoxylated terephthalate polymer
SRP 3 methyl capped ethoxylated terephthalate polymer
Silicone antifoam Polydimethylsiloxane foam controller with siloxane-
oxyalkylene copolymer as dispersing agent with a ratio of
said foam controller to said dispersing agent of 10:1 to
100:1.
SUDS 1 Poly(DMAM-co-DMA) (3:1) Copolymer prepared
according to Example 1 below
SUDS2 (DMAM), prepared according to Example 2 below
SUDS3 Poly(DMAM-co-AA) (2:1) Copolymer prepared according
to Example 3 below
SUDS4 Poly(DMAM-co-MAA) (2:1) Copolymer prepared
according to Example 4 below
SUDS5 Poly(DMAM-co-MAA-co-AA) (4:1:1) Terpolymer
prepared according to Example 5 below
SUDS6 Poly(DMAM-co-MAA-co-DMA) (4:1:1) Terpolymer
prepared according to Example 6 below
SUDS7 (DMAM), prepared according to Example 7 below
SUDS8 Poly(DMA -co-DMAM) (3:1) Copolymer, prepared
according to Example 8 below
SUDS9 zwitterionic polymer prepared according to Example 9
below
SUDS10 zwitterionic polymer prepared according to Example 10
below
SUDS 11 Polypeptide comprising Lys, Ala, Glu, Tyr (5:6:2:1) having
a molecular weight of approximately 52,000 daltons
SUDS 12 Lysozyme
SUDS 13 LX1279 available from Baker Petrolite
Isofol 16 Condea trademark for C 16 (average) Guerbet alcohols
CaCl2 Calcium chloride
MgC12 Magnesium chloride
DTPA Diethylene triamine pentaacetic acid
EXAMPLE 1
Preparation of Poly(DMAM-co-DMA) (3:1) Copolymer
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2-(Dimethylamino)ethyl methacrylate (20.00 g, 127.2 mmol), N,N-
dimethylacrylamide (4.20 g 42.4 mmol), 2,2'-azobisisobutyronitrile (0.14 g,
0.85 mmol),
1,4-dioxane (75 ml) and 2-propanol (15 ml) are placed into a 250 ml three-
necked round-
bottomed flask, fitted with a heating mantle, magnetic stirrer, internal
thermometer and
argon inlet. The mixture is subjected to three freeze-pump-thaw cycles to
remove
dissolved oxygen. The mixture is heated for 18 hours with stirring at 65 C.
TLC
(diethyl ether) indicates consumption of monomer. The mixture is concentrated
under
vacuum by rotary evaporation to remove the solvent. Water is added to make a
10%
solution and the mixture is dialyzed (3500 MWCO) against water, lyophilized
and then
pulverized in a blender to yield a white powder. NMR is consistent with the
desired
compound.
EXAMPLE 2
Preparation of Poly(DMAM) Polymer
2-(Dimethylamino)ethyl methacrylate (3000.00 g, 19.082 mol), 2,2'-
azobisisobutyronitrile (15.67 g, 0.095 mol), 1,4-dioxane (10.5 L) and 2-
propanol (2.1 L)
are placed into a 22 L three-necked round-bottomed flask, fitted with a reflux
condenser,
heating mantle, mechanical stirrer, internal thermometer and argon inlet. The
mixture is
sparged with argon for 45 minutes with vigorous stirring to remove dissolved
oxygen.
The mixture is heated for 18 hours with stirring at 65 C. TLC (diethyl ether)
indicates
consumption of monomer. The mixture is concentrated under vacuum by rotary
evaporation to remove the bulk of solvent. A 50:50 mixture of water:t-butanol
is added
to dissolve the product and the t-butanol is removed under vacuum by rotary
evaporation.
Water is added to make a 10% solution and the mixture is lyophilized and then
pulverized in a blender to yield a white powder. NMR is consistent with the
desired
compound.
EXAMPLE 3
Preparation of Poly(DMAM-co-AA) (2:1) Copolymer
2-(Dimethylamino)ethyl methacrylate (90.00 g, 572.4 mmol), acrylic acid (20.63
g, 286.2 mmol), 2,2'-azobisisobutyronitrile (0.70 g, 4.3 mmol), 1,4-dioxane
(345 ml) and
2-propanol (86 ml) are placed into a 1000 ml three-necked round-bottomed
flask, fitted
with a heating mantle, magnetic stirrer, internal thermometer and argon inlet.
The
mixture is sparged with nitrogen for 30 minutes to remove dissolved oxygen.
The
mixture is heated for 18 hours with stirring at 65 C. TLC (diethyl ether)
indicates
consumption of monomer. The mixture is concentrated under vacuum by rotary
evaporation to remove the solvent. Water is added to make a 10% solution and
the
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mixture is lyophilized and then pulverized in a blender to yield an off-white-
peach
powder. NMR is consistent with the desired compound.
EXAMPLE 4
Preparation of Poly(DMAM-co-MAA) (2:1) Copolymer
2-(Dimethylamino)ethyl methacrylate (98.00 g, 623.3 mmol), methacrylic acid
(26.83 g, 311.7 mmol), 2,2'-azobisisobutyronitrile (0.77 g, 4.7 mmol), 1,4-
dioxane (435
ml) and 2-propanol (108 ml) are placed into a 1000 ml three-necked round-
bottomed
flask, fitted with a heating mantle, magnetic stirrer, internal thermometer
and argon inlet.
The mixture is sparged with nitrogen for 30 minutes to remove dissolved
oxygen. The
mixture is heated for 18 hours with stirring at 65 C. TLC (diethyl ether)
indicates
consumption of monomer. The mixture is concentrated under vacuum by rotary
evaporation to remove the solvent. Water is added to make a 10% solution and
the
mixture is lyophilized and then pulverized in a blender to yield a white
powder. NMR is
consistent with the desired compound.
EXAMPLE 5
Poly(DMAM-co-MAA-co-AA) (4:1:1) Terpolymer
Poly(DMAM-co-MAA-co-AA) (4:1:1). The procedure of Example 4 is repeated
with the substitution of an equimolar amount of methacrylic acid with a 1:1
mixture of
methacrylic acid and acrylic acid.
EXAMPLE 6
Poly(DMAM-co-MAA-co-DMA) (4:1:1) Terpolymer
Poly(DMAM-co-MAA-co-AA) (4:1:1). The procedure of Example 4 is repeated
with the substitution of an equimolar amount of methacrylic acid with a 1:1
mixture of
methacrylic acid and N,N-dimethylacrylamide.
EXAMPLE 7
Preparation of Poly(DMAM) Polymer
Polyacrylic acid is esterified with 2-(dimethylamino)ethanol using well known
methods such as one described in Org. Syn. Coll. Vol. 3 610 (1955).
EXAMPLE 8
Preparation of Poly(DMA -co-DMAM) (3:1) Copolymer
The procedure of Example 1 is repeated except that 2-(dimethylamino)ethyl
methacrylate (6.67 g, 42.4 mmol), N,N-dimethylacrylamide (12.6 g 127.2 mmol)
is used
instead, to give a ratio in the polymer of DMA to DMAM of 3:1.
EXAMPLE 9
Preparation of zwitterionic polymer
Reaction of (1-octene/maleic anhydride) copolymer with 1 equivalent of DMAPA
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Poly(maleic anhydride-alt-l-octene) (15.00 g) and tetrahydrofuran (200 ml,
anhydrous) are placed into a 250 ml three-necked round-bottom flask, fitted
with a
heating mantle, magnetic stirrer, dropping funnel, internal thermometer and
argon inlet.
3-Dimethylaminopropylamine (7.65 g, 74.87 mmol) is added dropwise over 15
minutes,
with an exotherm to 30 C and heavy precipitation. The mixture is stirred for 4
hours at
55 C. The mixture is poured into 3:1 ethyl ether:hexanes to precipitate the
product
which is dried under vacuum to yield a white powder. NMR is consistent with
the
desired compound.
EXAMPLE 10
Reaction of (1-hexene/maleic anhydride) copolymer with 1 equivalent of DMAPA
Poly(maleic anhydride-alt-l-hexene) (15.00 g) and pyridine (450 ml, anhydrous)
are placed into a 250 ml three-necked round-bottom flask, fitted with a
heating mantle,
magnetic stirrer, dropping funnel, internal thermometer and argon inlet. There
is a slight
exotherm and the mixture is dark. 3-Dimethylaminopropylamine (9.25 g, 90.53
mmol) is
added dropwise over 15 minutes, with an exotherm to 45 C. The mixture is
stirred for 4
hours at 80 C. The mixture is concentrated by rotary evaporation, dissolved
into water
and lyophilized to yield a yellow powder. NMR is consistent with the desired
compound.
EXAMPLE 11
Preparation of LAS Powder for Use as a Structurant
Sodium C12 linear alkyl benzene sulfonate (NaLAS) is processed into a powder
containing two phases. One of these phases is soluble in the non-aqueous
liquid
detergent compositions herein and the other phase is insoluble. It is the
insoluble fraction
which serves to add structure and particle suspending capability to the non-
aqueous phase
of the compositions herein.
NaLAS powder is produced by taking a slurry of NaLAS in water (approximately
40-50% active) combined with dissolved sodium sulfate (3-15%) and hydrotrope,
sodium
sulfosuccinate (1-3%). The hydrotrope and sulfate are used to improve the
characteristics
of the dry powder. A drum dryer is used to dry the slurry into a flake. When
the NaLAS
is dried with the sodium sulfate, two distinct phases are created within the
flake. The
insoluble phase creates a network structure of aggregate small particles (0.4-
2 um) which
allows the finished non-aqueous detergent product to stably suspend solids.
The NaLAS powder prepared according to this example has the following makeup
shown below.
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LAS Powder
Component Wt. %
NaLAS 85%
Sulfate 11%
Sulfosuccinate 2%
Water 2.5%
Unreacted, etc. balance to 100%
% insoluble LAS 17%
# of phase (via X-ray diffraction) 2
EXAMPLE 12
Non-aqueous based heavy duty liquid laundry detergent compositions (A to E)
which comprise the mid-chain branched surfactants of the present invention are
presented
below.
Non-Aqueous Liquid Detergent Composition with Bleach
Component Wt % Wt % Wt % Wt % Wt %
A B C D E
LAS, From Example I 16 13 36 8 2
Mid-branched Surfactant 22 25 0 30 34
BPP 19 19 19 19 19
Sodium citrate dihydrate 3 3 3 3 3
Bleach activator 5.9 5.9 5.9 5.9 5.9
Sodium carbonate 9 9 9 9 9
SUDS3 0.2 0.5 1.0 0.1 0.5
Maleic-acrylic copolymer 3 3 3 3 3
Colored speckles 0.4 0.4 0.4 0.4 0.4
EDDS 1 1 1 1 1
Cellulase Prills 0.1 0.1 0.1 0.1 0.1
Amylase Prills 0.4 0.4 0.4 0.4 0.4
Ethoxylated diamine quat 1.3 1.3 1.3 1.3 1.3
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Sodium Perborate 15 15 15 15 15
Optionals including: brightener, balance balance balance balance balance
colorant, perfume, thickener,
suds suppressor, colored
speckles etc.
100% 100% 100% 100% 100%
The resulting compositions are stable, anhydrous heavy-duty liquid laundry
detergents which provide excellent stain and soil removal performance when
used in
normal fabric laundering operations.
EXAMPLE 13
A non-limiting example of bleach-containing nonaqueous liquid laundry
detergent is prepared having the composition as set forth below.
Component Wt. % Range (% wt.)
Liquid Phase
LAS 25.0 18-35
C24 E5 or MBAE14.3 13.6 10-20
Hexylene glycol 27.3 20-30
Perfume 0.4 0-1.0
SUDS 1 0.2 0.01 to 5.0
MBAE2S 14.4 2.3 1-3.0
Solid Phase
Protease 0.4 0-1.0
Citrate 4.3 3-6
PB 1 3.4 2-7
NOBS 8.0 2-12
Carbonate 13.9 5-20
DTPA 0.9 0-1.5
Brightener 1 0.4 0-0.6
Silicone antifoam 0.1 0-0.3
Minors Balance ----
The resulting composition is an anhydrous heavy duty liquid laundry detergent
which provides excellent stain and soil removal performance when used in
normal fabric
laundering operations.
EXAMPLE 14
Liquid detergent compositions are made according to the following.
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A B C D
C25 AE3S 2 8 17 5
MBAS 14.4 15 12 0 8
C 12-C 14 alkyldimethyl amine oxide - _ - 2
SUDS2 0.1 0.2 2.0 0.7
C25 AS 6 4 6 8
C24 N-methyl glucamide 5 4 3 3
C24 AE5 6 1 1 1
C 12-C 18 fatty acid 11 4 4 3
Citric acid 1 3 3 2
DTPMP 1 1 1 0.5
MEA 8 5 5 2
NaOH 1 2.5 1 1.5
PG 14.5 13.1 10.0 8
EtOH 1.8 4.7 5.4 1
Amylase (300KNU/ ) 0.1 0.1 0.1 0.1
Li ase D96/L (100KNU/g) 0.15 0.15 0.15 0.15
Protease (35g/1) 0.5 0.5 0.5 0.5)
Endolase 0.05 0.05 0.05 0.05
Cellulase 0.09 0.09 0.09 0.09
Terephthalate-based polymer 0.5 - 0.3 0.3
Boric acid 2.4 2.8 2.8 2.4
Sodium xylene sulfonate - 3 - -
2-butyl-octanol 1 1 1 1
Branched silicone 0.3 0.3 0.3 0.3
Water & minors Up to 100%
The above liquid detergent compositions (A-D) are found to be very efficient
in
the removal of a wide range of stains and soils from fabrics under various
usage
conditions.
The Following Examples illustrate aqueous based liquid detergent compositions
according to the present invention.
EXAMPLE 15
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Aqueous based heavy duty liquid laundry detergent compositions F to J which
comprise the mid-chain branched surfactants of the present invention are
presented
below.
Ingredient F G H I J
MBAE1.8S14.4 10 12 14 16 20
Na C25AE1.8S 10 8 6 4 0
C23E9 2 2 2 2 2
LMFAA 5 5 5 5 0
SUDS3 0.01 0.2 1.0 1.5 0.8
Citric acid builder 3 3 3 3 5
Fatty acid builder 2 2 2 2 0
PAE 1 1 1.2 1.2 0.5
PG 8 8 8 8 4.5
EtOH 4 4 4 4 2
Boric acid 3.5 3.5 3.5 3.5 2
Sodium Cumene 3 3 3 3 0
Sulfonate
pH 8.0 8.0 8.0 8.0 7.0
Enz es, dyes, water balance balance balance balance balance
100% 100% 100% 100% 100%
EXAMPLE 16
The following aqueous liquid laundry detergent compositions K to 0 are
prepared
in accord with the invention:
K L M N 0
MBAE1.8S14.4and/or 0 7-12 12-17 17-22 1-35
MBAS 14.4
Anycombinationof: 15-21 10-15 5-10 0-5 0-25
C25 AExS*Na (x = 1.8 - 2.5)
C25 AS (linear to high 2-alkyl)
C14-17 NaPS
C12-16 SAS
C18 1,4 disulfate
LAS
C12-16 MES
LMFAA 0-3.5 0-3.5 0-3.5 0-3.5 0-8
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C23E9orC23E6.5 0-2 0-2 0-2 0-2 0-8
SUDS13 0.15 0.35 0.55 1.75 0.3
APA 0.5 0.5 0.5 0.5 0.5 - 2
Citric Acid 5 5 5 5 0-8
Fatty Acid (TPK or C12/14) 2 2 2 2 0- 14
EtOH 4 4 4 4 0-8
PG 6 6 6 6 0-10
MEA 1 1 1 1 0-3
NaOH 3 3 3 3 0-7
Na TS 2.3 2.3 2.3 2.3 0-4
Na formate 0.1 0.1 0.1 0.1 0-1
Borax 2.5 2.5 2.5 2.5 0-5
Protease 0.9 0.9 0.9 0.9 0-1.3
Lipase 0.06 0.06 0.06 0.06 0- 0.3
Amylase 0.15 0.15 0.15 0.15 0-0.4
Cellulase 0.05 0.05 0.05 0.05 0- 0.2
PAE 0-0.6 0-0.6 0-0.6 0-0.6 0-2.5
PIE 1.2 1.2 1.2 1.2 0-2.5
PAEC 0-0.4 0-0.4 0-0.4 0-0.4 0-2
SRP 2 0.2 0.2 0.2 0.2 0-0.5
Brightener 1 or 2 0.15 0.15 0.15 0.15 0-0.5
Silicone antifoam 0.12 0.12 0.12 0.12 0- 0.3
Fumed Silica 0.0015 0.0015 0.0015 0.0015 0-0.003
Perfume 0.3 0.3 0.3 0.3 0- 0.6
Dye 0.0013 0.0013 0.0013 0.0013 0-0.003
Moisture/minors Balanc Balanc Balanc Balanc Balance
e e e e
Product pH in DI water) 7.7 7.7 7.7 7.7 6-9.5
Various bar compositions can be made using the method described above.
EXAMPLE 17
A B C D E F G H I
(weight percent)
NaCFAS (C12-18) 15.75 15.75 19.13 11.20 22.50 13.50
Na(C12-18)LAS 6.75 6.75 3.38 8.80 19.00 15.00 21.00
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Na2CO3 15.00 5.00 15.00 15.00 10.0 3.00 13.0 8.00 10.0
DTPP 1 0.70 0.70 0.70 0.70 0.70 0.70 0.60 0.60
SUDS 13 0.5 0.1
SUDS3 0.2 0.25 0.8 0.15 0.2
SUDS12 0.2 0.2
SUDS1 0.2 0.2 0.2 0.2
PEO-300M 2 0.30 0.30
PEO-600M 0.20 0.20
Bentonite clay 10.0 10.0 5.0
Sokolan CP-5 3 0.40 0.70 0.40 0.70 0.40 1.00 0.20
TSPP 5.00 5.00 5.00 5.00 5.00
STPP 5.00 10.00 5.00 10.00 10.00 15.00
Zeolite 1.25 1.25 1.25 1.25 1.25 1.25
Sodium laurate 9.00
SRP-A 4 0.30 0.30 0.30 0.30 0.30 0.30 0.22 0.22
Protease enzyme 5 0.08 0.12 0.08 0.08
Amylase enzyme 6 0.80 0.80
Lipase enzyme 0.10 0.10
Cellulase enzyme 7 0.15 0.15
------------------------ Balance 8 ----------------------
1. Sodium diethylenetriamine penta (phosphonate)
2. PEO is poly(ethylene oxide) having a molecular weight as indicated.
3. Sokolan CP-5 is maleic-acrylic copolymer
4. SRP-A is
Na03 S(CH2CH2O)2-C(O)-(C6H4)-C(O)O-[-CH2CRH-O-C(O)-(C6H4)-
C(O)O-]4-
-[-CH2CRH-O-C(O)-(C6H4)SO3Na-C(O)O-] 1-
CH2CH2OCH2CH2SO3Na,
wherein R is H or CH3 in a ratio of about 1.8:1.
5. Protease activity at 1 Au/gm stock.
6. Amylase activity at 100,000 amu/gm stock.
7. Carezyme cellulase, supplied by Novo Nordisk, activity at 5000 Cevu/gm
stock.
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8. Balance comprises water (about 2% to 8%, including water of hydration),
sodium sulfate, calcium carbonate, and other minor ingredients.
EXAMPLE 18
The following compositions were made by mixing the listed ingredients in the
listed
proportions. These compositions were used neat to clean marble and dilute to
clean
lacquered wooden floors. Excellent cleaning and surface safety performance was
observed.
A B C D E F G H
MLAS 3.0 3.0 5.0 3.2 3.2 3.2 8.0 8.0
Dobanol 0 23-3 1.0 1.0 1.5 1.3 1.3 1.5 3.0 3.5
TM
Empilan KBE21+ 2.0 2.0 2.5 1.9 1.9 2.0 5.0 6.0
NaPS 2.0 1.5 1.2 1.2 1.0 1.7 3.0 2.5
StJDS5 0.1 2.5 0.1 0.05 0.2 0.3 0.5 0.25
NaCS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0
MgSO 4 0.20 0.9 0.30 0.50 1.3 2.0 1.0 3.0
Citrate 0.3 1.0 0.5 0.75 1.8 3.0 1.5 6.0
NaHCO; 0.06 0.1 - 0.1 - 0.2 - -
Na HPOa - - 0.1 - 0.3 - - -
Na?HZP~07 - - - - - - 0.2 0.5
pH 8.0 7.5 7.0 7.25 8.0 7.4 7.5 7.2
Water and Minors q.s. to 100%
As used hereinabove:
-NaPS stands for Na paraffin sulphonate
-NaCS stands for Na cumene sulphonate
-Dobanol 23-3 is a C12-13 alcohol ethoxylated with an average ethoxylation
degree of
3.
-Empilan KBE21 is a C12-14 alcohol ethoxylated with an average ethoxylation
degree of
21.
EXAMPLE 19
I J K L M N
C13-15 E030 1 - - - - -
C12-14 E020 - - 1 1.7 - -
C12-14P03EO7 - - - - - 2
C12-14 EO10 - - - - 2 -
C10-12 EO10 - 1.5 - - - -
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SUDS7 0.2 0.1 0.3 0.5 0.2 0.1
MLAS - - 2.4 - 2.4 2.4
C11EO5 - - - 5 - -
C12-14 E05 4.2 3.0 3.6 - 3.6 3.6
C9-11 E04 - 3.0 - - - -
C12-OH - 0.3 - - - -
2-Hexyl decanol - - - 0.4 - -
2-Butyl octanol 0.3 - 0.3 - 0.3 0.3
MBAS - - 1.0 - 1.0 1.0
MBAES 1.0 1.3 - 1.5 - -
Citrate 0.7 1.0 0.7 1.0 0.7 0.7
Na2CO3 0.6 0.7 0.6 0.3 0.6 0.6
EXAMPLE 20
The following compositions were made by mixing the listed ingredients in the
listed
proportions:
Weight %
Ingredients FF GG HH II
MLAS 4 - 3 4
Alcohol ethoxylate 30E0 (1) 2 - - 2
Alcohol ethoxylate 12E0 (2) - 3 - -
Alcohol benzene ethoxylate 10EO (4) - - 3 -
SUDS8 0.1 0.2 0.2 0.5
Citric acid 2 2 2 3
Butylcarbitol R 4 4 4 7
n-butoxypropoxypropanol - - - 2.5
Triethanolamine 1 1 2 1
water & minors q.s. to 100%
In the examples hereinabove, (1) is a highly ethoxylated nonionic surfactant
wherein R
is a mixture of C13 and C15 alkyl chains and n is 30. (2) is a highly
ethoxylated
nonionic surfactant wherein R is a mixture of C 13 and C 15 alkyl chains and n
is 12. (3)
is a lower ethoxylated nonionic surfactant wherein n is 7. (4) is a highly
ethoxylated
nonionic surfactant wherein R is a mixture of C 19 and C21 alkyl benzene
chains and n
is 10.
Compositions FF-MM described hereinabove can be used neat or diluted. In a
method
according to the present invention, these compositions are diluted in 65 times
their
weight of water and applied to a hard surface.
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EXAMPLE 21
The following compositions were tested for their cleaning performance when
used diluted on greasy soil.
The following compositions were made by mixing the listed ingredients in the
listed proportions:
Weight %
Ingredients NN 00 PP
Sodium paraffin sulfonate 1.0 3 3
Alcohol ethoxylate 7E0 4 - -
Alcohol ethoxylate 30E0 - 3 2
C12-14 E021 alcohol ethoxylate 1.0 - -
SUDS3 0.2 0.3 4.0
MLAS 5.0 0 2
Sodium Citrate 3 3 3
Butylcarbitol R 4 4 4
Triethanolamine 1 1 1
water & minors up to 100%
EXAMPLE 22
A SHAMPOO COMPOSITION
Weight %
Components A B
TEA C12 -C14 Alkyl Sulfate 10.00 -
NH4 C 12-C 14 Alkyl (Ethoxy)3 Sulfate - 7.90
SUDS 1 0.2 1.0
Cocamide MEA 3.00 1.50
Dimethicone DC-200* 3.00 3.00
Ethylene Glycol Disterate 1.50 1.50
Citric acid 0.60 0.60
Trisodium citrate 0.30 -
Q.S. Color, preservative, Perfume and q.s. to 100% g.s. to 100%
water
EXAMPLE 23
The following are personal cleansing compositions of the present invention.
Component Weight %
C D
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Ammonium Lauryl Sulfate 2.5 9.5
Ammonium Laureth (3) Sulfate 8.5 8.5
JAGUAR C-171 0.5 0.5
MBAS 6.0 -
SUDS9 1.0 0.3
Coconut Monoethanol Amide 1.0 1.0
Ethylene Glycol Distearate 2.0 2.0
Isocetyl Stearoyl Stearate 1.0 1.0
Tricetyl Methyl Ammonium 0.5 0.5
Chloride
Polydimethylsiloxane2 2.0 2.0
Cetyl Alcohol 0.4 0.4
Stearyl Alcohol 0.2 0.2
Perfume 1.0 1.0
Color Solution 0.6 0.6
Preservative 0.4 0.4
Water and Minors q.s to 100% q.s to 100%
1. Trademark for guar hydroxypropyltrimonium chloride, a cationic polymer
available
from Rhone-Poulenc (Cranbury, NJ, USA).
2. A 40/60 weight ratio blend of poiydimethylsiloxane gum (GE SE 76, available
from
General Electric Co., Silicone Products Div., Waterford, NY, USA) and
polydimethylsiloxane fluid (about 350 centistokes).
The composition can provide excellent in-use hair cleaning and conditioning.
As an
alternative, the JAGUAR C-17 can be replaced with LUVIQUAT FC 370.
EXAMPLE 24
The following are personal cleansing compositions of the present invention.
Component Wei2ht %
E F
Ammonium Lauryl Sulfate 4.2 2.2
Ammonium Laureth (3) Sulfate 9.2 9.2
POLYMER LR 4001 1.0 1.0
MBAS - 6.0
Coconut Monoethanol Amide 1.0 1.0
Ethylene Glycol Distearate 2.0 2.0
Light Mineral Oil 1.0 1.0
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Tricetyl Methyl Ammonium 0.5 0.5
Chloride
SUDS 1 0.75 1.25
Polydimethylsiloxane2 1.5 1.5
Cetyl Alcohol 0.4 0.4
Stearyl Alcohol 0.2 0.2
Perfume 1.2 1.2
Color Solution 0.6 0.6
Preservative 0.4 0.4
Water and Minors q.s. to 100% q.s. to 100%
1. Cellulose, 2-[2-hydroxy-3-(trimethyl ammonio)propoxy] ethyl ether,
chloride, a
cationic polymer available from Amerchol Corp. (Edison, NJ, USA).
2. A 40/60 weight ratio blend of polydimethylsiloxane gum (GE SE 76, available
from
General Electric Co., Silicone Products Div., Waterford, NY, USA) and
polydimethylsiloxane fluid (about 350 centistokes).
The composition can provide excellent in-use hair cleaning and conditioning
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EXAMPLE 25
The following is an example of a personal cleansing composition of the present
invention
wherein the cationic polymer and anionic surfactant component form a complex
coacervate phase.
Component Weight.%
G
Ammonium Laureth (3) Sulfate 4.0
LUVIQUAT FC 3701 0.5
BAS2 13.5
Coconut Monoethanol Amide 1.0
Ethylene Glycol Distearate 2.0
Light Mineral Oil 0.5
SUDS8 0.45
Tricetyl Methyl Ammonium Chloride 0.5
Polydimethylsiloxane2 3.0
Cetyl Alcohol 0.4
Stearyl Alcohol 0.2
Perfume 1.0
Color Solution 0.6
Preservative 0.4
Water and Minors 73.8
1. Trademark of BASF Wyandotte Corporation (Parsippany, NJ, USA) for copolymer
of
vinyl pyrrolidone and methyl vinyl imidazolium chloride.
2. The Mid-Chain Branched surfactants according to example B.
3. A 40/60 weight ratio blend of polydimethylsiloxane gum (GE SE 76, available
from
General Electric Co., Silicone Products Div., Waterford, NY, USA) and
polydimethylsiloxane fluid (about 350 centistokes).
The composition can provide excellent in-use hair cleaning and conditioning.
As an
alternative, the LUVIQUAT FC 370 can be replaced with JAGUAR C-17.
EXAMPLE 26
The following is an example of a personal cleansing composition of the present
invention.
Component Weight %
H
Cocoamidopropyl Betaine 4.0
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Ammonium Laureth (3) Sulfate 8.0
Coconut Monoethanol Amide 2.0
Ethylene Glycol Distearate 2.0
Polymer JR-1251 1.0
MBAS 4.0
SUDS2 0.2
Isopropyl Isostearate 1.0
Tricetyl Methyl Ammonium Chloride 0.5
Polydimethylsiloxane2 1.5
Cetyl Alcohol 0.4
Stearyl Alcohol 0.2
Perfume 1.0
Color Solution 0.6
Preservative 0.4
Water and Minors q.s.to 100%
1. Cellulose, 2-[2-hydroxy-3-(trimethyl ammonio)propoxy] ethyl ether,
chloride,
available from Amerchol Corp. (Edison, NJ, USA).
TM
2. VISCASIL 12,500 cS silicone fluid, available from General Electric
(Waterford, NY,
USA).
EXAMPLE 27
The following are personal cleansing compositions of the present invention.
Component Weipht %
I J Ammonium Lauryl Sulfate 8.5 2.0
Ammonium Laureth (3) Sulfate 4.0 4.0
Polymer LM-2001 1.0 1.0
MBAS 5.0 11.5
Light Mineral Oil 1.0 1.0
Coconut Monoethanol Amide 1.0 1.0
Ethylene Glycol Distearate 2.0 2.0
SUDS6 0.6 0.1
Tricetyl Methyl Ammonium Chloride 0.5 0.5
Poiydimethylsiloxane2 3.0 3.0
Cetyl Alcohol 0.4 0.4
Stearyl Alcohol 0.2 0.2
Perfume 1.0 1.0
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Color Solution 0.6 0.6
Preservative 0.4 0.4
Water and Minors q.s. to q.s. to
100% 100%
1. Polyquatcrnium 24, a polymeric quaternary ammonium salt of hydroxyethyl
cellulose
reacted with lauryl dimethyl ammonium-substituted epoxide, available from
Amerchol
Corp. (Edison, NJ, USA).
2. A 40/60 weight ratio blend of polydimethylsiloxane gum (GE SE 76, available
from
General Electric Co., Silicone Products Div., Waterford, NY, USA) and
polydimethylsiloxane fluid (about 350 centistokes).
Example 28
The following is a personal cleansing composition of the present invention
wherein the
cationic polymer and anionic surfactant component form a complex coacervate
phase.
Component Weight %
K
Ammonium Laureth (3) Sulfate 8.5
GAFQUAT 755N1 0.5
FLEXAN 1303 0.5
Coconut Monoethanol Amide 1.0
Ethylene Glycol Distearate 2.0
MBAS 8.5
Isocetyl Stearoyl Stearate 1.0
Tricetyl Methyl Ammonium Chloride 0.5
Polydimethylsiloxane2 2.0
Cetyl Alcohol 0.4
SUDS5 0.1
Stearyl Alcohol 0.2
Perfume 1.0
Color Solution 0.6
Preservative 0.4
Water and Minors q.s. to 100%
1. Copolymer of 1-vinyl-2-pyrrolidone and dimethylamino-
ethylmethacrylate, available from GAF Corp., Wayne, NJ, USA.
2. VISCASIL, 600,000 cS, from General Electric, Waterford, NY, USA.
3. Sodium polystyrene sulfonate, an anionic polymer available from National
Starch and
Chemical Corp., Bridgewater, NJ, USA.
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The composition can provide excellent in-use hair cleaning and conditioning.
The example compositions hereof can be made by preparing a premix of the
entire
amount of silicone conditioning agent to be incorporated into the personal
cleansing,
along with sufficient ammonium sulfate and cetyl and stearyl alcohol such that
the
premix comprises about 30% silicone conditioning agent, about 69% surfactant,
and
about 1% of the alcohols. The premix ingredients are heated and stirred at
720C for
about 10 minutes and the premix is then conventionally mixed with the
remaining hot
(720C) ingredients. The composition is then pumped through a high shear mixer
and
cooled.
EXAMPLE 29
The following examples, (L to Z), further describe and demonstrate embodiments
within the scope of the present invention. The examples are given solely for
the purpose
of illustration and are not to be construed as limitations of the present
invention, as many
variations thereof are possible without departing from the spirit and scope of
the
invention. These exemplified embodiments of the shampoo compositions of the
present
invention provide cleansing of hair and improved hair conditioning
performance.
Ingredients are hereinafter identified by chemical, trade, or CTFA name.
Preparation The shampoo compositions of the present invention can be prepared
by using
conventional mixing and formulating techniques. The shampoo compositions
illustrated
hereinafter in Examples L to Z are prepared in the following manner.
About one-third to all of the total sulfate surfactant (added as a 25%
solution) is
added to a jacketed mix tank and heated to about 74 C with slow agitation to
form a
surfactant solution. Cocamide MEA and fatty alcohol, as applicable, are added
to the
tank and allowed to disperse. Ethylene glycol distearate (EGDS), as
applicable, is then
added to the mixing vessel, and melted. After the EGDS is well dispersed
(usually about
to 20 minutes) polyethylene glycol and the preservative, if used are added and
mixed
into the surfactant solution. This mixture is passed through a heat exchanger
where it is
cooled to about 35 C and collected in a finishing tank. As a result of this
cooling step,
the ethylene glycol distearate crystallizes to form a crystalline network in
the product.
The remainder of the surfactant and other ingredients including the silicone
emulsions are
added to the finishing tank with ample agitation to insure a homogeneous
mixture. A
sufficient amount of the silicone emulsions are added to provide the desired
level of
dimethicone in the final product. Water dispersible polymers are typically
dispersed in
water as a 1% to 10% solution before addition to the final mix. Once all
ingredients have
been added, ammonium xylene sulfonate or additional sodium chloride can be
added to
the mixture to thin or thicken respectively to achieve a desired product
viscosity.
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Preferred viscosities range from about 2500 to about 9000 cS at 25 C (as
measured by a
Wells-Brookfield cone and plate viscometer at 15/s).
Component L M N 0 P
Ammonium BAS 2 4 4 5 4
Ammonium BAES 8 6 12 10 12
Cocamidopropylbetaine 0 0 2.5 0 1
Jaguar C175 0.05 0.05 0.05 0.30 0.15
SUDS3 0.2 2.5 0.2 0.15 0.5
Cocamide MEA 0.5 0.5 0.80 0.80 0
Cetyl Alcohol 0 0 0.42 0.42 0.42
Stearyl Alcohol 0 0 0.18 0.18 0.18
Ethylene Glycol Distearate 1.50 1.50 1.50 1.50 1.50
EP Siliconel 3.0 2.5 3.0 2.0 3.0
Perfume Solution 0.70 0.70 0.70 0.70 0.70
DMDM Hydantoin 0.37 0.37 0.37 0.37 0.37
Color Solution (ppm) 64 64 64 64 64
Water and Minors --------- q.s. to 100% ---------
Component Q R S T U
Ammonium BAES 9.00 9.00 14.0 14.85 12.50
Cocamidopropylbetaine 1.70 1.70 2.70 1.85 4.20
Polyquaternium-103 0.05 0.02 0.15 0.15 0.15
Cocamide MEA 0.80 0.80 0.80 0.80 0
SUDS2 0.2 0.36 0.42 1.0 0.15
Cetyl Alcohol 0 0 0.42 0.42 0.42
Stearyl Alcohol 0 0 0.18 0.18 0.18
Ethylene Glycol Distearate 1.50 1.50 1.50 1.50 1.50
EP Silicone4 3.0 2.5 3.0 2.0 3.0
Perfume Solution 0.70 0.70 0.70 0.70 0.70
DMDM Hydantoin 0.37 0.37 0.37 0.37 0.37
Color Solution (ppm) 64 64 64 64 64
Water and Minors --------- q.s. to 100% ---------
Component V W X Y Z
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Ammonium BAES 14.0 14.00 14.00 9.00 9.00
Cocamidopropylbetaine 2.70 2.70 2.70 1.70 1.70
Polyquaternium-106 0. 0.15 0.15 0.05 0.02
Cocamide MEA 0.80 0.80 0 0.80 0.80
Cetyl Alcohol 0 0.42 0 0 0
SUDS9 0.2 0.36 0.58 0.37 1.25
Stearyl Alcohol 0 0.18 0 0 0
Ethylene Glycol Distearate 0 0 0 1.50 1.50
Carbopo19812 0.50 0.50 0.50 0 0
EP Siliconel 3.0 2.5 3.0 2.0 3.0
Perfume Solution 0.70 0.70 0.70 0.70 0.70
DMDM Hydantoin 0.37 0.37 0.37 0.37 0.37
Color Solution (ppm) 64 64 64 64 64
Water and Minors --------- q.s. to 100% ---------
1. EP Silicone is an experimental emulsion polymerized polydimethyl siloxane
of about
97,000 csk with particle size of approximately 300 nm made via linear
feedstock
available from Dow Corning (2-1520; 13556-34).
2. Carbopol 981 is a crosslinked polyacrylate available from B.F. Goodrich.
3. Polyquaternium-10 is JR30M, a cationic cellulose derived polymer available
from
Amerchol.
4. EP Silicone is an experimental emulsion polymerized polydimethyl siloxane
of about
335,000 csk with particle size of approximately 500 nm made via linear
feedstock
available from Dow Corning (2-1520; PE106004).
5. Jaguar C 17 is a cationic polymer available from Rhone-Poulenc
6. Polyquaternium-10 is JR400, a cationic cellulose derived polymer available
from
Amerchol.
EXAMPLE 30
A shampoo having the following formula is prepared
Component % weight
AA
BAS 17
Zinc Pyridinethione* 2.0
Coconut Monoethanolamide 3.0
Ethylene Glycol Distereate 5.0
Sodium Citrate 0.5
SUDS7 0.3
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Citric Acid 0.2
Color solution 0.1
Perfume 0.5
Water q.s. to 100.00%
* The Zinc pyridinethione salt crystals prepared according to the method
described in
U.S. Patent No. 4,379,753 to Bolich.
Component % weight
BB
Triethanolamine alkyl sulfate 10%
BAS 9
Zinc Pyridinethione* 2.0
Coconut Monoethanolamide 2.0
SUDS 1 0.33
Triethanolamine 3.0
Magnesium/Aluminium Silicate 0.5
Hydroxy Methyl Cellulose 0.6
Color solution 0.1
Perfume 0.3
Water q.s. to 100.00%
* The Zinc pyridinethione salt crystals prepared according to the method
described in
U.S. Patent No. 4,379,753 to Bolich.
Component % weight
CC
Sodium Alkyl Glyceryl Sulfonate 5%
BAS 15
Zinc Pyridinethione* 2.0
SUDS2 0.2
Sodium Chloride 5.0
Sodium N-Lauryl Sarcosinate 12.0
N-Cocoyl Sarcosine Acid 1.0
Lauric Diethanolamide 2.0
Color solution 0.12
Perfume 0.5
Water q.s. to 100.00%
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* The Zinc pyridinethione salt crystals prepared according to the method
described in
U.S. Patent No. 4,379,753 to Bolich.
EXAMPLE 31
The compositions illustrated in Example 31 (DD to TT), illustrate specific
embodiments of the shampoo compositions of the present invention, but are not
intended
to be limiting thereof. Other modifications can be undertaken by the skilled
artisan
without departing from the spirit and scope of this invention. These
exemplified
embodiments of the shampoo compositions of the present invention provide
excellent
cleansing of hair and dandruff control.
All exemplified compositions can be prepared by conventional formulation and
mixing techniques. Component amounts are listed as weight percents and exclude
minor materials such as diluents, filler, and so forth. The listed
formulations, therefore,
comprise the listed components and any minor materials associated with such
components.
Component DD EE FF GG HH
Ammonium Laureth Sulfate 15.00 15.00 15.00 15.00 7.50
BAS 5.00 5.00 5.00 5.00 2.50
Sodium Lauroyl Sarcosinate 1.50 1.50 1.50 1.50 0.75
Ethylene Glycol Distearate 1.50 1.50 1.50 1.50 1.50
SUDS3 0.2 0.55 0.75 0.8 1.25
Zinc Pyrithione 1.00 1.00 1.00 --- 1.00
Selenium Disulfide --- --- --- 1.00 ---
Jaguar C17S 0.10 0.05 0.50 0.10 0.10
Fragrance q.s. q.s. q.s. q.s. q.s.
Color q.s. q.s. q.s. q.s. q.s.
pH adjustment (Mono/Di sodium q.s. q.s. q.s. q.s. q.s.
Phosphate)
viscosity adjustment (Sodium q.s. q.s. q.s. q.s. q.s.
Chloride,
preservative (DMDM q.s. q.s. q.s. q.s. q.s.
Hydantoin); Water
Component JJ KK LL MM NN
BAES 7.50 15.00 15.00 10.00 10.00
BAS 2.50 5.00 5.00 2.50 2.50
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Cocamidopropyl Betaine --- --- --- 2.50 2.50
Sodium Lauroyl Sarcosinate 0.75 --- --- --- ---
Ethylene Glycol Distearate 1.50 1.50 1.50 1.50 1.50
SUDS6 0.1 0.85 0.15 0.2 0.3
Ketoconazole 1.00 1.00 1.00 1.00 1.00
Jaguar C 13 S --- 0.10 --- 0.10 ---
Jaguar C17S 0.05 --- 0.10 --- 0.10
Fragrance q.s. q.s. q.s. q.s. q.s.
Color q.s. q.s. q.s. q.s. q.s.
pH adjustment (Mono/Di q.s. q.s. q.s. q.s. q.s.
sodium Phosphate)
Sodium Sulfate, PEG-600, q.s. q.s. q.s. q.s. q.s.
Ammonium Xylene Sulfonate)
preservative (DMDM q.s. q.s. q.s. q.s. q.s.
Hydantoin) Water
Component 00 PP QQ RR SS TT
Ammonium Laureth Sulfate 0 15.00 0 15.00 15.00 0
BAS 5.00 5.00 5.00 5.00 5.00 5.00
BAES 15.00 0 15.00 0 0 15.00
Cocamidopropyl Betaine 2.00 --- --- --- --- ---
Sodium Lauroyl Sarcosinate --- 1.50 1.50 --- --- ---
Sodium Cocoyl Glutamate --- --- --- --- --- 1.50
SUDS5 0.2 0.9 0.1 0.2 0.2 1.5
Ethylene Glycol Distearate 1.50 1.50 1.50 1.50 1.50 1.50
Stearyl Alcohol --- --- --- --- --- ---
Zinc Pyrithione 1.00 0.30 0.30 0.30 0.30 1.00
Jaguar C 13 S 0.20 --- --- 0.10 0.05 ---
Jaguar C17S --- 0.10 0.05 --- --- 0.10
Fragrance q.s. q.s. q.s. q.s. q.s. q.s.
Color q.s. q.s. q.s. q.s. q.s. q.s.
pH adjustment (Mono/Di q.s. q.s. q.s. q.s. q.s. q.s.
sodium Phosphate)
viscosity adjustment q.s. q.s. q.s. q.s. q.s. q.s.
(Sodium Chloride,)
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preservative (DMDM q.s. q.s. q.s. q.s. q.s. q.s.
Hydantoin)
Water q.s. q.s. q.s. q.s. q.s. q.s.
In preparing each of the compositions described in Examples DD to TT, about
one-third of the surfactant (added as 25wt% solution) is added to a jacketed
mix tank and
heated to about 74 C with slow agitation to form a surfactant solution. Salts
(sodium
chloride) and pH modifiers (disodium phosphate, monosodium phosphate) are
added to
the tank and allowed to disperse. Ethylene glycol distearate (EGDS) is added
to the
mixing vessel and allowed to melt. After the EGDS is melted and dispersed
(e.g., after
about 5-20 minutes), preservative and additional viscosity modifier are added
to the
surfactant solution. The resulting mixture is passed through a heat exchanger
where it is
cooled to about 35 C and collected in a finishing tank. As a result of this
cooling step,
the EGDS crystallizes to form a crystalline network in the product. The
remainder of the
surfactant and other components are added to the finishing tank with agitation
to ensure a
homogeneous mixture. Cationic guar polymer is dispersed in water as a 0.5-2.5%
aqueous solution before addition to the final mix. Once all components have
been added,
viscosity and pH modifiers are added to the mixture to adjust product
viscosity and pH to
the extent desired.
Each exemplified composition provides excellent hair cleansing, lathering,
antimicrobial agent deposition on the scalp and dandruff control.
EXAMPLE 32
Component A B C
BAES 14.00 14.00 14.00
Cocamidopropyl Betaine --- 2.50 2.50
Cocoamphodiacetate 2.50 --- ---
Cocamide MEA 1.00 1.00 1.00
SUDS 12 0.2 0.2 0.6
Ethylene Glycol Distearate 1.50 1.50 1.50
Cetyl Alcohol 0.42 0.42 0.42
Stearyl Alcohol 0.18 0.18 0.18
Zinc Pyrithione 1.00 1.00 1.00
Jaguar C 13 S 0.15 0.15 ---
Jaguar C 17S --- --- 0.15
Fragrance q.s. q.s. q.s.
Color q.s. q.s. q.s.
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pH adjustment (Mono/Di sodium q.s. q.s. q.s.
Phosphate)
viscosity adjustment (Sodium q.s. q.s. q.s.
Chloride,
preservative (DMDM Hydantoin); q.s. q.s. q.s.
Water
In preparing each of the compositions described in (A to C), from 50% to 100%
by weight of the detersive surfactants are added to a jacketed mix tank and
heated to
about 74 C with slow agitation to form a surfactant solution. If used, pH
modifiers
(monosodium phosphate, disodium phosphate) are added to the tank and allowed
to
disperse. Ethylene glycol distearate (EGDS) and fatty alcohols (cetyl alcohol,
stearyl
alcohol) are then added to the mixing vessel and allowed to melt. After the
EGDS is
melted and dispersed (usually about 5-10 minutes), preservative (if used) is
added and
mixed into the surfactant solution. Additional viscosity modifier are added to
the
surfactant solution if necessary. The resulting mixture is passed through a
heat exchanger
where it is cooled to about 35 C and collected in a finishing tank. As a
result of this
cooling step, the EGDS crystallizes to form a crystalline network in the
product. Any
remaining surfactant and other components are added to the finishing tank with
agitation
to ensure a homogeneous mixture. Cationic guar polymer is dispersed in water
as a 0.5-
2.5% aqueous solution before addition to the final mix. Once all components
have been
added, viscosity and pH modifiers are added to the mixture to adjust product
viscosity
and pH to the extent desired.
Each exemplified composition provides excellent hair cleansing, lathering,
antimicrobial agent deposition on the scalp, and dandruff control.
EXAMPLE 33
Component Wei2ht %
UU W WW XX YY
BAS 2.0 2.0 3.0 2.0 3.0
Cocamidopropyl Betaine FB 6.0 6.0 9.0 6.0 9.0
Alkyl Glyceryl Sulfonate 10.0 10.0 6.0 10.0 6.0
Mixture A 3.0 6.0 --- --- ---
Mixture B --- --- 3.0 --- 6.0
Mixture C --- --- --- 3.0 ---
SUDS3 0.2 0.2 0.3 0.9 0.5
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Dihydrogenated Tallowamidoethyl
Hydroxyethylmonium Methosulfate (1) 0.25 0.50 --- 0.25 ---
Ditallowamidoethyl
Hydroxypropylmonium Methosulfate (2) --- --- 0.25 --- 0.25
Polyquaternium-16 (Luviquat 905) --- --- --- 0.25 ---
Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1
Disodium Phosphate 0.2 0.2 0.2 0.2 0.2
Glycol Distearate 2.0 2.0 2.0 2.0 2.0
Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6
Fragrance 1.0 1.0 1.0 1.0 1.0
Cetyl Alcohol 0.42 0.42 0.42 0.42 0.60
Stearyl Alcohol 0.18 0.18 0.18 0.18 ---
PEG-150 Pentaerythrityl Tetrastearate 0.1 0.1 0.1 0.1 0.1
Polyquatemium 10 (JR30M) 0.3 --- --- 0.1 ---
Polyquaternium 10 (JR400) --- 0.3 --- --- ---
Polyquaternium 10 (JR125) --- --- 0.3 --- 0.1
Dimethicone --- 0.3 0.3 --- ---
DMDM Hydantoin 0.2 0.2 0.2 0.2 0.2
Water qs 100 qs 100 qs 100 qs 100 qs 100
(1) Available under the trademark Varisoft 110 from Sherex Chemical Co.
(Dublin,
Ohio, USA)
(2) Available under the trademark Varisoft 238 from Sherex Chemical Co.
(Dublin,
Ohio, USA)
Component Weipht %
ZZ AAA BBB CCC DDD
BAES 4.0 5.0 6.0 3.0 4.0
SUDSI 0.2 0.2 0.25 1.0 2.5
BAS 1.0 1.0 1.0 1.0 1.0
Ammonium Laureth Sulfate 5.5 4.5 3.5 3.5 4.5
Sodium Lauroamphoacetate 7.5 7.5 7.5 8.5 7.5
Mixture A 4.0 6.0 --- --- 4.0
Mixture B --- --- 4.0 --- ---
Mixture C --- --- --- 4.0 ---
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Dihydrogenated Tallowamidoethyl
Hydroxyethylmonium Methosulfate (1) 1.0 --- --- --- ---
Ditallowamidoethyl
Hydroxypropyimonium Methosulfate (2) --- 0.75 --- --- ---
Ditallow Dimethyl Ammonium Chloride --- --- 1.0 --- 1.0
(3)
Ditallowamidoethyl
Hydroxyethylmonium Methosulfate (4) --- --- --- 0.75 ---
Polyquaternium-16 (Luviquat 905) --- --- --- 0.25 ---
Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1
Disodium Phosphate 0.2 0.2 0.2 0.2 0.2
Glycol Distearate 2.0 2.0 2.0 2.0 2.0
Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6
Fragrance 1.0 0.8 1.0 1.0 1.0
Cetyl Alcohol 0.42 0.42 0.42 0.42 0.42
Stearyl Alcohol 0.18 0.18 0.18 0.18 0.18
PEG-150 Pentaerythrityl Tetrastearate 0.08 0.1 0.1 0.1 0.1
Polyquaternium 10 (JR30M) 0.3 --- --- 0.1 0.3
Polyquaternium 10 (JR400) --- 0.3 --- --- ---
Polyquaternium 10 (JR125) --- --- 0.3 --- ---
Dimethicone --- 0.5 0.3 --- ---
DMDM Hydantoin 0.2 0.2 0.2 0.2 0.2
Water qs 100 qs 100 qs 100 qs 100 qs 100
(1) Available under the trademark Varisoft I10 from Sherex Chemical Co.
(Dublin,
Ohio, USA)
(2) Available under the trademark Varisoft 238 from Sherex Chemical Co.
(Dublin,
Ohio, USA)
(3) Available under the trademark Adogen 442-114P from Witco (Dublin, Ohio,
USA)
(4) Available under the trademark Varisoft 222 from Sherex Chemical Co.
(Dublin,
Ohio, USA)
Component Weight %
EEE FFF GGG HHH III
BAES 2.0 3.0 5.0 2.0 3.0
BAS --- 1.0 --- 1.0 1.0
Ammonium Laureth Sulfate 0 6.5 4.0 7.0 6.0
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Cocamidopropyl Betaine FB 6.0 --- 4.7 --- ---
Sodium Lauroamphoacetate --- 7.5 --- 7.5 7.5
SUDS 10 0.2 0.2 5.0 0.3 1.2
Alkyl Glyceryl Sulfonate 10.0 --- --- --- ---
Mixture A --- --- --- 4.0 ---
Mixture C --- --- --- --- 4.0
Mixture D 6.0 4.0 8.0 --- ---
Dihydrogenated Tallowamidoethyl
Hydroxyethylmonium Methosulfate (1) 0.25 --- --- 0.5 Ditallow Dimethyl
Ammonium Chloride --- 1.0 --- --- ---
(3)
Di(partially hardened soyoylethyl)
Hydroxyethylmonium Methosulfate (5) --- --- 0.75 --- 1.0
Polyquaternium-16 (Luviquat 905) --- --- --- 0.25 ---
Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1
Disodium Phosphate 0.2 0.2 0.2 0.2 0.2
Glycol Distearate 2.0 2.0 2.0 2.0 2.0
Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6
Fragrance 1.0 1.0 1.0 1.0 1.0
Cetyl Alcohol 0.42 0.42 0.42 0.42 0.42
Stearyl Alcohol 0.18 0.18 0.18 0.18 0.18
PEG-150 Pentaerythrityl Tetrastearate 0.10 0.08 1.0 0.10 0.08
Polyquatemium 10 (JR30M) --- --- 0.3 --- ---
Polyquaternium 10 (JR400) --- 0.3 --- --- ---
Polyquatemium 10 (JR125) 0.3 --- --- --- ---
Guar Hydroxypropyltrimonium Chloride --- --- --- 0.25 0.5
Dimethicone --- 0.5 --- --- ---
DMDM Hydantoin 0.2 0.2 0.2 0.2 0.2
Water qs 100 qs 100 qs 100 qs 100 qs 100
(1) Available under the trademark Varisoft 110 from Sherex Chemical Co.
(Dublin,
Ohio, USA)
(3) Available under the trademark Adogen 442-1 lOP from Witco Corporation
(Dublin,
Ohio, USA)
(5) Available under the trademark Armocare EQ-S from Akzo-Nobel Chemicals Inc.
(Chicago, Illinois, USA)
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Mixture A. ww/ratio
Styling Polymer: t-butyl acrylate/2-ethylhexyl methacrylate (90/10 w/w) 40
Volatile Solvent: isododecane 60
Mixture B. w/w ratio
Styling Polymer: t-butyl acrylate/2-ethylhexyl methacrylate (90/10 w/w) 50
Volatile Solvent: isododecane 50
Mixture C. w/w ratio
Styling Polymer: t-butyl acrylate/2-ethylhexyl methacrylate/ PDMS macromer
(81/9/10
w/w) 40
Volatile Solvent: isododecane 60
Mixture D. w/w ratio
Styling Polymer: vinyl pyrrolidone/vinyl acetate (5/95 w/w) 40
Volatile Solvent: diethyl succinate 60
EXAMPLE 34
The compositions of the present invention, in general, can be made by mixing
together at elevated temperature, e.g., about 72 C water and surfactants along
with any
solids (e.g., amphiphiles) that need to be melted, to speed mixing into the
personal
cleansing composition. Additional ingredients including the electrolytes can
be added
either to this hot premix or after cooling the premix. The nonionic or anionic
polymers
can be added as a water solution after cooling the premix. The ingredients are
mixed
thoroughly at the elevated temperature and then pumped through a high shear
mill and
then through a heat exchanger to cool them to ambient temperature. The
silicone may be
emulsified at room temperature in concentrated surfactant and then added to
the cooled
product. Alternately, for example, the silicone conditioning agent can be
mixed with
anionic surfactant and fatty alcohol, such as cetyl and stearyl alcohols, at
elevated
temperature, to form a premix containing dispersed silicone. The premix can
then be
added to and mixed with the remaining materials of the personal cleansing
composition,
pumped through a high shear mill, and cooled.
The personal cleansing compositions illustrated in Example XXII (JJJ to QQQ)
illustrate specific embodiments of the personal cleansing compositions of the
present
invention, but are not intended to be limiting thereof. Other modifications
can be
undertaken by the skilled artisan without departing from the spirit and scope
of this
invention. These exemplified embodiments of the personal cleansing
compositions of
the present invention provide cleansing of hair and/or skin and improved
conditioning.
All exemplified compositions can be prepared by conventional formulation and
mixing techniques. Component amounts are listed as weight percents and exclude
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minor materials such as diluents, filler, and so forth. The listed
formulations, therefore,
comprise the listed components and any minor materials associated with such
components.
In2redients JJJ KKK LLL MMM NNN
BAES 5.00 -- -- -- --
BAS 5.00 7.50 7.50 7.50 7.50
Sodium alkyl glycerol sulfonate 2.50 2.50 2.50 2.50 2.50
Cocoamidopropyl Betaine -- -- -- -- --
SUDS7 0.2 0.2 0.6 0.5 0.25
Glycol Distearate 2.00 1.50 2.00 2.00 2.00
Cocomonoethanol amide 0.60 0.85 0.85 0.85 0.85
Cetyl Alcohol 0.42 0.42 0.42 0.42 0.42
Stearyl Alcohol 0.18 0.18 0.18 0.18 0.18
EDTA (ethylenediamine tetra acetic 0.10 0.10 0.10 0.10 0.10
acid)
Monosodium phosphate 0.10 0.10 0.10 0.10 0.10
Disodium phosphate 0.20 0.20 0.20 0.20 0.20
Sodium Benzoate 0.25 0.25 0.25 0.25 0.25
Hydroxyethylcellulosel 0.10 0.25 -- -- --
Hydroxypropyl Guar2 -- -- 0.25 --
Hydroxyethylethylcellulose3 -- -- 0.25 --
Polystyrene Sulfonate -- -- -- 0.25
Tricetyl methylammonium chloride 0.58 -- -- -- --
Perfume 0.60 0.60 0.60 0.60 0.60
Dimethicone 1.00 1.50 1.50 1.50 1.50
Glydant 0.20 0.20 0.20 0.20 0.20
NaCl 0.20 0.30 0.30 1.00 0.30
Water and minors --------- q.s. to 100% ---------
Ingredients 000 PPP QQQ
BAES -- 9.00 8.00
BAS 6.00 -- --
Sodium alkyl glycerol sulfonate 1.00 2.50 --
SUDSB 0.2 0.2 0.2
Cocoamidopropyl Betaine -- 2.50 --
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Glycol Distearate 1.50 1.50 2.00
Cocomonoethanol amide 0.85 0.85 --
Cetyl Alcohol 0.42 0.42 0.40
Stearyl Alcohol 0.18 0.18 0.18
EDTA (ethylenediamine tetra acetic 0.10 0.10 0.10
acid)
Monosodium phosphate 0.10 0.10 0.10
Disodium phosphate 0.20 0.20 0.20
Sodium Benzoate 0.25 0.25 0.25
Hydroxyethylcellulosel 0.25 0.25 0.25
Hydroxypropyl Guar2 -- -- --
Hydroxyethylethylcellulose3 -- -- --
Polystyrene Sulfonate -- -- --
Tricetyl methylammonium chloride -- -- --
Perfume 0.60 0.60 0.60
Dimethicone 1.50 1.50 --
Glydant 0.20 0.20 0.20
Sodium Lauroamphoacetate -- -- 3.60
Polyquaternium-10 -- -- 0.20
NaCI 0.30 0.30 Water and minors --------- q.s. to 100% ---------
TM
1Natrosol 250 HHR from Aqualon
2Jaguar HP 60 from Rhone-Poulenc
TM
3Bermocoll E411 FQ from Akzo Nobel
184
