Note: Descriptions are shown in the official language in which they were submitted.
CA 02688927 2009-12-17
DETERGENT COMPOSITIONS COMPRISING POLYMERIC SUDS ENHANCERS
WHICH HAVE IMPROVED MILDNESS AND SKIN FEEL
This application has been divided out of Canadian Patent Application Serial
No. 2,372,894, derived from International Application No. PCT/US2000/014405
filed
May 25, 2000 and published internationally as WO 2000/071658 on November 30,
2000.
FIELD OF THE INVENTION
The present invention relates to compositions comprising one or more polymeric
suds volume and suds duration enhances which are mild on the users skin. The
polymeric suds enhances are suitable for use in methods which in use as
compositions
light duty liquid, LDL compositions, hand dishwashing compositions, laundry
bars,
personal cleansing compositions and the like.
BACKGROUND OF THE INVENTION
In formulating detergent compositions which will foreseeable contact the users
skin, such as Light-duty liquid or gel dishwashing detergent compositions
laundry bars,
personal cleansing compositions( such as shampoos and body washes) and the
like the
problem of mildness is of major concern. Furthermore, the formulator must also
produce
a composition which provides adequate cleaning for the desired end use.
However, it is
well know that the best cleaning surfactants, such as the anionic surfactants,
for example
LAS, AS etc., irritate the users skin. The alternative has been to use
surfactants which do
not irritate the users skin, however these are typically not the bets cleaning
surfactants
available. The formulator is presented with the difficult task of resolving
these two
seemingly conflicting, properties.
Consequently, their remains the need for a detergent composition which can
have
the best possible cleaning while being mild enough for prolonged contact with
users skin.
SUMMARY OF THE INVENTION
It has now been found that the suds boosting polymers described herein when
added to a detergent composition improves the mildness of the composition,
even
those compositions containing harsh surfactants, and surprisingly improves
skin
mildness.
The present invention meets the aforementioned needs in that it has been
surprisingly discovered that certain polymers serve not only as suds duration
and suds
volume extenders, but also enhance the mildness of a detergent composition.
The
CA 02688927 2009-12-17
448.0e
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 parent invention relates to a method for manually
cleaning
an object, preferably tableware, such as plates, glasses, flatware etc.,
fabrics, such as
clothing, bed linen, carpets, etc., skin or hair. The method comprising the
step of manually
washing said object in and contacting a user's hands with a washing solution
comprising
water and a detergent composition comprising a polymeric suds stabilizer and a
diamine,
wherein said diamine has a molecular weight of less than or equal to 400g/mol;
and said
suds stabilizer is selected from the group consisting of:
(a) polymers comprising at least one monomeric unit of the formula:
¨R2 RI
¨R3
A-(Z)z ¨L
wherein each of RI, R2 and R3 are independently selected from the group
consisting of hydrogen, C1 to C6 alkyl, and mixtures thereof; L is selected
from the group consisting of 0,
NR6, SR7R8 and mixtures thereof,
wherein R6 is selected from the group consisting of hydrogen, C1 to C8 alkyl
and mixtures thereof; each of R7 and R8 are independently hydrogen, 0,
C1 to C8 alkyl or mixtures thereof, or SR7R8 form a heterocyclic ring
containing from 4 to 7 carbon atoms, optionally containing additional hater
atoms; Z is selected from the group consisting of: -(CH2)-,-(CH2-CHH)-,
-(CH2-CHOH)-, -(CH2-CHNR6)-, -(CH2-CHR14-0)- and mixtures thereof;
wherein R14 is selected from the group consisting of hydrogen, C1 to C6 alkyl
and mixtures thereof; z is an integer selected from 0 to 12; A is NR4R5,
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
2
CA 02688927 2013-02-11
optionally substituted by C1 to C8 hydrocarbyl; and wherein said polymeric
suds stabilizer has a molecular weight of from 1,000 to 2,000,000 daltons;
(b) a proteinaceous suds stabilizer, said proteinaceous suds stabilizer having
an
isoelectric point of from 7.5 to 11.5;
(c) a zwitterionic polymeric suds stabilizer; and
(d) mixtures thereof;
and wherein said suds stabilizer is a mild, suds enhancing and suds stabilizer
such that
suds produced by said solution is maintained for an extended period of time by
said suds
stabilizer and the user's hands, after submersion in a solution containing
said suds
stabilizer, are not irritated.
A first aspect of the present invention relates to a method of enhancing
mildness of a detergent composition comprising a nonvolatile hair or skin
conditioning
agent and a surfactant system comprising an anionic surfactant or a mixture of
anionic
surfactants which method comprises adding a polymeric suds stabilizer to said
composition, wherein said polymeric suds stabilizer is selected from the group
consisting of:
(a) polymers comprising at least one monomeric unit of the formula:
Ri
¨R3
A ¨ (Z), L
wherein each of RI, R2, R3, L, Z, z and A are as hereinbefore defined; and
wherein said polymeric suds stabilizer has a molecular weight of from about
1,000 to about 2,000,000 daltons;
(b) a proteinaceous suds stabilizer, said proteinaceous suds stabilizer having
an
isoelectric point of from about 7 to about 11.5; and
(c) a zwitterionic polymeric suds stabilizer;
wherein said detergent composition further comprises an organic diamine having
a
pKa greater than 8.
A second aspect of the present invention relates to a method of cleaning the
skin
while avoiding the harsh effects on the skin of an anionic surfactant by
washing the skin
with the composition comprising a nonvolatile skin conditioning agent and a
polymeric
suds stabilizer selected from the group consisting of:
(a) polymers comprising at least one monomeric unit of the formula:
3
CA 02688927 2013-02-11
¨R3
A ¨ (Z), ¨ L 0
wherein each of RI, R2, R3, L, Z, z and A are as hereinbefore defined; and
wherein said polymeric suds stabilizer has a molecular weight of from about
1,000 to about 2,000,000 Daltons;
(b) a proteinaceous suds stabilizer, said proteinaceous suds stabilizer having
an
isoelectric point of from about 7 to about 11.5; and
(c) a zwitterionic polymeric suds stabilizer;
wherein said composition further comprises an organic diamine having a pKa
greater than 8.
A third aspect of the present invention relates to a method for manually
cleaning an
object comprising contacting a user's hands with a washing solution comprising
water, a
nonvolatile skin conditioning agent and a detergent composition in which suds
produced
by the solution is maintained for an extended period of time by a suds
stabilizer, said
suds 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 of
at least
about I unit per 100 Daltons molecular weight at a pH of from about 4 to about
12;
and
ii) an organic diamine having a pKa greater than 8;
wherein said method further including the step of washing the object with said
solution; and wherein said suds stabilizer is a, mild, suds enhancing, suds
stabilizer such that
a user's hands, after submersion in a solution containing said suds
stabilizer, are not irritated.
A fourth aspect of the present invention relates to a method of enhancing
mildness
of a detergent composition comprising a surfactant system comprising a
nonvolatile
hair or skin conditioning agent and an anionic surfactant or a mixture of
anionic surfactants
which method comprises adding a polymeric suds stabilizer to said composition,
wherein
said polymeric suds stabilizer comprising:
i) units capable of having a cationic charge at a pH of from about 4 to about
12; and.
4
CA 02688927 2013-02-11
ii) an organic diamine having a pKa greater than 8;
provided that said suds stabilizer has an average cationic charge density of
at least
about 1 unit per 100 Daltons molecular weight at a pH of from about 4 to about
12.
A fifth aspect of the present invention relates to a method of cleaning the
skin
while avoiding the harsh effects on the skin of an anionic surfactant by
washing the skin
with the composition comprising a nonvolatile skin conditioning agent and an
effective
amount of a polymeric suds stabilizer, said polymeric suds stabilizer
comprising:
i) units capable of having a cationic charge at a pH of from about 4 to about
12;
and
ii) an organic diamine having a pKa greater than 8;
provided that said suds stabilizer has an average cationic charge density of
at
least about 1 unit per 100 Daltons molecular weight at a pH of from about 4 to
about 12.
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.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified. All temperatures are in degrees Celsius ( C) unless otherwise
specified.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to methods which in addition to providing
increased
suds volume and increase suds duration, are mild. The methods of the present
invention
comprise suds boosting polymers selected from (1) polymers comprising at least
one
monomeric unit; (2) proteinaceous suds stabilizer; (3) zwitterionic polymeric
suds
stabilizer; and (4) polymers comprising units capable of having a cationic
charge.
Suitable polymeric suds stabilizers, include be a homopolymers, as well as
copolymers,
terpolymers, and higher multimers. Mixtures of the polymeric suds stabilizers
are also
within the scope of the invention.
CA 02688927 2009-12-17
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.
It is believed, while not wanting to be limited by theory, that the suds
boosting
polymers functions primarily by providing a desquamatory action to the
composition. It
is believed that the suds boosting polymers remove damaged (e.g. dry) skin
cells on the
surface of the skin, thereby reducing the rough feel associated therewith. The
suds
boosting polymers removes the effect of prior damage to the skin, giving the
skin a
fresher, more youthful appearance and feel. When the suds boosting polymers is
combined with a detergent surfactant the overall effect is to promote the
health of the
skin and to provide the consumer with a perceived mildness or skin
feel/appearance
advantage over other similar compositions which do not contain the suds
boosting
polymers while still maintaining good cleaning performance.
Alternatively, the polymeric suds stabilizers may, again while not wanting to
be
limited by theory, just improve the overall feel of the composition to the
user.
1. Polymers Comprising at least one monomeric unit
In one aspect of the present invention the polymeric suds stabilizers comprise
at
least one monomeric unit of the formula:
¨R2 RI
¨R3
A¨ (Z), ¨L 0
wherein each of RI, R2 and R3 are independently selected from the group
consisting of
hydrogen, CI to C6 alkyl, and mixtures thereof, preferably hydrogen, Ci to C3
alkyl, more
preferably, hydrogen or methyl. L is selected from the group consisting of a
bond, 0,
NR6, SR2R8 and mixtures thereof, preferably, 0, NR6, wherein R6 is selected
from the
group consisting of hydrogen, C1 to C8 alkyl and mixtures thereof, preferably,
hydrogen,
Ci to C3, and mixtures thereof, more preferably hydrogen, methyl; each of 112
and R8 are
independently hydrogen, 0, C1 to Cs alkyl and mixtures thereof, preferably,
hydrogen, C1
to C3, and mixtures thereof, more preferably hydrogen or methyl. By "0", an
oxygen
6
CA 02688927 2009-12-17
linked via a double bond is meant, such as a carbonyl group. Furthermore this
means
that when either or both R7R8 is "0", SR7R8 can have the following structures:
0 R8
0
II I II
¨S¨ ¨S¨ ¨S-
17 II II
00
or
Alternatively, SR7R8 form a heterocyclic ring containing from 4 to 7 carbon
atoms,
optionally containing additional hetero atoms and optionally substituted. For
example
SR7R8 can be:
"N. \ / \ /
K S
I II fl
I
, N ¨ NR6
or
However, it is preferred that SR7R8, 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
CH3/ 0 /
0\
When L is a bond and z is zero, it means L is a bond from the carbonyl atom to
A. For
example:
NO
}IN N u
=
Z is selected from the group consisting of: -(CH2)-, (CH2-CH=CH)-, -(CH2-
CHOH)-, (CH2-CHNR6)-, -(CH2-CHRI4-0)- and mixtures thereof, preferably -(CH2)-
=
7
CA 02688927 2009-12-17
e*-*
".
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.
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, allcyleneoxy
having the
formula:
(R100)yR11
wherein R1 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, C1 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 C1 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 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, 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
8
CA 02688927 2009-12-17
*4.0
monomeric unit and one, two or more monomeric units other than the at least
one
monomeric unit. For example a suitable homopolymer is:
R4
N¨(CH2)z-0 0
R"
wherein RI, R4, R5 and z are as hereinbefore defined. For example a suitable
copolymer
is:
(i)
_
RI
R4
/0
N¨(CH2)z--
n
R5/
wherein RI, R4, R5 and z are as hereinbefore defined; and
(ii)
¨ B_ V0
/0
wherein RI and L are as hereinbefore defined, and B is selected from the group
consisting of hydrogen, C1 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 C1 to
C8
hydrocarbyl;
wherein ratio of (i) to (ii) is from about 99:1 to about 1:10.
Some preferred examples of
9
CA 02688927 2009-12-17
¨ RI¨
B¨LO
are:
0
___ 0 "0
0 0 HO or
HO 0.
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:
RI
R4
N¨(CH2),-00
ivD5/
0
wherein RI, R4, R5 and z are as hereinbefore defined; and
CA 02688927 2009-12-17
Rt¨
RI
/\../
R13
N R12
0
0 R15¨ (Z)f
ii) either or
wherein R1 Z and z are as hereinbefore defined, each of R12 and R13 are
independently selected from the group consisting of hydrogen, C1 to C8 alkyl
and
mixtures thereof, preferably, hydrogen, CI to C3, and mixtures thereof, more
preferably hydrogen, methyl, or R12 and R13 form a heterocyclic ring
containing
from 4 to 7 carbon atoms; and R15 is selected from the group consisting of
hydrogen, CI to C8 alkyl and mixtures thereof, preferably, hydrogen, C1 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:
CH3 CH3CH2
1
N
CH3CH2/ -0 H2N
CH3' -0 0
NC)
0
NH or )
An example of a preferred homopolymer is 2-dimethylaminoethyl methacrylate
(DMAM) having the formula:
CH3
CH3' -0
11
CA 02688927 2009-12-17
=44we
Some preferred copolymers include:
copolymers of
CH3
CH3õ
0()
CH3
CH3
E
CH3 \
CH3/ 0
HO^0
Ei
CH3
o
µ1\I
and CH3/ HO^C)
An example of a preferred copolymer is the (DMA)/(DMAM) copolymer having
the general formula:
CH3
CH3
''1=1
CH3
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:
12
CA 02688927 2009-12-17
CH3
C H3
N
CH3 0'
CH3
wherein the ratio of (DMAM) to (DMA) is about 1 to about 5, preferably about 1
to
about 3.
These polymeric suds stabilizers when used in the methods of the present
invention are present at 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.
These and other suitable polymeric suds stabilizers and methods of preparing
them, can be found in WO 99/27058.
2 .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.
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.
13
CA 02688927 2009-12-17
e"
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
1 1 1 II
H2N ¨()x¨C¨(C)y¨C¨OH
, ,.,
R2 Ri
wherein R and R1 are each independently hydrogen, C1-C6 linear or branched
alkyl, C1-
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 C1-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, C1-C4 alkyl, or comprises a carbon chain
which
14
CA 02688927 2009-12-17
Nrme
can be taken together with R, R1 any R2 units to form an aromatic or non-
aromatic ring
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:
CO2H
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 40, co2H
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.
CA 02688927 2009-12-17
"0*
*4400.,
The preferred amino acids suitable for use in the proteinaceous suds
stabilizers of
the present invention have the formula:
0
I It
H2N ¨(CH2)x¨C¨(C HDy-C-OH
R1
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 0
I II
H2N¨C¨C¨OH
wherein R is hydrogen, C1-C6 linear or branched alkyl, C1-C6 substituted
alkyl, and
mixtures thereof. R is preferably C1-C6 substituted alkyl wherein preferred
moieties
which are substituted on said C1-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:
16
CA 02688927 2009-12-17
NNW"' '41 1.0
NH2
0
I I
H2N ¨v ¨C¨OH
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,
further non-limiting examples of amino acids include homoserine,
hydroxyproline,
norleucine, norvaline, omithine, penicillamine, and phenylglycine, preferably
omithine.
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.
Polyamino Acid Proteinaceous Suds Stabilizer - One type of suitable
proteinaceous suds
stabilizer according to the present invention is comprised entirely of the
amino acids
17
CA 02688927 2009-12-17
Owe+,
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
lysozyrne.
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
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
18
CA 02688927 2009-12-17
increased suds stabilization and suds volume. However, the relative amount of
cationic
amino acid present, as well as the resulting isoelectric point of the
polyaznino 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.
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:
_________ [HN-R]n+1 [NI Rim [N Rin 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
19
CA 02688927 2009-12-17
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¨Gly CO¨His
¨ x ¨ ¨ ¨ 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 proteinaceous polymeric suds stabilizers when used in the methods of the
present invention are present at 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.
These and other suitable polymeric suds stabilizers and methods for preparing
them, can be found in WO 99/27054.
3.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.
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
CA 02688927 2009-12-17
ow-
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 (C})y (CH)z ______________________________
¨ n
wherein R is C1-C12 linear alkylene, C1-C12 branched alkylene, and mixtures
thereof;
preferably C1-C4 linear alkylene, C3-C4 branched alkylene; more preferably
methylene
and 1,2-propylene. RI 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)1¨(S)¨R3
wherein L is a linking unit independently selected from the following:
21
CA 02688927 2009-12-17
New
0 0 0
II II II II
¨ 0¨ C-- NR¨ ¨C ¨0 ¨ ¨0 ¨C ¨ ¨0 ¨C ¨0 ¨ ¨0¨
,
,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:
0
¨C-0---
can suitably have this moiety introduced into the polymer via a carboxylate
containing
monomer, for example, a monomer having the general formula:
CO2H 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 C1-C12 linear alkylene, C1-C12 branched alkylene, C3-C12 linear
alkenylene, C3-C12 branched alkenylene, C3-C12 hydroxyalkylene, C4-C12
dihydroxyalkylene, C6-C10 aryl ene, C8-C12
dialkylarylene, -(R50)kR5-,
-(R50)kR6(0R5)k-, -CH2CH(0R7)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
22
CA 02688927 2009-12-17
#====,
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, -0O2M, -S03M, -0S03M, -
CH2P(0)(0M)2, -0P(0)(0M)2, units having the formula:
¨CR8R9R10
wherein each R8, R9, and R10 is independently selected from the group
consisting of
hydrogen, -(CH2)mR11, and mixtures thereof, wherein R11 is -CO2H, -S03M,
-0S03M, -CH(CO2H)CH2CO2H, -CH2P(0)(OH)2, -0P(0)(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 R113 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:
wherein L1 is a linking unit independently selected from the following:
o 0 0
II
¨C-0-- , ¨0¨C¨, ¨0¨C-0¨ ,
OR' R' 0 R' 0 R'
II I I II I II I
¨C¨N ¨ , ¨N ¨C¨ , ¨N¨C¨N¨ ,
R'S R' R' R' 0
I II I II I I II
¨N¨C¨N ¨ , ¨0¨C¨N¨ , ¨N ¨C-0¨ ,
R' R' R'
¨N=C---, ¨C=N¨ , ¨N¨, ¨U¨,
23
CA 02688927 2009-12-17
'',441we
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 LI has the formula:
OH HO
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 C1-C12 linear alkylene, C1-C12 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(0R5)k-, -CH2CH(0R7)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, 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(R1 1)2
24
CA 02688927 2009-12-17
Nkft,of
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 C
_________________ CH2¨CH ¨CH CH
0=C
¨n
NH
CH2CH2CH2N+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 ¨
(R)x (aDy __________________________ (R)x (CE)z __
¨ n1 ¨ _n2
wherein R, R1, x, y, and z are the same as defined herein above; n1 + 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.
An example of a polymer having monomers with only an anionic unit or a
cationic unit has the formula:
CO2-
_____________ CH2 ¨CH _______ CH2 ¨CH ______
¨ n1
NH
CH2 CH2CH2N+H(CH3)2
CA 02688927 2009-12-17
-...,,
wherein the sum aril 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
+R)x¨(L)y¨(c}1)zi [(R)x (LOy (r) ]
ni n'
LI
I
(S)j.
jr112
(p'
LI
RI
¨E-- I ¨ RI R2 i
F0y¨(CH)--(R)x¨(F)y¨(L-1)z _________________________________
n2
wherein R, R1, LI, S, j', x, y, and z are the same as defined herein above; n'
is equal to
n", and the value n' + n" is less than or equal to 5% of the value of n1 + n2
= n; n
provides a polymer with an average molecular weight of from about 1,000 to
about
2,000,000 daltons. R12 is nitrogen, C1-C12 linear alkylene amino alkylene
having the
formula:
-R13-N-R13-
L1, and mixtures thereof, wherein each R13 is independently L1, ethylene or
mixtures thereof.
The zwitterionic polymers of the present invention may comprise any
combination of monomer units, for example, several different monomers having
various
R1 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 zwitterionic polymeric suds stabilizers when used in the methods of the
present invention are present at an effective amount, 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 zwitterionic polymeric suds stabilizer" is that the suds produced by
the
presently described compositions are sustained for an increased amount of time
relative
26
CA 02688927 2009-12-17
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.
These and other suitable polymeric suds stabilizers and methods of preparing
them, can be found in WO 99/27053.
4.Polymers Comprising Units Capable of Having a Cationic Charge
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 charge 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 unit per 100
daltons
molecular weight.
It is preferred that the polymeric suds stabilizer 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 charge 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 present invention can be 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
27
CA 02688927 2009-12-17
,kva0
the range of about 4 to about 12." Non-limiting examples of units which
comprise a
cationic moiety include lysine, omithine, the monomeric unit having the
formula:
CH3
_________________ CH2 CH2¨CH CH
I -
NH
ii2CH2CH2N+H(CH3)2.
the monomeric unit having the formula:
CH
H 3 -
CH3'
the monomeric unit having the formula:
CH3
__________________ CH2 CH2¨CH CH
I -
NH
CH2CH2CH2N+(CH3)3
the monomeric unit having the formula:
CH3 CO2H
_________________ CH2 CH¨CH CH
I -
NH
H2CH2CH2N+H(CH3)2
and the monomeric unit having the formula:
CH3 CO2H
I I
_________________ CH2-CH¨CH CH
0=C
I -
NH
H2CH2CH21-1N+(CH3)3
28
CA 02688927 2009-12-17
`,=4.4v
the latter of which also comprises a moiety capable of having an anionic
charge at a pH
of about 4 to about 12.
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:
C 02-
_______________________ CH2-CH2 ¨CH ¨CH2 ___
;
and the monomeric unit having the formula:
CH3 CO2-
___________________ CH2 CH¨H CH
0=C
I ¨
NH
CH2CH2CH2N(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",
29
CA 02688927 2009-12-17
-
0.dr
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 polymers which contain units capable of having
a
cationic charge also include polymers comprising at least one monomeric unit
of the
formula:
¨R2 Ri
¨R3
"
A¨(Z)z¨L -0
wherein each of RI, R,R3, R4, L, Z, z, and A are hereinbefore defined.
Furthermore,
suitable polymers include copolymers of
¨R2 RI
¨R3
^n
A- (Z)z ¨L and
B--
T
wherein RI L and B are as hereinbefore defined, and
copolymers of
¨R2 RI
¨R3
A¨(Z),¨L and
CA 02688927 2009-12-17
%too %mate
r-
RI
R13
1"1.R12
0 R15¨ (Z) /
either or
12,
-
wherein R1, i(R13, Z and z are as hereinbefore defined,
The suds stabilizers polymers which contain units capable of having a cationic
charge may 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.
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
I II
H2N ¨(C)x¨C¨(C)y¨C¨OH
, I
Rz RI Rz
wherein R, RI, R2, x and y and are as hereinbefore defined.
The polymeric suds stabilizers polymers which contain units capable of having
a
cationic charge may be 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.
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:
31
CA 02688927 2009-12-17
R1 R2
1
CH)y¨(CH)z
wherein R, RI, R2, x, y, z, and n are hereinbefore defined. Furthermore
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 11 -
NH2 units. If at a specific pH within the range of from about 4 to about 12, 2
of the -N1-12
units are protonated in the form of -NH, 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.
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
32
CA 02688927 2009-12-17
pro*.
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%.
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
E nocCi
Cationic Charge Density = ____________________
E
where Ili is the number of charged unit. fi is the fraction of unit being
charged. In the case
of protonated species (AH+), f can be calculated from the measured pH and pKa.
Pxa-PH
f (AH+) = _____________________________
1+ 10PK"H
In the case of deprotonated anionic species (A")
33
CA 02688927 2009-12-17
=44.1
10PH-Pial
f(A-) =
1 + 1 OPH-
pKa
C, is the charge of the unit, mi 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
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
34
CA 02688927 2009-12-17
steady reading is achieved. Maintain temperature throughout the test at 25 C
with a
water bath and stir continuously. Raise pH of 50 mls of the aqueous polymer
solution to
12 using NaOH (1N, 12.5M). Titrate 5 mls of 0.1N HC1 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 for use in the methods of the present invention
comprising polymers which contain units capable of having a cationic charge
comprise at
least an effective amount of one or more polymeric suds stabilizers 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.
These and other suitable polymeric suds stabilizers and methods of preparing
them, can be found in WO 99/27057.
Detersive Surfactants
The compositions of the present invention preferably contain a detersive
surfactant.
The detersive surfacatnt is typically selected from the group consisting of
anionic,
nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof. By
selecting the
type and amount of detersive surfactant, along with other adjunct ingredients
disclosed
herein, the present detergent compositions can be formulated to be used in the
context of
CA 02688927 2009-12-17
laundry cleaning or in other different cleaning applications, particularly
including
dishwashing. The particular surfactants used can therefore vary widely
depending upon
the particular end-use envisioned. Suitable surfactants are described below.
Examples
of suitable nonionic, anionic, cationic amphoteric and zwitterionic
surfactants 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.
Anionic Surfactants - 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. In particular, the anionic
surfactant is an
anionic surfactant having skin irritating characteristics and is selected from
the group
consisting of C 8-C 18 alkyl benzene sulfonates, C8-C18 alkyl sulfates
containing from 0 to
3 ethenoxy groups in the molecule, C8-C25 olefin sulfonates, Cio-C20 paraffin
sulfonates,
C8-C9 alkyl phenol ethoxamer sulfates and mixtures thereof. An effective
amount,
typically from about 0.5% to about 90%, preferably about 5% to about 60%, more
preferably from about 10 to about 30%, by weight of anionic detersive
surfactant can be
used in the present invention.
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 ROSO3M
wherein
R preferably is a C10-G24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a
C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and
M is H
36
CA 02688927 2009-12-17
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 ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium
and dimethyl piperdinium, and cations derived from alkanolamines such as
ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the
like.
Typically, alkyl chains of Cl2-16 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).
36a
CA 02688927 2009-12-17
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)mS03M 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 quaternary ammonium 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.
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 99/18929; 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
37
CA 02688927 2009-12-17
WOO
branched surfactants with conventional linear surfactants are also suitable
for use in the
present compositions.
Another prefered 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.
Examples of suitable anionic surfactants are given in "Surface Active Agents
and
Detergents" (Vol. I and U by Schwartz, Perry and Berch).
Nonionic Detergent Surfactants - 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: amine
oxides,
alkyl ethoxylate, alkanoyl glucose amide, alkyl betaines, sulfobetaine and
mixtures
thereof.
Amine oxides are semi-polar nonionic surfactants and include water-soluble
amine
oxides containing one alkyl moiety of from about 10 to abc,rt 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.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the formula
0
3 4 I 5
38
CA 02688927 2009-12-17
wherein R3 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 R5 is an alkyl or hydroxyalkyl group containing from
about 1 to
about 3 carbon atoms or a polyethylene oxide group containing from about 1 to
about 3
ethylene oxide groups. The R5 groups 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 Cip-C18 alkyl dimethyl
amine
oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferably the
amine
oxide is present in the composition in an effective amount, more preferably
from about
0.1% to about 20%, even more preferably about 0.1% to about 15%, even more
preferably still from about 0.5% to about 10%,by weight.
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 allcylene 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
Igepal CO-630, marketed by the GAF Corporation; and Triton 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 Tergitol 15-S-9 (the condensation
product of
39
CA 02688927 2009-12-17
C11-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol 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; Neodol 45-9 (the condensation product of C14-C15 linear alcohol
with 9
moles of ethylene oxide), Neodol 23-6.5 (the condensation product of C12-C13
linear
alcohol with 6.5 moles of ethylene oxide), Neodol 45-7 (the condensation
product of
C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol 45-4 (the
condensation product of C 4-C15 linear alcohol with 4 moles of ethylene
oxide),
marketed by Shell Chemical Company, and Kyro 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-
8
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 preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(g1ycosy1)x
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyalkyl,
hydroxyallcylphenyl, 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,
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
allcylpolyethoxy 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.
Fatty acid amide surfactants having the formula:
0
611 7
R CN(R )2
CA 02688927 2009-12-17
wherein R6 is an alkyl group containing from about 7 to about 21 (preferably
from about
9 to about 17) carbon atoms and each R7 is selected from the group consisting
of
hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H40)xH where x varies from
about 1 to about 3.
Preferred amides are C8-C213 ammonia amides, monoethanolamides,
diethanolamides, and isopropanolamides.
Preferably the nonionic surfactant, when present in the composition, is
present in an
effective amount, more preferably from about 0.1% to about 20%, even more
preferably
about 0.1% to about 15%, even more preferably still from about 0.5% to about
10%,by
weight.
Polyhydroxy Fatty Acid Amide Surfactant - The detergent compositions hereof
may
also contain an effective amount of polyhydroxy fatty acid amide surfactant.
By
"effective amount" is meant that the formulator of the composition can select
an amount
of polyhydroxy fatty acid amide to be incorporated into the compositions that
will
improve the cleaning performance of the detergent composition. In general, for
conventional levels, the incorporation of about 1%, by weight, polyhydroxy
fatty acid
amide will enhance cleaning performance.
The detergent compositions herein will typically comprise about 1% weight
basis,
polyhydroxy fatty acid amide surfactant, preferably from about 3% to about
30%, of the
polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant
component
comprises compounds of the structural formula:
0
2 11
R CNZ
wherein: R1 is H, C 1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture
thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most
preferably C1
alkyl (i.e., methyl); and R2 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 C11-C15 alkyl or alkenyl, or mixtures thereof; and Z is a
41
CA 02688927 2009-12-17
Sikriev
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 glycityl. 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)n-CH2OH, -CH(CH2OH)-(CHOH)n_1 -
CH2011, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, 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 -CH2-
(CHOH)4-CH2OH.
R.' can be, for example, 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, oleamide, 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
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. Processes 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,
42
CA 02688927 2009-12-17
1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott.
Diamines - The preferred liquid detergent compositions, such as light duty
liquid, LDL
compositions, useful in the methods of the present invention may further
comprise one or
more diamines, preferably an amount of diamine such that the ratio of anionic
surfactant
present to the diamine is from about '40: 1 to about 2: 1. The diamine can be
an organic diamine
having a molecular weight less than or equal to 400gimol. Said diamines
provide for increased
removal of grease and gteasy food material while maintaining suitable levels
of suds.
The diamines suitable for use in the compositions of the present invention
have
the formula:
R20
R20
N ¨X ¨N
R20 \ R20
wherein each R2 is independently selected from the group consisting of
hydrogen, C1-C4 linear or branched alkyl, alkyleneoxy having the formula:
_at210)yR22
wherein R21 is C2-C4 linear or branched alkylene, and mixtures thereof; R22 is
hydrogen, C1-C4 alkyl, and mixtures thereof; y is from 1 to about 10; X is a
unit
selected from:
i) C3-C10 linear alkylene, C3-C10 branched alkylene, C3-C10 cyclic
alkylene, C3-C10 branched cyclic alkylene, an alkyleneoxyallcylene
having the formula:
¨(R210)yR21¨
wherein R21. and y are the same as defined herein above;
ii) C3-C10 linear, C3-C10 branched linear, C3-C10 cyclic, C3-C10 branched
cyclic alkylene, C6-Ci 0 arylene, wherein said unit comprises one or more
electron donating or electron withdrawing moieties which provide said
diamine with a pKa greater than about 8; and
=
iii) mixtures of (i) and (ii)
43
CA 02688927 2009-12-17
provided said diamine has a pKa of at least about 8.
The preferred diamines of the present invention have a pKi and pK2 which are
each in the range of from about 8 to about 11.5, preferably in the range of
from about 8.4
to about 11, more preferably from about 8.6 to about 10.75. For the purposes
of the
present invention the term "pKa" stands equally well for the terms "pKi" and
"p1(2"
either separately or collectively. The term pKa as used herein throughout the
present
specification in the same manner as used by those of ordinary skill in the
art. pKa values
are readily obtained from standard literature sources, for example, "Critical
Stability
Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, N.Y. and
London,
(1975).
As an applied definition herein, the pKa values of the diamines are specified
as
being measured in an aqueous solution at 250 C having an ionic strength of
from about
0.1 to about 0.5 M. As used herein, the pKa is an equilibrium constant
dependent upon
temperature and ionic strength, therefore, value reported by literature
references, not
measured in the above described manner, may not be within full agreement with
the
values and ranges which comprise the present invention. To eliminate
ambiguity, the
relevant conditions and/or references used for pKa's of this invention are as
defined
herein or in "Critical Stability Constants: Volume 2, Amines". One typical
method of
measurement is the potentiometric titration of the acid with sodium hydroxide
and
determination of the pKa by suitable methods as described and referenced in
"The
Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY, 1990.
Preferred diamines for performance and supply considerations are 1,3-
bis(methylamino)cyclohexane, 1,3-
diaminopropane (pK1=10.5; pK2=8.8), 1,6-
di aminohexane (pKi =11; pK2=10), 1,3-diaminopentane (Dytek EP) (pK1=10.5;
TM
pK2=8.9), 2-methyl 1,5-diaminopentane (Dytek A) (pKi=11.2; p12=10.0). Other
preferred materials are the primary/primary diamines having allcylene spacers
ranging
from C4-C8. In general, primary diamines are preferred over secondary and
tertiary
diamines.
44
CA 02688927 2009-12-17
µ44.1e
The following are non-limiting examples of diamines suitable for use in the
present invention.
1-N,N-dimethylamino-3-aminopropane having the formula:
NH2
1,6-diaminohexane having the formula:
NH2
1,3-diaminopropane having the formula:
2-methyl-1,5-diaminopentane having the formula:
H2NWNH2
I,3-diaminopentane, available under the tradename Dytek EP, having the
formula:
NH2
1,3-diaminobutane having the formula:
Jeffamine EDR 148, a diamine having an alkyleneoxy backbone, having the
formula:
H2N
0
3-methyl-3-aminoethy1-5-dimethyl-l-aminocyclohexane (isophorone diamine)
having the
formula:
CA 02688927 2009-12-17
fr
NH2
, and
1,3-bis(methylamino)cyclohexane having the formula:
CH2NH2
aCH2NH2
ADJUNCT INGREDIENTS
The compositions used in the methods of the present invention may further
comprise an adjunct ingredient. These will be selected depending upon the
desired form
and/or application, LDL, personal cleansing composition, etc., of the
composition. More
than one adjunct ingredient can be incorporated in to the compositions used in
the
methods.
One highly prefered composition suitable for use in the methods of the present
invention includes in addition to the polymeric suds stabilizer, an anionic
surfactant,
more preferably an alky ethoxy sulfonate, even more preferably an alky ethoxy
sulfonate
which contains about 0.6 ethoxylates, an amine oxide surfactant, and an enzyme
selected
from the group consisting of amylase, protease, and mixtures thereof
Builder - The compositions used in the methods of the according to the present
invention may further comprise a builder system. Any conventional builder
system is
suitable for use herein including aluminosilicate materials, silicates,
polycarboxylates and
fatty acids, materials such as ethylene-diamine tetraacetate, metal ion
sequestrants such as
aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic
acid
and diethylene triamine pentamethylene-phosphonic acid. Though less preferred
for
obvious environmental reasons, phosphate builders can also be used herein.
Suitable polycarboxylates builders for use herein include citric acid,
preferably in
the form of a water-soluble salt, derivatives of succinic acid of the formula
R-
46
CA 02688927 2009-12-17
'44111W
CH(COO1i)CH2(COOH) wherein R is C10-20 alkyl or allcenyl, preferably C12-16,
or
wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone
substituents.
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.
Detergency builder salts are normally included in amounts of from 3% to 50% by
weight of the composition preferably from 5% to 30% and most usually from 5%
to 25%
by weight.
Enzymes - Detergent compositions used in the methods of the present invention
may further comprise one or more enzymes which provide cleaning performance
benefits.
Said enzymes include enzymes selected from cellulases, hemicellulases,
peroxidases,
proteases, gluco-amylases, amylases, lipases, cutinases, pectinases,
xylanases, reductases,
oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tamiases,
pentosanases, malanases, B-glucanases, arabinosidases or mixtures thereof. A
preferred
combination is a detergent composition having a cocktail of conventional
applicable
enzymes like protease, amylase, lipase, cutinase and/or cellulase. Enzymes
when present
in the compositions, at from about 0.0001% to about 5% of active enzyme by
weight of
the detergent composition.
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
proteases. Preferred for use herein are subtilisin-type proteolytic enzymes.
Particularly
47
CA 02688927 2009-12-17
go,
preferred is bacterial serine proteolytic enzyme obtained from Bacillus
subtilis and/or
Bacillus licheniformis.
Suitable proteolytic enzymes include Novo Industri AJS Alcalase (preferred),
Esperase , Savinase- (Copenhagen, Denmark), Gist-brocades' Maxatase , Maxacal
and Maxapem 150 (protein engineered Maxacale) (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
International) 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.
Other proteases can be included in the detergent composition of the invention.
included in the detergent composition of the invention.
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
amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20,
1995 by
48
CA 02688927 2009-12-17
e-
swe
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 Company; WO 95/30011 published
November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published
November 9, 1995 by The Procter & Gamble 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.
Amylase - Amylases (a 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. Amylase enzymes are normally
incorporated in
the detergent composition at levels from 0.0001% to 2%, preferably from about
0.0001%
to about 0.5%, more preferably from about 0.0005% to about 0.1%, even more
preferably
from about 0.001% to about 0.05% of active enzyme by weight of the detergent
composition.
Amylase enzymes also include those described in
WO 95/26397 and in WO 96/23873. Other specific amylase
enzymes for use in the detergent compositions of the present invention
therefore include :
(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 ID listing.
(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.
49
CA 02688927 2009-12-17
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 NOB 12289, NO13
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
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 amino 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 haying 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
CA 02688927 2012-01-13
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 the WO 96/23873.
Other amylases suitable herein include, for example, a-amylases described in
GB
1,296,839 to Novo; RAPDASE , International Bio-Synthetics, Inc. and
TERMAMYL , Novo. FUNGAMYLe 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 TERMAMYLO 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 600C; or alkaline stability,
e.g., at a pH
from about 8 to about II, 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 WO 9402597, Novo, Feb. 3, 1994, as further illustrated
by a mutant in which substitution is made, using alanine or threonine,
51
CA 02688927 2009-12-17
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. licheniforrnis NClB8061. 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
example as derived by site-directed mutagenesis from known chimeric, hybrid or
simple
mutant parent forms of available airnylases. Other preferred enzyme
modifications are
accessible. See WO 9509909 A to Novo.
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.
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.
52
CA 02688927 2009-12-17
,Arnati
Perfumes - Perfumes and perfumery ingredients useful in the present methods
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-
trimethy1-
2,5,9-cyclododecatrien-l-y1 ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;
4-acety1-6-
tert-buty1-1,1-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone;
methyl
beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acety1-3-
isopropyl-
1,1,2,6-tetramethyl indane; 1-dodecanal, 4-(4-hydroxy-4-methylpenty1)-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-methy1-3-
(para-
tert-butylpheny1)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic
aldehyde;
amyl cinnamic aldehyde; 2-methyl-2-(para-iso-propylpheny1)-propionaldehyde;
coumarin; decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic
acid
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]fitran; cedrol, 5-(2,2,3-trimethylcyclopent-3-eny1)-3-
methylpentan-2-ol; 2-
ethy1-4-(2,2,3-trim ethy1-3-cyclopenten-l-y1)-2-buten-1-ol;
caryophyllene alcohol;
tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl
acetate; and
para-(tert-butyl) cyclohexyl acetate.
53
CA 02688927 2009-12-17
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-methy1-3-(para-tert-
butylpheny1)-propionaldehyde; 7-acetyl-I
,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-propylpheny1)-propionaldehyde;
1,3,4,6,7,8-
hex ahydro-4,6,6,7,8 ,8-hexamethyl-cycl openta-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.
Chelating Agents - The detergent compositions used in the methods herein may
also optionally contain one or more iron and/or manganese chelating agents.
Such
chelating agents can be selected from the group consisting of amino
carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures
therein, all as hereinafter defined. Without intending to be bound by theory,
it is believed
that the benefit of these materials is due in part to their exceptional
ability to remove iron
and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetrace-tates, N-hydroxyethylethylenediaminetriacetates,
nitrilo-tri-
acetates, ethylenediamine tetrapro-pnionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldi-glycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted
54
CA 02688927 2009-12-17
0-*
in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates)
as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or
alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3 ,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November
3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine diacetic
acid (MGDA) salts (or acid form) as a chelant or co-builder. Similarly, the so
called
"weak" builders such as citrate can also be used as chelating agents.
If utilized, these chelating agents will generally comprise from about 0.1% to
about 15% by weight of the detergent compositions herein. More preferably, if
utilized,
the chelating agents will comprise from about 0.1% to about 3.0% by weight of
such
compositions.
Composition pH - The compositions used in the methods of the invention will be
subjected to acidic stresses created by soils, such as food, when put to use,
i.e., diluted
and applied to soiled dishes. If a composition with a pH greater than 7 is to
be more
effective, it preferably should contain a buffering agent capable of providing
a generally
more alkaline pH in the composition and in dilute solutions, i.e., about 0.1%
to 0.4% by
weight aqueous solution, of the composition. The pKa value of this buffering
agent
should be about 0.5 to 1.0 pH units below the desired pH value of the
composition
(determined as described above). Preferably, the pKa of the buffering agent
should be
from about 7 to about 10. Under these conditions the buffering agent most
effectively
controls the pH while using the least amount thereof.
The buffering agent may be an active detergent in its own right, or it may be
a low
molecular weight, organic or inorganic material that is used in this
composition solely for
maintaining an alkaline pH. Preferred buffering agents for compositions of
this
CA 02688927 2009-12-17
itt."=
invention are nitrogen-containing materials. Some examples are amino acids
such as
lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine. Other
preferred
nitrogen-containing buffering agents are Tri(hydroxymethypamino methane
(HOCH2)3CNH3 (TRIS), 2-amino-2-ethy1-1,3-propanediol, 2-amino-2-methyl-
propanol,
2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyl diethanolamide,
1,3-
diamino-propanol N,N'-tetra-methyl-1,3-di amino-2 -prop anol, N,N-bis(2-
hydroxyethyl)glycine (bicine) and N-tris (hydroxymethyl)methyl glycine
(tricine).
Mixtures of any of the above are also acceptable. Useful inorganic
buffers/alkalinity
sources include the alkali metal carbonates and alkali metal phosphates, e.g.,
sodium
carbonate, sodium polyphosphate. For
additional buffers see McCutcheon's
EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon
Division, MC Publishing Company Kirk and WO 95/07971.
The buffering agent, if used, is present in the compositions of the invention
herein
at a level of from about 0.1% to 15%, preferably from about 1% to 10%, most
preferably
from about 2% to 8%, by weight of the composition.
Calcium and/or Magnesium Ions - For LDL compositions the presence of calcium
and/or
magnesium (divalent) ions improves the cleaning of greasy soils for various
compositions, i.e., compositions containing alkyl ethoxy sulfates and/or
polyhydroxy
fatty acid amides. This is especially true when the compositions are used in
softened
water that contains few divalent ions. It is believed that calcium and/or
magnesium ions
increase the packing of the surfactants at the oil/water interface, thereby
reducing
interfacial tension and improving grease cleaning.
Compositions used in the methods of the invention herein containing magnesium
and/or calcium ions exhibit good grease removal, manifest mildness to the
skin, and
provide good storage stability. These ions may be optionally present in the
compositions
herein at an active level of from about 0.1% to 4%, preferably from about 0.3%
to 3.5%,
more preferably from about 0.5% to 1%, by weight.
56
CA 02688927 2009-12-17
Preferably, the magnesium or calcium ions are added as a hydroxide, chloride,
acetate, formate, oxide or nitrate salt to the compositions of the present
invention.
Calcium ions may also be added as salts of the hydrotrope.
The amount of calcium or magnesium ions present in compositions of the
invention
will be dependent upon the amount of total surfactant present therein. When
calcium
ions are present in the compositions of this invention, the molar ratio of
calcium ions to
total anionic surfactant should be from about 0.25:1 to about 2:1.
Formulating such divalent ion-containing compositions in alkaline pH matrices
may be difficult due to the incompatibility of the divalent ions, particularly
magnesium,
with hydroxide ions. When both divalent ions and alkaline pH are combined with
the
surfactant mixture of this invention, grease cleaning is achieved that is
superior to that
obtained by either alkaline pH or divalent ions alone. Yet, during storage,
the stability of
these compositions becomes poor due to the formation of hydroxide
precipitates.
Therefore, chelating agents discussed hereinbefore may also be necessary.
Other Ingredients - The detergent compositions used in the methods of the
present
invention may further preferably comprise one or more detersive adjuncts
selected from
the following: soil release polymers, polymeric dispersants, polysaccharides,
abrasives,
bactericides, tarnish inhibitors, builders, enzymes, opacifiers, dyes,
buffers, antifungal or
mildew control agents, insect repellents, perfumes, hydrotropes, thickeners,
processing
aids, suds boosters, brighteners, anti-corrosive aids, stabilizers
antioxidants and chelants.
A wide variety of other ingredients useful in detergent compositions can be
included in
the compositions herein, including other active ingredients, carriers,
hydrotropes,
antioxidants, processing aids, dyes or pigments, solvents for liquid
formulations, solid
fillers for bar compositions, etc. If high sudsing is desired, suds boosters
such as the
C10-C16 alkanolamides can be incorporated into the compositions, typically at
1%-10%
levels. The Ci0-C14 monoethanol and diethanol amides illustrate a typical
class of such
suds boosters. Use of such suds boosters with high sudsing adjunct surfactants
such as
the amine oxides, betaines and sultaines noted above is also advantageous.
An antioxidant can be optionally added to the detergent compositions of the
present invention. They can be any conventional antioxidant used in detergent
57
CA 02688927 2009-12-17
compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate,
ascorbate,
thiosulfate, monoethanolamine(MEA), diethanolamine, triethanolamine, etc. It
is
preferred that the antioxidant, when present, be present in the composition
from about
0.001% to about 5% by weight.
Various detersive ingredients employed in the present compositions optionally
can be further stabilized by absorbing said ingredients onto a porous
hydrophobic
substrate, then coating said substrate with a hydrophobic coating. Preferably,
the
detersive ingredient is admixed with a surfactant before being absorbed into
the porous
substrate. In use, the detersive ingredient is released from the substrate
into the
aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT Dl 0, DeGussa) is admixed with a proteolytic enzyme
solution
containing 3%-5% of C13.15 ethoxylated alcohol (EO 7) nonionic surfactant.
Typically,
the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting
powder is
dispersed with stirring in silicone oil (various silicone oil viscosities in
the range of
500-12,500 can be used). The resulting silicone oil dispersion is emulsified
or
otherwise added to the final detergent matrix. By this means, ingredients such
as the
aforementioned enzymes, bleaches, bleach activators, bleach catalysts,
photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable
surfactants can
be "protected" for use in detergents, including liquid laundry detergent
compositions.
Further, these hand dishwashing detergent embodiments preferably further
comprises a hydrotrope. Suitable hydrotropes include sodium, potassium,
ammonium
or water-soluble substituted amononium salts of toluene sulfonic acid,
naphthalene
sulfonic acid, cumene sulfonic acid, xylene sulfonic acid.
The detergent compositions of this invention can be in any form, including
granular, paste, gel or liquid. In particular, the composition is selected
from the group
consisting of granules, tablets, liquids, liqui-gels, gels, microemulsion,
thixatropic
liquid, bars, pastes, powders and mixtures thereof. Highly preferred
embodiments are
58
CA 02688927 2009-12-17
in liquid or gel form. Liquid detergent compositions can contain water and
other
solvents as carriers. Low molecular weight primary or secondary alcohols
exemplified
by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric
alcohols
are preferred for solubilizing surfactant, but polyols such as those
containing from 2 to
about 6 carbon
58a
CA 02688927 2009-12-17
atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene
glycol,
glycerine, and 1,2-propariediol) can also be used. The compositions may
contain from
5% to 90%, typically 10% to 50% of such carriers.
An example of the procedure for making granules of the detergent compositions
herein is as follows: - Linear aklylbenzenesulfonate, citric acid, sodium
silicate, sodium
sulfate perfume, diamine and water are added to, heated and mixed via a
crutcher. The
resulting slurry is spray dried into a granular form.
An example of the procedure for making liquid detergent compositions herein is
as follows: - To the free water and citrate are added and dissolved. To this
solution
amine oxide, betaine, ethanol, hydrotrope and nonionic surfactant are added.
If free
water isn't available, the citrate are added to the above mix then stirred
until dissolved.
At this point, an acid is added to neutralize the formulation. It is preferred
that the acid
be chosen from organic acids such as maleic and citric, however, inorganic
mineral acids
may be employed as well. In preferred embodiments these acids are added to the
formulation followed by diamine addition. AExS is added last.
Non-Aqueous Liquid Detergents
The manufacture of liquid detergent compositions which comprise a non-aqueous
carrier medium can be prepared according to the disclosures of U.S. Patents
4,753,570;
4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-
A-
2,195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-225,654 (6/16/87); EP-A-
510,762
(10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S. 4,615,820; EP-A-
6 5,0 1 7 (10/13/93); EP-A-030,096 (6/10/81). Such
compositions can contain various particulate detersive ingredients stably
suspended
therein. Such non-aqueous compositions thus comprise a LIQUID PHASE and,
optionally but preferably, a SOLID PHASE, all as described in more detail
hereinafter
and in the cited references.
The compositions of this invention can be used to form aqueous washing
solutions for use hand dishwashing. Generally, an effective amount of such
compositions
is added to water to form such aqueous cleaning or soaking solutions. The
aqueous
59
CA 02688927 2009-12-17
Nor,
solution so formed is then contacted with the dishware, tableware, flatware
and cooking
utensils.
An effective amount of the detergent compositions herein added to water to
form
aqueous cleaning solutions can comprise amounts sufficient to form from about
500 to
20,000 ppm of composition in aqueous solution. More preferably, from about 800
to
5,000 ppm of the detergent compositions herein will be provided in aqueous
cleaning
liquor.
Personal Cleansing compositions
The compositions used in the methods 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-1 shampoos and conditioners, toilet bars,
hand soap
(including liquid or bar), deodorant soap, and the like.
The conventional personal cleansing composition used in the methods of the
present invention additionally contains a conventional personal cleansing
additive. The
conventional personal cleansing additive is 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. Additionally, the conventional personal 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 personal cleansing 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;
CA 02688927 2009-12-17
or's% Apmek
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 used in the methods 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
known in the art for determining average particle size for emulsified liquids.
One such
TM
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.
61
CA 02688927 2009-12-17
See also U.S. Patent application 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., 1 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 form 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 Coming 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
1 1 1
A¨Si¨O¨Si ________________________ 0 Si¨A
1 1 1
R R
- x
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
62
CA 02688927 2009-12-17
%IOW µ,410'
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 pre-
ferred 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 silicones are available, for example, from the
General
Electric Company in their Viscasil 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)
63
CA 02688927 2009-12-17
- OH3 OH
I I
HO-Si H
I ICH2)3
CH3
- x NH
IcH2)2
NH2
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
(DE)
(R1)aG3_a-Si-(-0SiG2)n-(-0SiGb(R1)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 1 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;
R1 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):
64
CA 02688927 2009-12-17
_
TI-1 TH3
(CH3)3Si-Oli ______________________ il ___ osi(CH3)3
CH (CH2)
_ I
n NH
I
(CH2
I
NH2
01
In this formula n and m are selected depending on the exact molecular weight
of
the compound desired.
Other silicone cationic polymers which can be used in the personal cleansing
compositions are represented by the formula (V):
R4 CH2-CHOH-CH2-N+(R3)3Q-
-
R3
I
I
(R3)3Si-OTi 0 _________________________ Si-0 Si-O-Si(R3)3
f
R3R3
_i- - _
S
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 C1-C18 allcylene radical or a C1-C18, and more preferably C1-C8,
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; and 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.
CA 02688927 2009-12-17
*14:1===
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
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 difimctional, or both, silanes
during
manufacture of the silicone resin. As is well understood in the art, the
degree of
crosslinking 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 tetrachlorosilarie, with the
66
CA 02688927 2009-12-17
00,
methyl-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.
Silicone materials 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
presence of various siloxane monomer units which make up the silicone.
Briefly, the
symbol M denotes the monofunctional unit (CH3)3Si00.5; D denotes the
difunctional
unit (CH3)2Si0; 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
67
CA 02688927 2009-12-17
44.40
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-C12 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
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,
68
CA 02688927 2009-12-17
Nkim, =¨x.=#s
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. Isododecane, isohexadeance, and
isoeicosene are
TM
commercially available as Permethyl 99A, Permethyl 101A, and Permethyl 1082,
from
Presperse, South Plainfield, NJ. A copolymer of isobutene and normal butene is
TM
commercially available as Indopol H-100 from Amoco Chemicals. Preferred among
these hydrocarbons are mineral oil, isododecane, isohexadecane, polybutene,
polyisobutene, and mixtures thereof.
Optional Suspending Agent - The personal cleansing compositions used in the
methods
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
diethanolamide, 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
69
CA 02688927 2009-12-17
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 commercially 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
CA 02688927 2009-12-17
011WM,
'SlimFe
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.,
methylcellulose, hydroxybutyl
methylcellulose,hydroxypropylcellulose,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 used in the methods 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 used in the
methods 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
71
CA 02688927 2009-12-17
*woo
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.
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
performance, 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
72
CA 02688927 2009-12-17
".4.40e
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 Dictionwy, 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 Cl-C7 alkyl groups, more preferably Cl -
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.
Amines substituted vinyl monomers and amines can be polymerized in the amine
form and then converted to ammonium by quaternization.
Suitable cationic amino and quaternary ammonium monomers include, for
example, vinyl compounds substituted with dialkyl aminoalkyl acrylate,
dialkylamino
allcylmethacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl
methacrylate,
trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium
sale, diallyl
quaternary arrunonium salts, and vinyl quaternary ammonium monomers having
cyclic
cationic nitrogen-containing rings such as pyridinium, imidazolium, and
quaternized
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 C1-C3 alkyls, more
preferably
C1 and C2 alkyls.
Suitable amine-substituted vinyl monomers for use herein include
dialkylaminoalkyl acrylate, dialkylaminoallcyl methacrylate,
diallcylaminoallcyl
73
CA 02688927 2009-12-17
ifierwe
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-
viny1-2-pyrrolidine and 1-vinyl-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 LUV1QUAT trademark (e.g., LUVIQUAT FC 370);
copolymers of 1-viny1-2-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., GAFQAT 755N);
cationic diallyl quaternary amnionium-containing polymers including, for
example,
dimethyldiallyammonium chloride homopolymer and copolymers of acrylamide and
dimethyldiallyarnmonium 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 formula:
R1
A-0--ER-N+-R3X)
R2
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, arylallcyl, alkoxyalkyl, or alkoxyaryl groups, each group
containing up to
about 18 carbon atoms, and the total number of carbon atoms for each cationic
moiety
74
CA 02688927 2012-01-13
(i.e., the sum of carbon atoms in R1, 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 Polyquaternium 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
Polyquatemium 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 quaternary
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
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.
CA 02688927 2009-12-17
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
TM
deposition polymers are Jaguar Cl3S, Jaguar C15, Jaguar C17 and Jaguar C16 and
Jaguar C162. Other preferred cationic cellulose ethers include Polymer JR400,
JR3OM
and JR125.
Surfactant soluble Conditioning Oil - The shampoo compositions used in the
methods 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
76
CA 02688927 2009-12-17
,A.AN
N%1110
1.5%, more preferably from about 0.1% to about 1%, 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
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 to
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-dimethy1-10-methylundecane and 2, 2,
4, 4, 6, 6-
77
CA 02688927 2009-12-17
466,e
dimethy1-8-methylnonane, sold by Pennethyl 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.
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-l-
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 used in the methods
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.
78
CA 02688927 2009-12-17
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.
Organic styling polymer - The styling polymers suitable for use in the methods
of
the present invention include organic styling polymers well known in the 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,
79
CA 02688927 2009-12-17
.00.1ht
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,
methacrylic acid, N,N-dimethylacrylamide, dimethyl aminoethyl methacrylate,
quatemized 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, ally1 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
CA 02688927 2009-12-17
*we
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 CI-CH 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-1 -pentanol, 3-methyl- I -
pentanol, t-
butanol(2-methy1-2-propanol), cyclohexanol, neodecanol, 2-ethyl- I -butanol, 3-
heptanol,
benzyl alcohol, 2-octanol, 6-methyl-l-heptanol, 2-ethyl-l-hexanol, 3,5-
dimethyl-1-
hexanol, 3,5 ,5-tri methyl-l-hexanol, 1-decanol, 1-dodecanol, 1 -h exadecanol,
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
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
81
CA 02688927 2009-12-17
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-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 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 Gelman et
al.,
issued April 1, 1980.
82
CA 02688927 2009-12-17
a=wair..
Silicone-srafted styling polymer - Other suitable styling polymers for use in
the
methods of the present invention are silicone-grafted hair styling resins.
These polymers
may be used alone or in combination with the organic styling polymers
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
83
CA 02688927 2009-12-17
p =
*00, 'VW"
(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
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)nSi(R)3,m7m
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. C1-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 =reactive 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:
84
CA 02688927 2009-12-17
- ---'1*,
0
II
X -C-0- (CHAT- (0)[:S I (RmZni
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, allcylamino, aryl, or alkaryl
(preferably 121 is
alkyl); X conforms to the formula
C I-1----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
I
R4¨S i 0--
I
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
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=0, and q=3.
Another preferred polysiloxane monomer conforms to either of the following
formulas
¨9--
X (C H2)s¨S i (R1)3-m¨Zrn
(R2)n
or
X¨C H2 ¨(C H2 )s¨S i (R1 )3-m¨Zrn
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,
CA 02688927 2009-12-17
%two vatiO
preferably Cl -C6 alkyl or C7-C10 alkylaryl, more preferably Cl -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-ethylhex I -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
(iii) t-butylm ethacrylate/2-ethylhex yl-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-butylacryl ate/2- ethylhex yl-m ethacrylate/PDM S 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
86
CA 02688927 2012-01-13
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. Serial
No.
07/758,319, Bolich et al, filed August 27, 1991.
Solvent - The personal cleansing composition used in the methods 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
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
87
CA 02688927 2009-12-17
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 include commercially available isoparaffins
from Exxon
TM
Chemical Company such as Isopar H and K (C11-C12 isoparaffins), and Isopar L
(C11-
C13 isoparaffins). Preferred branched hydrocarbons are isohexadecane,
isododecane,
2,5-dimethyl decane, isotetradecane, and combinations thereof. Commercially
available
branched hydrocarbons include Permethyl 99A and 101A (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-
pentany1-3-
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.
88
CA 02688927 2009-12-17
'tek4e
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
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
R2
wherein R1 and R2 are independently selected from C1 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:
R4 R6
R3 R5 R8
-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:
R2 R4
R3 R5
wherein R1, R2, R3, R4, R5, and R6 are independently selected from saturated
or
unsaturated C1 to C7 alkyl, aryl and alkyl aryl and R7 is C1 to C4 alkylene.
Silane compounds have the general formula:
89
CA 02688927 2009-12-17
-.woe
IT1
R4 11¨R2
R3
wherein R1, R2, R3, and R4 can independently be selected from C1 - C8 alkyl,
aryl,
allcylaryl, hydroxyalkyl and alkylsiloxy.
Silicones of the above type, both cyclic and linear, are offered by Dow Coming
Corporation, Dow Coming 344, 345 and 200 fluids, Union Carbide, Silicone 7202
and
Silicone 7158, and Stauffer Chemical, SWS-03314.
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 used in the
methods 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. In 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
CA 02688927 2009-12-17
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 quaternary 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, allcylester moieties, and mixtures thereof. Suitable hycirophile-
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 8.
Select cationic spreading agents for use in the composition include those
corresponding to the to the formula:
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
91
,
CA 02688927 2009-12-17
,04',,
'4610" ',WOO
hydrophilic moieties selected from the alkoxy, polyoxyalkylene, alkylarnido,
hydroxyallcyl, 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-
1
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
I I I II
R"¨CNH(¨CH2¨)m¨N¨(¨CH2¨)fl¨NHCR X-
I
4
_
wherein Z1 and Z2 are independently saturated or unsaturated, substituted or
unsubstituted, linear or branched hydrocarbons, and preferably Z1 is an alkyl,
more
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)
92
CA 02688927 2009-12-17
*ow
dimethyl ammonium acetate, dihexadecyl dimethyl ammonium acetate, ditallow
dipropyl
ammonium phosphate, ditallow dimethyl ammonium nitrate, di-(coconutalkyl)
dimethyl
ammonium chloride, ditallowamidoethyl hydroxypropylmonium methosulfate
(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 methosulfate,
ditallowamidoethyl
hydroxyethylmonium methosulfate, and di(partially hardened soyoylethyl)
hydroxyethylmonium methosulfate are particularly preferred quaternary ammonium
cationic surfactants useful herein.
Other suitable quaternary ammonium cationic surfactants are described in M.C.
Publishing Co., McCutcheion'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, 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 personal cleansing compositions used in the
methods 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 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,
93
CA 02688927 2009-12-17
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.
94
CA 02688927 2009-12-17
Nwrif
Most preferred for use in the present invention are ethyl hydroxyethyl
cellulose,
hydroxyethyl cellulose, hydroxypropyl guar and polystyrene sulfonate.
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 used in the methods 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. Arnphiphiles
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.
Amides, 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 /X
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,
CA 02688927 2009-12-17
lanolinamide DEA, lauramide DEA, lauramide MEA, lauramide MIPA, linoleamide
DEA, linoleamide MEA, linoleamide MIPA, myristamide DEA, myristamide MEA,
myristamide MIPA, Oleamide DEA, Oleamide MBA, Oleamide MIPA, palmamide
DEA, palmamide MEA, palmamide MIPA, palmitamide DEA, palmitamide MEA, palm
kernelamide DEA, palm kernelamide MEA, palm kernelamide MIPA, peanutamide
MEA, peanutamide MIPA, soyamide DEA, stearamide DEA, stearamide MEA,
stearamide M1PA, tallamide DEA, tallowamide DEA, tallowamide MEA,
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 20H
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
96
CA 02688927 2009-12-17
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 C1.3 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.
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%.
97
CA 02688927 2009-12-17
"oak.
v..noov
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 used in the methods 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 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, WO 98/18434 and
WO 97/35548.
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
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CA 02688927 2009-12-17
Nft00
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
urn, 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 antidandruff agents, especially 1-hydroxy-2-pyridinethione
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
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
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CA 02688927 2009-12-17
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
R2)(../xR4
RI 0
(!)11
wherein R1 is hydrogen, alkyl of 1 to 17 carbon atoms, cycloallcyl-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 1 to 4 alkyl carbon atoms, aryl-alkenyl 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 1 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 1 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 and/or 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
Alcitengeselfschafl under the trade mark Octopirox.
(b) magnesium sulfate adducts of 2,2'-dithiobis(pyridine-l-oxide) of the
formula
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CA 02688927 2009-12-17
AfA.ipt,
/1
=Ava"gSO4
-1µ1,
0 0
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
(NSH
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 21.1 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
15p.,
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.
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CA 02688927 2009-12-17
The diameter of a sphere of equivalent volume for a particle can be determined
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.
The sphericity of a particle is also described by Stockham and Fochtman at
page
113 as
= (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/-d5)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.
(d) Co-surfactants
The surfactant system of the personal cleansing compositions used in the
methods
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 used in the
methods herein
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%,
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CA 02688927 2009-12-17
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.
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)xS03M, 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
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CA 02688927 2009-12-17
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 R1 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.
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
sul fo succin ate ; tetrasodium N-(1,2 -dicarboxyethyl)-N-octad ecylsul fo
succinnate; di amyl
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
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CA 02688927 2009-12-17
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 form.
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.
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
Ri _________________________________ so3M
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 anunonium lauryl sulfate, ammonium laureth sulfate, triethylamine
lauryl sulfate,
triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine
laureth
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CA 02688927 2009-12-17
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, lauryl
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 used in the methods herein 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.
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 --> 0] where
R1
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
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CA 02688927 2009-12-17
about 1 glyceryl moiety and R and R" are each alkyl or monohydroxyalkyl groups
containing from about 1 to about 3 carbon atoms.
Suitable arnphoteric 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 ¨C H2- 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
carbon atoms; X is 1 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,
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CA 02688927 2009-12-17
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-C18 hydrocarbyl amidopropyl hydroxy-
sultaines, especially C12-C14 hydrocarbyl amido propyl hydroxysultaines, e.g.,
laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other
sul-
taMes are described in U.S. Patent 3,950,417.
Other suitable amphoteric co-surfactants are the aminoalkanoates of the
formula R-NH (CH2)nC
00M, the iminodialkanoates of the formula
R-NRCH2)/nCOOMJ2
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, ammonium 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
R1CON¨(C112)n¨NtCH2Z
1
R4 R2
wherein R1 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,
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
108
CA 02688927 2009-12-17
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
intermediate.
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 MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. 0.P., MIRANOL
C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2C113 (Alkaril
Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-3 8,
MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical
Group); and SCHERCOTERIC MS-2 (Scher Chemicals).
Betaine co-surfactants (zwittetionic) suitable for use in the personal
cleansing
compositions are those represented by the formula:
o R4 tr2
R5 II NI-(cH2)n., -N+¨Y ¨R1
_ n
wherein:
R1 is a member selected from the group consisting of
COOM and CH(OH)-CH2S03M
R2 is lower alkyl or hydroxyalkyli
R3 is lower alkyl or hydroxyalkyl;
109
CA 02688927 2009-12-17
em's
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;
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 "hydroxyallcyl" 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, cety1,-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
dim ethyl-alph a-c arboxyethylb etaine,
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-
110
CA 02688927 2009-12-17
*me
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-hydroxyethyp-sulfopropylbetaine, and the like.
Nonionic co-surfactant - The personal cleansing compositions used in the
methods 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,
111
CA 02688927 2009-12-17
Nur"
and which discloses A P S 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(0)0CH2CH(011)CH2(OCH2CH2)n0H 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.
Cationic Co-surfactants - Optional cationic co-surfactants for use as
conditioning agents
in the methods of the present invention will typically contain quaternary
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:
X-
R2Z 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, allcylamido,
hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and
X is a salt-
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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 RI, 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 1 to
about 3
carbon atoms, preferably from 1 to about 2 carbon atoms.
Form of Personal Cleansing Composition
The personal cleansing compositions used in the methods herein may be of an
conventional form. That is , they can be liquids, gels, mousses, solids, bars,
pastes and
the like. The physical form will be selected depending upon the desired
properties and
the intended use of the composition.
Aqueous Liquid Carrier
The personal cleansing compositions used in the methods herein may further
contain from about 50% to 99.899%, preferably from about 60% to about 95%,
more
preferably from about 70% to 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.
Hydrotropes - The aqueous liquid carrier may comprise one or more materials
which are hydrotropes. Hydrotropes suitable for use in the compositions herein
include
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New50
the C1-C3 alkyl aryl sulfonates, C6-C12 alkanols, C1-C6 carboxylic sulfates
and
sulfonates, urea, C1-C6 hydrocarboxylates, C1-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 C1-C8 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 C1-C4 hydrocarboxylates and C1-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
mixtures thereof. These preferred hydrotrope materials can be present in the
composition
to the extent of from about 0.1% to 8% by weight.
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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 C1-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.
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Optional Components
The personal cleansing compositions used in the methods 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.
Laundry Bars
The compositions used in the methods 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 used in the methods 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
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--
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 allcylsulfate, 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 used in the methods 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 silicates are particularly useful herein.
Specific preferred
examples of builders include sodium tripolyphosphates (STPP) and sodium
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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 sulfuric 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 used in the methods 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
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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%.
While any of the smectite-type clays described herein are useful in the
present
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 Ingredients - A particularly preferred optional component of
the laundry
bars used in the methods 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,
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CA 02688927 2009-12-17
.roAelq,
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.
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
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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-vinylpyn-olidone 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
of the formula R4R5R6N, wherein R4 is C5 to C22 hydrocarbyl, R5 and R6 are.
independently Ci to Ci 0 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(0)(OH)-0R9 and HO-P(0)(OH)-0R9, 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 1 to 4 carbons, such as described in UK Patent
Application GB 2,173,827; and quaternary ammonium compounds of the formula
R1OR11 R12R13N+X-, wherein RIO is alkyl having 8 to 20 carbons, Ri i is alkyl
having
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1 to 10 carbons, R12 and R13 are alkyl having 1 to 4 carbons, preferably
methyl, and X
is an anion, preferably Cl- or Br-, such as C12_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 -00H group, such as sodium perborate
monohydrate, sodium perborate tetrahydrate and sodium percarbonate. Sodium
percarbonate (2Na2CO3.3H202) 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 pg se, such as a formula:
CH3(CH2)w-NH-C(0)-(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%.
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-
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methylcellulose. A preferred soil suspending agent is an acrylic/maleic
copolymer,
commercially available as Sokolane, 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-y1) 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.
Processing - The detergent laundry bars used in the methods 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
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
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(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 sulfonatt
MBASx Mid-chain branched primary alkyl (average total carbons
=
x) sulfate
MBAExSz Mid-chain branched primary alkyl (average total carbons
=
z) ethoxylate (average E0 = 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
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Et0H Ethanol
NaOH Solution of sodium hydroxide
NaTS Sodium toluene sulfonate
Citric acid Anhydrous citric acid
CxyFA C1x-Cly fatty acid
CxyEz A Cix_i y branched primary alcohol condensed with an
average of z moles of ethylene oxide
Carbonate Anhydrous sodium carbonate with a particle size between
200gm and 900gm
Citrate Tri-sodium citrate dihydrate of activity 86.4% with a
particle size distribution between 425gm and 850 gm
TFAA C16-18 alkyl N-methyl glucamide
LMFAA C12-14 alkyl N-methyl glucamide
APA C8-C10 amido propyl dimethyl amine
Fatty Acid (C12/14) C12-C14 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 C y alkyl sulfate (or other salt if specified)
CxyEzS Sodium C1-C1, alkyl sulfate condensed with z moles of
ethylene oxide (or other salt if specified)
CxyEz A Cix_iy branched primary alcohol condensed with an
average of z moles of ethylene oxide
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'qvami %%01
AQA R2.N4-(CH3)x((C2H40)yH)z with R2 = C8 - C18x+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(A102Si02)12. 27H20 having a primary particle size
in the range from 0.1 to 10 micrometers
NaSKS-6 Crystalline layered silicate of formula 8 -Na2Si205
Carbonate Anhydrous sodium carbonate with a particle size between
2001.tm and 90011m
Bicarbonate Anhydrous sodium bicarbonate with a particle size
distribution between 4001Am and 1200p.m
Silicate Amorphous Sodium Silicate (Si02:Na20; 2.0 ratio)
Sulfate Anhydrous sodium sulfate
PAE ethoxylated (15-18) tetraethylene pentamine
PIE ethoxylated polyethylene imine
PAEC methyl quatemized 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 AJS under the trademark Termamyl 60T
Lipase Lipolytic enzyme of activity 1001cLU/g sold by NOVO
Industries AJS under the trademark Lipolase
PB1 Anhydrous sodium perborate bleach of nominal formula
NaB02.H202
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Percarbonate Sodium Percarbonate of nominal formula
2Na2CO3.3H202
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
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.
SUDS1 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
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dommk
SUDS6 Poly(DMAM-co-MAA-co-DMA) (4:1:1) Tefpolymer
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
SUDS11 Polypeptide comprising Lys, Ala, Glu, Tyr (5:6:2:1)
having
a molecular weight of approximately 52,000 daltons
SUDS 12 Lysozyme
SUDS13 LX1279 available from Baker Petrolite
Isofol 16 Condea trademark for C16 (average) Guerbet alcohols
CaC12 Calcium chloride
MgC12 Magnesium chloride
DTPA Diethylene triamine pentaacetic acid
EXAMPLE 1
Preparation of Poly(DMAM-co-DMA) (3:1) Copolymer
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. NNW is consistent with the
desired
compound.
128
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er,"frt1/4
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 watent-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), T,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
mixture is lyophilized and then pulverized in a blender to yield an off-white-
peach
powder. NMR is consistent with the desired compound.
129
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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
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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
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- 1 -hexene) (15.00 g) and pyridine (150 ml,
anhydrous)
are placed into a 250 ml three-necked round-bottom flask, fitted with a
heating mantle,
magnetic stirrer, dropping finmel, 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. NNW 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
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*10,0e
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 urn) 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.
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
132
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- ....ow.,
..._ =-....64"
Component Wt % Wt % Wt %
Wt % Wt %
A B C D E
LAS, From Example 1 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
Sodium Perborate 15 - 15 15 15 15
Optionals including: brightener, balanc balance balance balance balance
colorant, perfume, thickener, suds e
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
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v.011
Perfume 0.4 0-1.0
SUDS1 0.2 0.01 to 5.0
MBAE2S14.4 2.3 1-3.0
Solid Phase
Protease 0.4 0-1.0
Citrate 4.3 3-6
PB1 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.
A B
C25 AE3S 2 8 17 5
MBAS14.4 15 12 0 8
C12-C14 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
C12-C18 fatty acid 11 4 4 3
Citric acid 1 3 3 2
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%Ear,
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
Et0H 1.8 4.7 5.4 1
Amylase (300KNU/g) 0.1 0.1 0.1 0.1
Lipase 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
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
MBAE1.8S 14.4 10 12 14 16 20
Na C25AE1.8S 10 8 6 4
C23E9 2 2 2 2 2
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LMFAA 5 5 5 5 0
SIJDS3 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
Et0H 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
Enzymes, 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:
M I N 0
MBAE1.8S14.4 and / or 0 7-12 12 - 17 17-22 1-35
MBAS14.4
Any combination of: 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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C23E9 or C23E6.5 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
Et0H 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 Balance Balance
Balance Balance Balanc
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CA 02688927 2009-12-17
Product pH (10% 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
AB CDE F GH I
(weight percent)
NaCFAS (C12_18) 15.75 15.75 19.13 11.20 22.50 13.50
Na(C1218)LAS 6.75 6.75 3.38 8.80 19.00 15.00 21.00
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
SUDS13 0.5 0.1
SUDS3 0.2 0.25 0.8 0.15 0.2
SUDS12 0.2 0.2
SUDS] 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 0.80 0.80
6
Lipase enzyme 0.10 0.10
Cellulase enzyme 0.15 0.15
7
Balance 8 -----------
1. Sodium diethylenetriamine penta (phosphonate)
2. PEO is poly(ethylene oxide) having a molecular weight as indicated.
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CA 02688927 2009-12-17
.44,401
3. Sokolan CP-5 is maleic-acrylic copolymer
4. SRP-A is
Na03S(CH2CH20)2-C(0)-(C6H4)-C(0)0-[-CH2CRH-O-C(0)-(C6H4)-
C(0)0-]4-
-[-CH2CRH-O-C(0)-(C6H4)S03Na-C(0)011-
CH2CH2OCH2CH2S03Na
wherein R is H or CH3 in a ratio of about 1.8:1.
5. Protease activity at 1 Au/gin stock.
6. Amylase activity at 100,000 amu/gm stock.
7. Carezyme cellulase, supplied by Novo Nordisk, activity at 5000 Cevu/gm
stock.
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
MLAS 3.0 3.0 5.0 3.2 3.2 3.2 8.0 8.0
Dobanol 23-3 1.0 1.0 1.5 1.3
1.3 1.5 3.0 3.5
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
SUDS5 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
MgSO4 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 3 0.06 0.1 - 0.1 - 0.2
Na2HPO4 0.1 - 0.3 -
Na21-12P20 7 0.2 0.5
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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 ctunene sulphonate
-Dobanol 23-3 is a C12-13 alcohol ethoxylated with an average ethoxylation
degree of
3.
TM
-Empilan 1CBE21 is a C12-14 alcohol ethoxylated with an average ethoxylation
degree of
21.
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CA 02688927 2009-12-17
EXAMPLE 19
I J K L M N
C13-15 E030 1 - - - - -
C12-14 E020 - - 1 1.7 -
-
C12-14P03E07 - - - - 2
C12-14 E010 - - - - 2 -
C10-12 E010 - 1.5 - - - -
SUDS7 0.2 0.1 0.3 0.5 0.2 0.1
MLAS - - 2.4 - 2.4 2.4
C11E05 - - - 5 - -
C12-14E05 4.2 3.0 3.6- 3.6 3.6
C9-11E04 - 3.0 - - - -
C12-0H - 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 10E0 (4) - - 3 -
SUDS8 0.1 0.2 0.2 0.5
Citric acid 2 2 2 3
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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 C13 and C15 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 C19 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.
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
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Butylcarbitol R 4 4 4
Triethanolamine 1 1 1
water & minors up to 100%
EXAMPLE 22
A shampoo composition
Weiglq %
Components A
TEA C12 -C14 Alkyl Sulfate 10.00
NH4 C12-C14 Alkyl (Ethoxy)3 Sulfate 7.90
SUDS1 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% q.s. to 100%
water
EXAMPLE 23
The following are personal cleansing compositions of the present invention.
Component Weight %
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
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#4 N,
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 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 JAGUAR C-17 can be replaced with LUVIQUAT FC 370.
EXAMPLE 24
The following are personal cleansing compositions of the present invention.
Component Wei2ht %
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
Tricetyl Methyl Ammonium 0.5 0.5
Chloride
SUDS1 0.75 1.25
144
CA 02688927 2009-12-17
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 arnmonio)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
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 %
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
145
CA 02688927 2009-12-17
er"k
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 11
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 %
Cocoamidopropyl Betaine 4.0
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
146
CA 02688927 2009-12-17
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).
2. VISCAS1L 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 Weight %
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
Polydimethylsiloxane2 3.0 3.0
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 q.s. to
100% 100%
147
CA 02688927 2009-12-17
=0,=`"-
1. Polyquatemium 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 %
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.
148
CA 02688927 2012-01-13
3. Sodium polystyrene sulfonate, an anionic polymer available from National
Starch and
Chemical Corp., Bridgewater, NJ, USA.
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 72
C for
about 10 minutes and the premix is then conventionally mixed with the
remaining hot
(72 C) 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. 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,
149
CA 02688927 2009-12-17
s...0, ....."
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.
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 Silicone' 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
150
CA 02688927 2009-12-17
....,., -....1
Cocamidopropylbetaine 1.70 1.70 2.70 1.85 4.20
Polyquatemium-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
Ammonium BAES 14.0 14.00 14.00 9.00 9.00
Cocarnidopropylbetaine 2.70 2.70 2.70 1.70 1.70
Polyquatemium-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
Carbopol 9812 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% --
151
CA 02688927 2009-12-17
%roe
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. Polyquatemium-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 rim made via linear
feedstock
available from Dow Coming (2-1520; PE106004).
5. Jaguar C17 is a cationic polymer available from Rhone-Poulenc
6. Polyquatemium-10 is JR400, a cationic cellulose derived polymer available
from
Amerchol.
EXAMPLE 30
A shampoo having the following formula is prepared
Component A weight
AA
17
Zinc Pyridinethione* 2.0
Coconut Monoethanolamide 3.0
Ethylene Glycol Distereate 5.0
Sodium Citrate 0.5
SUDS7 0.3
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
152
CA 02688927 2009-12-17
eg"N 0,*11.4,
BB
Triethanolamine alkyl sulfate 10%
BAS 9
Zinc Pyridinethione* 2.0
Coconut Monoethanolamide 2.0
SUDS! 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 Diethanolarnide 2.0
Color solution 0.12
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 Bach.
EXAMPLE 31
153
'
CA 02688927 2012-01-13
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. 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 1111
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 LOU 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 q.s. q.s. q.s. q.s. q.s.
sodium 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 ICK LL MM NN
154
CA 02688927 2009-12-17
BAES 7.50 15.00 15.00 10.00 10.00
BAS 2.50 5.00 5.00 2.50 2.50
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 Cl3S --- 0.10 --- 0.10
Jaguar Cl7S 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
Sodium Lauroyl Sarcosinate 1.50 1.50 --- ---
Sodium Cocoyl Glutamate
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 Cl3S 0.20 --- --- 0.10 0.05 ---
155
CA 02688927 2009-12-17
00¨ =029.6i
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 (Sodium q.s. q.s. q.s. q.s. q.s. q.s.
Chloride,)
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 fmishing
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
BAES 14.00 14.00 14.00
156
CA 02688927 2009-12-17
S61.0,
Cocamidopropyl Betaine 2.50 2.50
Cocoamphodiacetate 2.50
Cocamide MEA 1.00 1.00 1.00
SUDS12 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 Cl3S 0.15 0.15
Jaguar Cl7S 0.15
Fragrance q.s. q.s. q.s.
Color q.s. q.s. q.s.
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
157
CA 02688927 2009-12-17
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 Weight %
UU 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
SUDS 3 0.2 0.2 0.3 0.9 0.5
Dihydrogenated
Tallowamidoethyl 0.25 0.50 --- 0.25 ---
Hydroxyethylmonium
Methosulfate (1)
Ditallowamidoethyl
Hydroxypropylmonium 0.25 --- 0.25
Methosulfate (2)
Polyquatemium-16 (Luviquat --- 0.25 ---
905)
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
158
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+60.,
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 0.1 0.1 0.1 0.1 0.1
Tetrastearate
Polyquatemium 10 (JR30M) 0.3 --- --- 0.1
Polyquaternium 10 (JR400) --- 0.3 ---
Polyquatemium 10 (1R125) --- 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 Weight %
ZZ AAA BBB CCC DDD
BAES 4.0 5.0 6.0 3.0 4.0
SUDS1 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
Dihydrogenated
Tallowamidoethyl 1.0 --- --
Hydroxyethylmonium
Methosulfate (1)
159
CA 02688927 2009-12-17
Ditallowamidoethyl
Hydroxypropylmonium --- 0.75 ---
Methosulfate (2)
Ditallow Dimethyl Ammonium --- 1.0 --- 1.0
Chloride (3)
Ditallowamidoethyl
Hydroxyethylmonium
Methosulfate (4)
Po lyquatemi um-16 (Luviquat
905)
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 0.08 0.1 0.1 0.1 0.1
Tetrastearate
Polyquatemium 10 (JR30M) 0.3 --- --- 0.1 0.3
Polyquatemium 10 (JR400) --- 0.3 ---
Polyquatemium 10 (JR125)
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 110 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 442-11OP from Witco (Dublin, Ohio,
USA)
160
CA 02688927 2009-12-17
**-
(4) Available under the trademark Varisoft 222 from Sherex Chemical Co.
(Dublin,
Ohio, USA)
Component Weight %
EEE FFF GGG 111111 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
Cocamidopropyl Betaine FB 6.0 --- 4.7 ---
Sodium Lauroamphoacetate --- 7.5 --- 7.5 7.5
SUDS10 0.2 0.2 5.0 0.3 1.2
Alkyl Glyceryl Sulfonate 10.0 ---
Mixture A
Mixture C --- 4.0
Mixture D 6.0 4.0 8.0 ---
Dihydrogenated
Tallowamidoethyl 0.25 0.5 ---
Hydroxyethylmonium
Methosulfate (1)
Ditallow Dimethyl Anunonium --- 1.0 ---
Chloride (3)
Di(partially hardened
soyoylethyl) --- 0.75 --- 1.0
Hydroxyethylmonium
Methosulfate (5)
Polyquatemium-16 (Luviquat 0.25
905)
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
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CA 02688927 2009-12-17
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 0.10 0.08 1.0 0.10 0.08
Tetrastearate
Polyquatemium 10 (JR30M)
Polyquaternium 10 (JR400) --- 0.3 ---
Polyquatemium 10 (JR125) 0.3 ---
Guar Hydroxypropyltrimonium 0.25 0.5
Chloride
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 442-11OP from Witco Corporation
(Dublin,
Ohio, USA)
(5) Available under the trademark Armocare EQ-S from Alczo-Nobel Chemicals
Inc.
(Chicago, Illinois, USA)
Mixture A. why 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
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CA 02688927 2012-01-13
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. 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
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.
Ingredients JJJ KKK LLL MIVLM NNN
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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
NaCI 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
SUDS8 0.2 0.2 0.2
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.0- Artiek
'µ...- -,...."
Cocoamidopropyl Betaine -- 2.50 --
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
Hydroxyethylcellulose I 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
Polyquatemium-10 -- -- 0.20
NaC1 0.30 0.30 --
Water and minors -------------------------- q.s. to 100% --
1Natros=7250 HHR from Aqualon
2Jaguar HP 60 from Rhone-Poulenc
TM
3Bermocoll E411 FQ from Alczo Nobel
The following are non-limiting examples of liquid detergent compositions
comprising the polymeric suds extenders according to the present invention.
EXAMPLE 35
TABLE I
165
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weight %
Ingredients A
C12-C15 Alkyl sulphate 28.0 25.0
C12-C13 Alkyl (E0.6_3) sulfate 30
C12 Amine oxide 5.0 3.0 7.0
C12.C14Betaine 3.0 1.0
C12-C14 Polyhydroxy fatty acid amide 1.5
C10 Alcohol Ethoxylate E9 1 2.0 4.0
Diamine 2 1.0 7.0
Mg2+ (as MgC12) 0.25
Citrate (cit2K3) 0.25
Polymeric suds booster 3 1.25 2.6 0.9
Minors and water 4 balance balance balance
pH of a 10% aqueous solution 9 10 10
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co.
2. 1,3-diaminopentane sold as Dytek EP.
3. Polypeptide comprising Lys, Ala, Glu, Tyr (5:6:2:1) having a molecular
weight of
approximately 52,000 daltons.
4. Includes perfumes, dyes, ethanol, etc.
EXAMPLE 36
TABLE II
weight %
Ingredients A
C12-C13 Alkyl (E0.6_3) sulfate 15.0 10.0
Paraffin sulfonate 20.0
Na C12-C13 linear alkylbenzene sulfonate 5.0 15.0 12.0
C12-C14 Betaine 3.0 1.0
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C12-C14 Polyhydroxy fatty acid amide 3.0 1.0
C10 Alcohol Ethoxylate E9 20.0
Diamine 2 1.0 7.0
DTPA 3 0.2
Mg2+ (as MgC12) 1.0
Ca2+ (as Ca(citrate)2) 0.5
Protease 4 0.01 0.05
Amylase 5 0.05 0.05
Hydrotrope 6 2.0 1.5 3.0
Polymeric suds booster 7 0.5 3.0 0.5
Minors and water 8 balance balance balance
pH of a 10% aqueous solution 9.3 8.5 11
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co.
2. 1,3-bis(methylamino)cyclohexane.
3. Diethylenetriaminepentaacetate.
4. Suitable protease enzymes include Savinasee; Maxatase8; Maxacale; Maxapem
158; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primasel4;
Durazyme; Opticlean0;and Optimasee; and Alcalase O.
5. Suitable amylase enzymes include Termamyl , Fungamyle; Duramy10; BAN , and
the amylases as described in W095/26397 and in WO 96/23873.
6. Suitable hydrotropes include sodium, potassium, ammonium or water-soluble
substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic
acid,
cumene sulfonic acid, xylene sulfonic acid.
7. Poly(DMAM-co-AA) (2:1) Copolymer of Example 3
8. Includes perfumes, dyes, ethanol, etc.
EXAMPLE 37
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TABLE III
weight %
Ingredients A
C12-C15 Alkyl (El) sulfate -- 30.0 --
C12-C15 Alkyl (ELL') sulfate 30.0 -- 27.0 --
C12-C15 Alkyl (E2.2) sulfate 15
C12 Amine oxide 5.0 5.0 5.0 3.0
C12-C14 Betaine 3.0 3.0
C10 Alcohol Ethoxylate E9 1 2.0 2.0 2.0 2.0
Diamine 2 1.0 2.0 4.0 2.0
Mg2+ (as MgC12) 0.25 0.25 --
Ca2+ (as Ca(citrate)2) 0.4
Polymeric suds booster 3 0.5 1.0 0.75 5.0
Minors and water 4 balanc balanc
balanc balanc
pH of a 10% aqueous solution 7.4 7.6 7.4 7.8
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co.
2. 1,3-diaminopentane sold as Dytek EP.
TM
3. LX1279 available from Baker Petrolite.
4. Includes perfumes, dyes, ethanol, etc.
EXAMPLE 38
TABLE IV
weight %
Ingredients A
C12-C13 Alkyl (4.6..3) sulfate 15.0 10.0
Paraffin sulfonate 20.0
Na C12-C13 linear alkylbenzene sulfonate 5.0 15.0 12.0
168
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C12-C14 Betaine 3.0 1.0
C12-C14 Polyhydroxy fatty acid amide 3.0 1.0
C 10 Alcohol Ethoxylate E9 1 20.0
Diamine 2 1.0 7.0
Mg2+ (as MgC12) 1.0
Ca2+ (as Ca(citrate)2) 0.5
Protease 3 0.1
Amylase 4 0.02
Lipase 5 0.025
DTPA 6 0.3
Citrate (cit2K3) 0.65
Polymeric suds booster 7 1.5 2.2 3.0
Minors and water 8 balance balance balance
pH of a 10% aqueous solution 9.3 8.5 11
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co.
2. 1,3-bis(methylamino)cyclohexane.
3. Suitable protease enzymes include Savinasee; Maxatasee; Maxacale; Maxapem
158; subtilisin BPN and BPN; Protease B; Protease A; Protease D; Primasee;
Durazyme; Opticleane;and Optimasee; and Alcalase e.
4. Suitable amylase enzymes include Terrnamyl , Fungamyle; Duramyle; BAN , and
the amylases as described in W095/26397 and WO 96/23873.
5. Suitable lipase enzymes include Amano-P; M1 Lipase ; Lipomaxe; Lipolasee;
D96L - lipolytic enzyme variant of the native lipase derived from Humicola
lanuginosa and the Humicola lanuginosa strain DSM 4106
6. Diethylenetriaminepentaacetate.
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7. Lysozyme.
8. Includes perfumes, dyes, ethanol, etc.
EXAMPLE 39
TABLE V
weight %
Ingredients A
C12-C13 Alkyl (4.6_3) sulfate 27.0
C12-C14 Betaine - 2.0 2.0
C14 Amine oxide 2.0 5.0 7.0
C12-C14 Polyhydroxy fatty acid amide 2.0
C10 Alcohol Ethoxylate E9 1 1.0 2.0
Hydrotrope 5.0
Diamine 2 4.0 2.0 5.0
Ca2+ (as Ca(citrate)2) 0.1 0.1
Protease 3 0.06 0.1
Amylase 4 0.005 0.05
Lipase 5 0.05
DTPA 6 0.1 0.1
Citrate (cit2K3) 0.3
Polymeric suds booster 7 0.5 0.8 2.5
Minors and water 8 balance balance balance
pH of a 10% aqueous solution 10 9 9.2
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co.
2. 1,3-diaminopentane sold as Dytek EP.
3. Suitable protease enzymes include Savinasee; Maxatasee; Maxacale; Maxapem
158; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primasee;
Durazym; Opticleane;and Optimasee; and Alcalase .
170
CA 02688927 2009-12-17
4. Suitable amylase enzymes include Termamyl , Fungamyle; Duramy10; BAN , and
the amylases as described in W095/26397 and WO 96/23873.
5. Suitable lipase enzymes include Amano-P; Ml Lipase ; Lipomaxe; Lipolase('),
D96L - lipolytic enzyme variant of the native lipase derived from Humicola
lanuginosa and the Humicola lanuginosa strain DSM 4106
6. Diethylenetriaminepentaacetate.
7. Poly(DMAM) homolymer of Example 2.
8. Includes perfumes, dyes, ethanol, etc.
171
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EXAMPLE 40
TABLE VI
weight %
Ingredients A
C12-C13 Alkyl (E1.4) sulfate 33.29 24.0
C12-C13 Alkyl (E0.6) sulfate 26.26
C12-C14 Polyhydroxy fatty acid amide 4.2 3.0 1.37
C14 Amine oxide 4.8 2.0 1.73
C11 Alcohol Ethoxylate E9 1 1.0 4.0 4.56
C12-C14 Betaine 2.0 1.73
MgC12 0.72 0.47 0.46
Calcium citrate 0.35
Polymeric suds booster 2 0.5 1.0 2.0
Minors and water 3 balance balance balance
pH of a 10% aqueous solution 7.4 7.8 7.8
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co.
2. Dimethylaminoethyl methacrylate/dimethylacrylamide copolyi-ner according to
any
one of Examples 1.
3. Includes perfumes, dyes, ethanol, etc.
EXAMPLE 41
A
AE0.6S1 28.80 28.80 26.09 26.09 26.09
Amine oxide2 7.20 7.20 6.50 6.50 6.50
Citric acid 3.00 ----
Maleic acid ---- 2.50 ----
Suds boosting 0.22 0.22 0.20 0.20 0.20
polymer3
Sodium 3.30 3.30 3.50 3.50 3.50
172
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Cumene
Sulfonate
Ethanol 40B 6.50 6.50 6.50 6.50 6.50
CIOE8 ---- ---- 3.00 3.00 3.00
C11E94 3.33 3.33 ---- ---- ----
' Diamine5 0.55 0.55 0.50 0.50 0.50
Perfume 0.31 0.31 ' ---- ---- ----
Water BAL. BAL. BAL. BAL. BAL.
...
Viscosity (cps 330 330 150 330 650
@ 70F)
pH @ 10% 9.0 9.0 8.3 ' 9.0 9.0
F G H I J
AE0.6S I 26 26 26 26 26
Amine oxide2 6.5 6.5 - 7.5 7.5 7.5
Citric acid . 3.0 - 2.5 - 3.0
Maleic acid - 2.5 3.0 -
C10E86 3 3 4.5 4.5 4.5
-Diamine5 0.5 0.5 1.25 0 1.25
Diamine7 0 0 0 1
Suds boosting 0 0.2 0.5 0.5 0.5
polymer3
Sodium cumene 3.5 3.5 2 2 2
sulphonate
Ethanol 8 8 ' 8 8 8
_
pH 9 9 9 8 10
173
CA 02688927 2012-01-13
. ,
1: C12-13 alkyl ethoxy sulfonate containing an average of 0.6 ethoxy groups.
2: C32-C 1 4 Amine oxide.
3: Polymer is (N,N-dimethylamino)ethyl methacrylate homopolymer
4: C11 Alkyl ethoxylated surfactant containing 9 ethoxy groups.
5: 1,3 bis(methylamine)-cyclohexane.
6: C10 Alkyl ethoxylated surfactant containing 8 ethoxy groups.
7: 1,3 pentane diamine.
EXAMPLE 42
Skin feel is determined by the modified acid phosphatase, or MAP method.
This method describes a rapid screening enzyme assay which predicts skin
mildness of
surfactant systems by measuring acid phosphatase inhibition as a result of
exposure
to surfactants.
PROCEDURE
Equipment
96 well flat bottom microtiter plate,
FinnipipetteTM (Labsystems) digital multichannel pipette (50-300u1) with
reservoir and tips,
Eppendorfrm repeater pipette with tips (1.25 and 5 ml),
gloves
plate shaker
plate reader(EL312 microplate by Bio Tek Instruments- Bio Kinetics Reader)
microtiter plate heating block
pH meter
Gilson PipetmanTM pipettes (10-100u1; 100-1000W) with tips
Reagents
purified acid phosphatase (typically, potato, type II lyophilized, from Sigma,
P3752)
174
CA 02688927 2009-12-17
wr.Ar%
Disodium p-nitrophenylphosphate (typically, Sigma 104 phosphatase
substrate)
citric acid (reagent grade)
sodium citrate (reagent grade)
HPLC grade water (or distilled/deionizecUhigh quality water(HQW))
water hardness concentrate (3:1 Ca++/Mg++, ITC supply)
Sodium hydroxide (0.5N NaOH)
Predried porcine stratum comeum
Preparation of solutions:
Prepare enzyme solution by making a 1-2mg/m1 solution (to give O.D. at
405nm of 1.2-1.7 with a target of 1.5) of purified acid phosphatase (0.5-1.0
units of activity/mg at room temperature) in HPLC water and keep on ice.
Make fresh prior to use.
Prepare citrate buffer at pH4.5 by combining 0.82g citric acid, 2.25g sodium
citrate, and Q.S. to 100m1 with HPLC water.
Prepare substrate/buffer solution: 3.0mM p-nitrophenylphosphatase(F.W.263)
in 10mM citrate buffer @pH 4.5 (add 8 mg PNPP in 10 ml citrate buffer.
Prepare development solution: 0.5N NaOH.
Make 7 gpg water: Add 0.6m1 of hardness concentrate to 1000m1 of HPLC
water
Partitioning followed by extraction of surfactants into stratum comeutn
Place the surfactant solution (300g) at the desired water hardness in a 115F
waterbath to get to temperature.
Cut and weigh the predried porcine stratum comeum to get approximately the
same size by weight sample from the same piece of pigskin for the treatments
to be tested and compared.
175
CA 02688927 2009-12-17
-e,re
Place the pigskins in the appropriate solutions, making sure the pigskins stay
at the bottom of beaker to insure all surface is exposed to solution, and let
soak for 30 minutes at the 115 F temperature.
After the soak, the pigskin is rinsed (or placed) in fresh room temperature 0
gpg water for 30 seconds.
After the rinse the pigskin is placed in a clean 15 ml vial and HQW( 12-14m1)
is added to the vial and aluminum foil is placed on the top of vial before lid
is
screwed on.
The vial is placed in the 115F waterbath for 2 hours and during the 2 hours
inverted every 1/2 hr.
After the extraction for 2 hrs the pigskin is removed and discarded and the
extract is evaporated to dryness using dry N2( overnight drying).
Reconstitute the dried extract with 0.4m1HQW and place back into waterbath
set at 50-55C to insure surfactant goes in solution- the solution should be
clear.
Addition of Surfactants to Microtiter Wells
Place empty microtiter plate on pre-heated plate warming block (115F). Place
thermometer in plate and wait for temperature to reach @ 113F.
Add 50 ul of the heated extracted surfactant solutions (400 ul) to designated
wells. Add 50 ul of 115F water (hardness in which soak was conducted) to
control wells and the blanks. Generally, blanks are run as the first well in
each row.
Add 25 ul of the enzyme solution to each well except blanks (the control will
have enzyme, but no surfactant, and will show the highest enzyme activity) as
quickly as possible(< 30 sec.). Add 25 ul of the 115F water (hardness in
which soak was conducted) to the blanks. Once enzyme added to first well
set timer for five minutes.
176
CA 02688927 2009-12-17
..=""= APO%
Move microtiter plate to plate shaker. Shake for 30 seconds.
Return microtiter plate to plate warming block for the duration of the five
minutes. After the five minutes remove from heating block.
Add 75 ul of the substrate/buffer solution to each well using the multi-
channel
pipette. This step activates the enzyme to liberate product, so the solution
must be added as quickly and as accurately as possible(< 30 sec.). Activate
wells of a single row first before adding solution to wells of the next row.
After 3 minutes, quickly add 100 ul of 0.5N NaOH to each well using the
multi-channel pipette. This step stops the reaction and develops the color for
the spectrophotometric measurement at 405nm using the plate reader, so this
solution must also be added as quickly and as accurately as possible (<30
sec.). The color will be stable for up to 30 minutes if the plate is covered.
Obtain absorbance results using plate reader set at 405 nm.
Background Correction
Some surfactants may interfere at 405nm and background correction is
required for these materials. The correction is made by simply redoing the
above 8 steps with the exception of adding the enzyme solution. This is
replaced with 25 ul of water. Read wells at 405nm and subtract background
absorbance values from absorbances (average) derived from corresponding
reacted wells. A background subtraction should be performed for every
surfactant and product tested.
Calculation
Subtract blank absorbance value from control absorbance value to obtain the
absorbance of the control wells(maximum enzyme introduced in the
experiment). Subtract surfactant absorbance backgrounds from appropriate
surfactant - acid phosphatase absorbances to obtain absorbance of surfactant
wells.
177
CA 02688927 2009-12-17
Derive Ratio of Inhibition (or % enzyme deactivation) for each concentration
as follows:
[ 1-(absorbance of surfactant/absorbance of control) ] * 100
Reporting
Report the % enzyme deactivation of the different formulae tested and
compare to a control product. An increase in % deactivation corresponds to
greater product harshness outside the standard deviation of test method (+1-
4%).
Effect of including polymeric suds booster in an LDL composition
The LDL composition tested has the formula
AE0.6S 26.6
Amine Oxide 6.60
C11E9/C10E8 3.1
Diamine 0.5
Polymer 0.22
water minors qs to 100%
The polymer used is the polymer of Example 2 above. MAP results are in %
deactivation
Hardness, in LDL with LDL with nil-
grains per 0.22% polmer
gallon polymer
2 gpg 27B 46
7gpg 37BC 50
This result clearly shows the mildness benefit gained from including the suds
boosting polymers of the present invention.
178
