Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY DETERGENT COMPOSITIONS WITH FABRIC CARE
10
TECHNICAL FIELD
The present invention relates to laundry detergent compositions comprising a
semi-polar nonionic surfactant and certain cyclic amine based polymer,
oligomer
or copolymer materials.
BACKGROUND OF THE INVENTION
It is well known that alternating cycles of using and laundering fabrics and
textiles, such as articles of worn clothing and apparel, will inevitably
adversely
affect the appearance and integrity of the fabric and textile items so used
and
laundered. Fabrics and textiles simply wear out over time and with use.
Laundering of fabrics and textiles is necessary to remove soils and stains
which
accumulate therein and thereon during ordinary use. However, the laundering
operation itself, over many cycles, can accentuate and contribute to the
deterioration of the integrity and the appearance of such fabrics and
textiles.
Deterioration of fabric integrity and appearance can manifest itself in
several
ways. Short fibers are dislodged from woven and knit fabric/textile structures
by
the mechanical action of laundering. These dislodged fibers may form lint,
fuzz
or "pills" which are visible on the surface of fabrics and diminish the
appearance
of newness of the fabric. Further, repeated laundering of fabrics and
textiles,
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especially with bleach-containing laundry products, can remove dye from
fabrics
and textiles and impart a faded, worn out appearance as a result of diminished
color intensity, and in many cases, as a result of changes in hues or shades
of
color.
Given the foregoing, several materials which could be added to laundry
detergent
products that would associate themselves with the fibers of the fabrics and
textiles laundered using such detergent products and thereby reduce or
minimize
the tendency of the laundered fabric/textiles to deteriorate in appearance,
have
been identified in the art. Examples of such materials are cationic softening
surfactants, cyclic amine based polymers, dye transfer inhibitors, chelating
agents, crystal growth inhibitors.
However, it has been found that the fabric care cationic cyclic amine based
polymers are not highly compatible with the high levels of anionic surfactants
usually formulated within the conventional laundry detergent compositions. It
has
been found further that those anionic surfactants significantly decrease the
efficiency of such cyclic amine based compounds. Such high levels of anionic
surfactants are generally used to provide good cleaning properties. Therefore,
in
order to formulate compositions with such cationic cyclic amine based
polymers,
detergent compositions have been formulated without anionic surfactants but
with nonionic surfactants. However, it has been found that detergent
compositions with a high level of nonionic surfactants do not provide the same
cleaning performance as comparable high level of anionic surfactants and are
more difficult to formulate, especially at high electrolyte content.
In view of the above, the object of the present invention is therefore to
formulate
a laundry detergent composition which provide excellent cleaning properties
together with excellent fabric care benefits. It has been surprisingly found
that the
combination of a semi-polar nonionic surfactant with the above mentioned
cationic cyclic amine based polymer provide both excellent cleaning properties
together with excellent fabric care benefits.
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It has been further found that the combination of the semi-polar nonionic
surfactants with the cyclic amine based polymers, of the present invention
provide good dye transfer inhibition and antifading.
Furthermore, it has been found that that the compositions of the present
invention demonstrate high physical stability when formulated in a liquid
form.
SUMMARY OF THE INVENTION
The present invention is directed to laundry detergent compositions comprising
a
semi-polar nonionic surfactant and a cyclic amine based polymer, oligomer or
copolymer. Such compositions provide good cleaning performance as well as the
desired fabric appearance and integrity benefits. The cyclic amine based
polymer, oligomer or copolymer is characterized by the following formula as
defined below.
T W-R2 W-T Ab
x
In its method aspect, the present invention relates to the laundering of
fabrics
and textiles in aqueous washing or treating solutions formed from effective
amounts of the detergent compositions described herein, or formed from the
individual components of such compositions. Laundering of fabrics and textiles
in
such washing solutions, followed by rinsing and drying, imparts fabric
cleaning as
well as fabric appearance benefits to the fabric and textile articles so
treated.
Such fabric care benefits can include improved overall appearance, pill/fuzz
reduction, antifading, improved dye transfer inhibition, improved abrasion
resistance, and/or enhanced softness.
DETAILED DESCRIPTION OF THE INVENTION
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The laundry detergent compositions of the present invention comprise a cyclic
amine based polymer and an amine oxide surfactants and provide excellent
cleaning properties together with excellent fabric care benefits.
Without wishing to be bound by theory, it is believed that the semi-polar
nonionic
surfactants by their chemical nature, introduce some 'hidden' anionic
character.
Therefore, those semi-polar nonionic surfactants so provide good cleaning
properties while not interacting with the cationic polymers, thereby providing
excellent fabric cleaning and fabric care properties.
In addition, it has also been surprisingly found that such semi-polar nonionic
surfactants act as hydrotropes within compositions of the present invention,
when
formulated in the liquid form. Indeed, without wishing to be bound by theory,
it is
known in the art that high levels of nonionic surfactants within liquid
compositions
lead to phase separation. It has been found that the semi-polar nonionic
surfactants of the present invention, act as hydrotropes and reduce greatly
phase
separation. These semi-polar nonionic surfactants therefore are found to
facilitate the formulation of high nonionic detergent compositions and to
increase
the physical stability of liquid products. This allows to formulate laundry
detergent
compositions comprising a high level of nonionic surfactants, which are
perfectly
fluid isotropic liquids.
The first essential element of the laundry detergent compositions of the
present
invention is the cyclic amine based polymer, oligomer or copolymer as
described
hereinafter :
A) Cyclic amine Based Polymer, Oligomer or Copolymer Materials
The first essential component of the compositions of the present invention is
one
or more cyclic amine based polymer, oligomer or copolymer. Such materials
have been found to impart a number of appearance benefits to fabrics and
textiles laundered in aqueous washing solutions formed from detergent
compositions which contain such cyclic amine based fabric treatment materials.
Such fabric appearance benefits can include, for example, improved overall
appearance of the laundered fabrics, reduction of the formation of pills and
fuzz,
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improved dye transfer inhibition, protection against color fading, improved
abrasion resistance, etc.
As mentioned above, the combination of semi-polar nonionic surfactants with
the
cyclic amine based fabric treatment materials used in the compositions and
methods according to the present invention can provide such fabric appearance
benefits while maintaining good cleaning performance.
The cyclic amine based polymer, oligomer or copolymer component of the
compositions herein may comprise combinations of these cyclic amine based
materials. For example, a mixture of piperadine and epihalohydrin condensates
can be combined with a mixture of morpholine and epihalohydrin condensates to
achieve the desired fabric treatment results. Moreover, the molecular weight
of
cyclic amine based fabric treatment materials can vary within the mixture as
is
illustrated in the Examples below.
As will be apparent to those skilled in the art, an oligomer is a molecule
consisting of only a few monomer units while polymers comprise considerably
more monomer units. For the present invention, oligomers are defined as
molecules having an average molecular weight below about 1,000 and polymers
are molecules having an average molecular weight of greater=than about 1,000.
Copolymers are polymers or oligomers wherein two or more dissimilar monomers
have been simultaneously or sequentially polymerized. Copolymers of the
present invention can include, for example, polymers or oligomers polymerized
from a mixture of a primary cyclic amine based monomer, e.g., piperidine, and
a
secondary cyclic amine monomer, e.g., morpholine.
The cyclic amine based fabric treatment component of the detergent
compositions herein will generally be comprised at a level of from 0.01% to 5%
by the weight of the detergent composition, preferably at a level of from 0.1
% to
4% by weight, more preferably at a level of from 0.75% to 3%.
The cyclic amine based polymers, oligomers or copolymers suitable for the
purpose of the present invention are characterized by the following general
formula:
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T W- R2 W-T Ab
x
wherein;
each T is independently selected from the group consisting of H, C1-C12
alkyl, substituted alkyl, C7-C12 alkylaryl,
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
COOM
-CH COOM
CH-COOM -CH COOM
' ~COOM
H CH2-COOM -CH2
COOM
-CHZ COOM
COOM
Rj\ Ri
, and -R2Q;
-wherein W comprises at least one cyclic constituent selected from the group
consisting of:
iR3c (R3)c ~D~ I~3)c ~3)c
N-D N N D-N R4
R3 (D)c i 3 N
q
q , and
R4
N" \N~
in addition to the at least one cyclic constituent, W may also comprise an
aliphatic or substituted aliphatic moiety of the general structure;
6
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f 3)c (R3 1
N- N
1
L JR3 qR3
-each B is independently Cl-C12 alkylene, Cl-C12 substituted alkylene,
C3-C12 alkenylene, C8-C12 dialkylarylene, C8-C12 dialkylaryienediyl, or
- (R50)nR5-;
-each D is independently C2-C6 alkylene;
-each Q is independently selected from the group consisting of hydroxy,
Cl-C1g alkoxy, C2-C18 hydroxyalkoxy, amino, Cl-C1g alkylamino,
dialkylamino, trialkylamino groups, heterocyclic monoamino groups and
diamino groups;
-each R, is independently selected from the group consisting of H, C1-C$ alkyl
and Cl-C$ hydroxyalkyl;
-each R2 is independently selected from the group consisting of
Cl-C12 alkylene, CI-C12 alkenylene, -CH2-CH(ORj)-CH2,
C8-C12 alkarylene, C4-C12 dihydroxyalkylene, and
poly(C2-C4 alkyleneoxy)alkylene;
-each R3 is independently selected from the group consisting of H, R2, 0,
CI-C20 hydroxyalkyl, CI-C20 alkyl, substituted alkyl, Cs-CII aryl,
substituted aryl, C7-C11 alkylaryl, Cl-C20 aminoalkyl,
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
cooM
~ COOM
-CH cOOM Coom
CH-COOM -CH -CHY-____COOM
OfH CH2-COOM -~COOM
CHz COOM 20
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-each R4 is independently selected from the group consisting of H, Cl-C22
alkyl,
C1-C22 hydroxyalkyl, aryl and C7-C22 alkylaryl;
-each R5 is independently selected from the group consisting of C2-C8
alkylene,
C2-C8 alkyl substituted alkylene; and
A is a compatible monovalent or di or poiyvalent anion;
M is a compatible cation;
b = number necessary to balance the charge;
each x is independently from 3 to about 1000, preferably from 3 to 25,
more preferably from 4 to 20;
each c is independently 0 or 1;
each h is independently from about 1 to about 8;
each q is independently from 0 to about 6;
each n is independently from 1 to about 20;
each r is independently from 0 to about 20; and
each t is independently from 0 to 1.
Amongst suitable cyclic amine based compounds of the present invention
are those compounds wherein at least about 10 mole%, preferably at least
about 20 mole%, more preferably at least about 30 mole%, and most
preferably at least about 50 mole% of the R3 groups are 0, provided that
O is only present on a tertiary N.
Amongst further suitable cyclic amine based compounds of the present
invention are those compounds wherein :
-at least about 1.0 %, preferably at least abut 5.0 %, and more preferably
at least about 10 %, and most preferably at least about 20 % of the total
number of T and R3 groups are anionic moieties selected from the group
consisting of
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
COOM
-CH COOM COOM
COOM -CH2~COOM
CH-COOM -CH
~
O/H CH2-COOM COOM COOM
, > >
and mixtures thereof.
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These cyclic amine based polymers can be linear or branched. One specific type
of branching can be introduced using a polyfunctional crosslinking agent. An
example of such polymer is exemplified below.
T
I
L X2
k x
H
HO O OH
T~R~ ~__'~~W-R2~T
x
The Example section below contains numerous non-limiting examples of cyclic
amine polymers according to the present invention.
1) a cyclic amine such as imidazole, alkyl imidazole, aminoalkyl imidazole,
benzimidazole, piperazine, aminoalkyl piperazine, bis(N-aminoalkyl)piperazine,
aminoalkyl morpholine, aminoalkyl piperidine, and optionally an acyclic amine
and mixtures thereof;
2) a cross linking agent selected from the group consisting of 1,2
dichloroethane,
1,2 dichloropropane, 1,3 dichloropropane, 1,3 dichloropronae-2-ol, 1,4
dichlorobutane, 1,6 dichlorohexane, epichlorohydrin, bisepoxybutane,
bisglicedyl
ether of 4,4'didihydroxydiphenyl-dimethylmethane, bishalohydrins of C2-C8
diols,
bisglycidyl ethers C2-C18 diols, bisglycidyl ethers of polyalkyleneglycols and
mixtures thereof
Preferred cyclic amine based compounds that fall within the above general
structure include compounds:
- wherein each R1 is H; and
-at least one W is selected from the group consisting of:
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(RA (R3)C (R3)C (RA
I 1~/
N-D N N D-N
R3 R3
q q
(RA (R3)C~ (R3)C (RA
I:Dq
R4 R4
/ N I~ and u
Even more preferred compounds for the fabric appearance and integrity
benefits are those:
-wherein each Rl is H; and
-at least one W is selected from the group consisting of:
(RA (RA
I ~~ R4
N-D N N D-N
R3 ~3)c/ (R3)c N \ N/
R3 and
,
R4
N" \N~
And most preferred compounds for the fabric appearance and integrity benefits
are those:
-wherein each Rl is H; and
-at least one W is selected from the group consisting of:
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R4 R4
/
U and
Preferred compounds to be used as the linking group R2 include, but are not
limited to: polyepoxides, ethylenecarbonate, propylenecarbonate, urea, a, R-
unsaturated carboxylic acids, esters of a, P-unsaturated carboxylic acids,
amides
of a, P-unsaturated carboxylic acids, anhydrides of a, P-unsaturated
carboxylic
acids, di- or polycarboxylic acids, esters of di- or polycarboxylic acids,
amides of
di- or polycarboxylic acids, anhydrides of di- or polycarboxylic acids,
glycidylhalogens, chloroformic esters, chloroacetic esters, derivatives of
chloroformic esters, derivatives of chloroacetic esters, epihalohydrins,
glycerol
dichtorohydrins, bis-(halohydrins), polyetherdihalo-compounds, phosgene,
polyhalogens, functionalized glycidyl ethers and mixtures thereof.
Moreover, R2 can also comprise a reaction product formed by reacting
one or more of polyetherdiamines, alkylenediamines, polyalkylenepolyamines,
alcohols, alkyleneglycols and polyalkyleneglycols with a, P-unsaturated
carboxylic acids, esters of a, P-unsaturated carboxylic acids, amides of (X, R-
unsaturated carboxylic acids and anhydrides of a, P-unsaturated carboxylic
acids
provided that the reaction products contain at least two double bonds, two
carboxylic groups, two amide groups or two ester groups.
Additionally preferred cyclic amine based polymer, oligomer or copolymer
materials for use herein include adducts of two or more compositions selected
from the group consisting of piperazine, piperadine, imidazole,
epichlorohydrin
benzyl quat, epichlorohydrin methyl quat, morpholine and mixtures thereof.
B) The Semi-polar nonionic Surfactant
The second essential element of the laundry detergent compositions of the
present invention is a semi-polar nonionic surfactant, preferably an amine
oxide
surfactant.
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Semi-polar nonionic surfactants are a special category of nonionic surfactants
which include water-soluble amine oxides containing one alkyl moiety of from
about 8 to about 18 carbon atoms and 2 moieties selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to
about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of from about 8 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 8 to about 18 carbon atoms and a moiety selected
from the group consisting of alkyl and hydroxyalkyl moieties of from about 1
to
about 3 carbon atoms.
Preferred semi-polar nonionic detergent surfactants for the purpose of the
present invention are the amine oxide surfactants having the formula
0
T
R3(OR4)xN(R5)2
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 C10-C18 alkyl dimethyl
amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides, more
preferably the C12-C14 alkyl dimethyl amine oxide.
The laundry detergent compositions of the present invention typically comprise
from 0.1 % to 20%, preferably from about 1% to about 10%, more preferably from
2% to 7% by weight of such semi-polar nonionic surfactants.
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Detergent components
The laundry detergent compositions of the present invention may contain
additional detergent components. The precise nature of these additional
component, and levels of incorporation thereof will depend on the physical
form
of the composition, and the nature of the cleaning operation for which it is
to be
used.
The laundry detergent compositions of the present invention preferably further
comprise a detergent ingredient selected from nonionic and/or cationic
surfactants, a cellulosic based polymers or oligomers, dye transfer inhibiting
polymers, a mannanase enzyme and/or mixtures thereof.
When formulated as compositions suitable for use in a laundry machine washing
method, the compositions of the invention preferably contain both a surfactant
and a builder compound and additionally one or more detergent components
preferably selected from organic polymeric compounds, bleaching agents,
additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil
suspension and anti-redeposition agents and corrosion inhibitors. Laundry
compositions can also contain softening agents, as additional detergent
components.
The compositions of the invention can also be used as detergent additive
products. Such additive products are intended to supplement or boost the
performance of conventional detergent compositions.
The laundry detergent compositions according to the invention can be liquid,
paste, gels, bars, tablets, spray, foam, powder or granular. Granular
compositions can also be in "compact" form and the liquid compositions can
also
be in a "concentrated" form.
If needed the density of the laundry detergent compositions herein ranges from
400 to 1200 g/litre, preferably 500 to 950 g/litre of composition measured at
20 C.
The "compact" form of the compositions herein is best reflected by density
and,
in terms of composition, by the amount of inorganic filler salt; inorganic
filler salts
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are conventional ingredients of detergent compositions in powder form; in
conventional detergent compositions, the filler salts are present in
substantial
amounts, typically 17-35% by weight of the total composition. In the compact
compositions, the filler salt is present in amounts not exceeding 15% of the
total
composition, preferably not exceeding 10%, most preferably not exceeding 5%
by weight of the composition. The inorganic filler salts, such as meant in the
present compositions are selected from the alkali and alkaline-earth-metal
salts
of sulphates and chlorides. A preferred filler salt is sodium sulphate.
Liquid detergent compositions according to the present invention can also be
in a
"concentrated form", in such case, the liquid detergent compositions according
the present invention will contain a lower amount of water, compared to
conventional liquid detergents. Typically the water content of the
concentrated
liquid detergent is preferably less than 40%, more preferably less than 30%,
most
preferably less than 20% by weight of the detergent composition.
Suitable detergent compounds for use herein are selected from the group
consisting of the below described compounds.
Surfactants
The laundry detergent compositions of the present invention can further
comprise other detersive surfactants selected from anionic, nonionic,
zwitterionic,
ampholytic or cationic type or can comprise compatible mixtures of these
types.
Preferably the laundry detergent compositions of the present invention will
comprise a high level of nonionic surfactants - one or more- and a low level
of
anionic surfactants -one or more. More preferably the nonionic surfactants
will be
comprised within the laundry detergent composition of the present invention at
a
level of from 1%-50%, most preferably at a level of from 5%-30%, even most
preferably at a level of from 15%-25% by weight of the total composition. More
preferably the anionic surfactants will be comprised within the laundry
detergent
compositions of the present invention at a level of from 0%-10%, most
preferably
at a level of from 0%-5%. Even most preferably, the laundry detergent
compositions of the present invention will comprise no anionic surfactants.
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Preferred nonionic surfactants for the laundry detergent compositions of the
present invention are the condensation products of primary and secondary
aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide,
and/mixtures thereof. 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. Preferred are the condensation products of alcohols
having an alkyl group containing from about 8 to about 20 carbon atoms, more
preferably from about 10 to about 18 carbon atoms, with from about 2 to about
10 moles of ethylene oxide per mole of alcohol. About 3 to about 9 moles of
ethylene oxide and most preferably from 5 to 7 moles of ethylene oxide per
mole
of alcohol are present in said condensation products. Examples of commercially
available nonionic surfactants of this type include TergitolTM 15-S-9 (the
condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide),
TergitolTM 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; NeodolTM 45-9 (the condensation
product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-
3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of
ethylene
oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with
7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C14-
C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical
Company, KyroTM EOB (the condensation product of C13-C15 alcohol with 9
moles ethylene oxide), marketed by The Procter & Gamble Company, and
GenapdT"~ LA 030 or 050 (the condensation product of C12-C14 alcohol with 3
or 5 moles- of ethylene oxide) marketed by Hoechst. Preferred range of HLB in
these products is from 8-11 and most preferred from 8-10.
Also useful as the nonionic surfactant of the present invention are the
alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued
January 21, 1986, having a hydrophobic group containing from about 6 to about
30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a
polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about
1.3
to about 10, preferably from about 1.3 to about 3, most preferably from about
1.3
to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6
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atoms can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the glucosyl moieties (optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose
as
opposed to a glucoside or galactoside). The intersaccharide bonds can be,
e.g.,
between the one position of the additional saccharide units and the 2-, 3-, 4-
,
and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula :
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups
contain from about 10 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 alkylpolyethoxy alcohol is formed
first
and then reacted with glucose, or a source of glucose, to form the glucoside
(attachment at the 1-position). The additional glycosyl units can then be
attached
between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-
position, preferably predominately the 2-position.
Also useful as nonionic surfactants are the condensation products of ethylene
oxide with a hydrophobic base formed by the condensation of propylene oxide
with propylene glycol. The hydrophobic portion of these compounds will
preferably have a molecular weight of from about 1500 to about 1800 and will
exhibit water insolubility. The addition of polyoxyethylene moieties to this
hydrophobic portion tends to increase the water solubility of the molecule as
a
whole, and the liquid character of the product is retained up to the point
where
the polyoxyethylene content is about 50% of the total weight of the
condensation
product, which corresponds to condensation with up to about 40 moles of
ethylene oxide. Examples of compounds of this type include certain of the
commercially-available PlurafacTM LF404 and PluronicTM surfactants, marketed
by BASF.
Also suitable for use as the nonionic surfactant are the condensation products
of
ethylene oxide with the product resulting from the reaction of propylene oxide
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and ethylenediamine. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and generally
has a molecular weight of from about 2500 to about 3000. This hydrophobic
moiety is condensed with ethylene oxide to the extent that the condensation
product contains from about 40% to about 80% by weight of polyoxyethylene and
has a molecular weight of from about 5,000 to about 11,000. Examples of this
type of nonionic surfactant include certain of the commercially available
TetronicTM compounds, marketed by BASF.
Further useful nonionic surfactants are polyhydroxy fatty acid amide
surfactants
of the formula :
R2-C-N-Z,
11 1
O R1
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl
or
a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected
to
the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2
is a
straight C11-15 alkyl or C16-18 alkyl or alkenyl chain such as coconut alkyl
or
mixtures thereof, and Z is derived from a reducing sugar such as glucose,
fructose, maltose, lactose, in a reductive amination reaction.
Further nonionic surfactants are Polyethylene, polypropylene, and polybutylene
oxide condensates of alkyl phenols, with the polyethylene oxide condensates
being preferred. These compounds include the condensation products of alkyl
phenols having an alkyl group containing from about 6 to about 14 carbon
atoms,
preferably from about 8 to about 14 carbon atoms, in either a straight-chain
or
branched-chain configuration with the alkylene oxide. In a preferred
embodiment,
the ethylene oxide is present in an amount equal to from about 2 to about 25
moles, more preferably from about 3 to about 15 moles, of ethylene oxide per
mole of alkyl phenol. Commercially available nonionic surfactants of this type
include lgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X-
45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These
surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl
phenol ethoxylates).
17
CA 02386914 2005-05-19
Cationic detersive surfactants suitable for use in the laundry detergent
compositions of the present invention are those having one long-chain
hydrocarbyl group. Examples of such cationic surfactants include the ammonium
surfactants such as alkyitrimethylammonium halogenides, and those surfactants
having the formula :
[R2(OR3)y][R4(OR3)y]2R5N+x-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon atoms in the alkyl chain, each R3 is selected from the group consisting
of
-CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4
hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -
CH2CHOH-CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose
polymer having a molecular weight less than about 1000, and hydrogen when y
is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number
of
carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to
about
10 and the sum of the y values is from 0 to about 15; and X is any compatible
anion.
Quatemary ammonium surfactant suitable for the present invention has the
formula (I):
R3
3
I ,,A-
RI~o
x-
Formula I 25 whereby R, is a short chainlength alkyl (C6-C10) or
alkylamidoalkyl of the
formula (II) :
Cscvy N~O
O
Formula II
y is 2-4, preferably 3.
whereby R2 is H or a C1-C3 alkyl,
18
CA 02386914 2005-05-19
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and can be either a
short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,
whereby X- is a counterion, preferably a halide, e.g. chloride or
methylsulfate.
Rs
yH
~ )z
Formula III
R6 is C1-C4 and z is 1 or 2.
Prefen-ed quat ammonium surfactants are those as defined in formula I whereby
R1 is C8, C10 or mixtures thereof, x=o,
R3, R4 = CH3 and R5 = CH2CH2OH.
Highly preferred cationic surfactants are the water-soluble quatemary
ammonium compounds useful in the present composition having the formula :
R1 R2R3R4N+X- (i)
wherein R1 is C8-C16 alkyl, each of R2, R3 and R4 is independently C1-C4
alkyl,
C1-C4 hydroxy alkyl, benzyl, and -(C2H40)xH where x has a value from 2 to 5,
and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is C12-C15 particularly where the
alkyl
group is a mixture of chain lengths derived from coconut or palm kemel fat or
is
derived synthetically by olefin build up or OXO alcohols synthesis. Preferred
groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X
may be selected from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quatemary ammonium compounds of formulae (i) for use
herein are :
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyt triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
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lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
CH2-CH2-O-C-C12-14 alkyl and R2R3R4 are methyl).
11
0
di-alkyl imidazolines [compounds of formula (i)].
Other cationic surfactants useful herein are also described in U.S. Patent
4,228,044, Cambre, issued October 14, 1980 and in European Patent
Application EP 000,224.
Other cationic materials are the fabric softening components including the
water-
insoluble quaternary-ammonium fabric softening actives or their corresponding
amine precursor, the most commonly used having been di-long alkyl chain
ammonium chloride or methyl sulfate.
Preferred cationic softeners among these include the following:
1) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipaimityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium chloride;
11) C12-18 alkyl dihydroxyethyl methylammonium chloride;
12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallow-oxy-ethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowylamidoethyl)-2-tallowyl imidazolinium methylsulfate.
Biodegradable quaternary ammonium compounds have been presented as
alternatives to the traditionally used di-long alkyl chain ammonium chlorides
and
methyl sulfates. Such quaternary ammonium compounds contain long chain
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alk(en)yl groups interrupted by functional groups such as carboxy groups. Said
materials and fabric softening compositions containing them are disclosed in
numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.
The quaternary ammonium compounds and amine precursors herein have the
formula (I) or (II), below :
R2 R3 R3
3
R~ + N~ (CH2)n-CH -CH, X
+ I(CH2}ri-Q-'T X R3 Q
I
R1
Tl TZ
or,
(I) (II)
wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-0-, -NR4-C(O)-, -C(O)-
N R4-;
R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
R4 is H or C1-C4 alkyl or C1-C4 hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C11-C22 alkyl or alkenyl;
n and m are integers from 1 to 4; and
X- is a softener-compatible anion. Non-limiting examples of softener-
compatible
anions include chloride or methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11
carbon
atoms, preferably at least 16 carbon atoms. The chain may be straight or
branched. Tallow is a convenient and inexpensive source of long chain alkyl
and
alkenyl material. The compounds wherein T1, T2, T3, T4, T5 represents the
mixture of long chain materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds suitable for use in the
aqueous fabric softening compositions herein include :
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
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N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl )-N, N-dimethyl
ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N, N-dimethyl
ammonium chloride;
N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1 ,2-dital lowyloxy-3-N, N, N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
When included therein, the laundry detergent compositions of the present
invention typically comprise from 0.2% to about 25%, preferably from about 1 %
to about 8% by weight of such cationic surfactants.
Conventional useful anionic surfactants can themselves be of several different
types. For example, water-soluble salts of the higher fatty acids, i.e.,
"soaps",
are useful anionic surfactants in the compositions herein. This includes
alkali
metal soaps such as the sodium, potassium, ammonium, and alkylolammonium
salts of higher fatty acids containing from about 8 to about 24 carbon atoms,
and
preferably from about 12 to about 18 carbon atoms. Soaps can be made by
direct saponification of fats and oils or by the neutralization of free fatty
acids.
Particularly useful are the sodium and potassium salts of the mixtures of
fatty
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acids derived from coconut oil and tallow, i.e., sodium or potassium tallow
and
coconut soap.
Additional non-soap anionic surfactants which are suitable for use herein
include the water-soluble salts, preferably the alkali metal, and ammonium
salts,
of organic sulfuric reaction products having in their molecular structure an
alkyl
group containing from about 10 to about 20 carbon atoms and a sulfonic acid or
sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion
of acyl
groups.) Examples of this group of synthetic surfactants are a) the sodium,
potassium and ammonium alkyl sulfates, especially those obtained by sulfating
the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing
the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium
alkyl polyethoxylate sulfates, particularly those in which the alkyl group
contains
from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the
polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate
moieties;
and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl
group contains from about 9 to about 15 carbon atoms, in straight chain or
branched chain configuration, e.g., those of the type described in U.S.
Patents
2,220,099 and 2,477,383. Especially valuable are linear straight chain
alkylbenzene sulfonates in which the average number of carbon atoms in the
alkyl group is from about 11 to 13, abbreviated as C11-13 LAS.
Further suitable surfactants for use in the laundry detergent compositions
described herein are amine based surfactants of the general formula:
R3
Rl -X-(CH2)n-N
R4
wherein R1 is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging
group which is selected from NH, CONH, COO, or 0 or X can be absent; and R3
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WO 01/32816 PCT/US00/28438
and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(R5))
wherein R5 is H or methyl. Especially preferred amines based surfactants
include
the following:
R1-(CH2)2-NH2
Rl-O-(CH2)3-NH2
Rl-C(O)-NH-(CH2)3-N(CH3)2
CH2-CH(OH)-R5
I
Rl-N
CH2-CH(OH)-R5
wherein Rl is a C6-C12 alkyl group and R5 is H or CH3. Particularly preferred
amines for use in the surfactants defined above include those selected from
the
group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, C8-
C12 bis(hydroxyethyl)amine, C8-C12 bis(hydroxyisopropyl)amine, C8-C12 amido-
propyl dimethyl amine, or mixtures thereof. In a highly preferred embodiment,
the
amine based surfactant is described by the formula: Rl-C(O)-NH-(CH2)3-
N(CH3)2 wherein Rl is Cg-Cl 2 alkyl.
Cellulosic based polymer or oligomer
The laundry detergent compositions of the present invention can further
comprise one or more cellulosic based polymer or oligomer. Such materials
have been found to impart a number of appearance benefits to fabrics and
textiles laundered in aqueous washing solutions formed from detergent
compositions which contain such cellulosic based fabric treatment materials.
Such fabric appearance benefits can include, for example, improved overall
appearance of the laundered fabrics, reduction of the formation of pills and
fuzz,
protection against color fading, improved abrasion resistance, etc.
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WO 01/32816 PCT/US00/28438
One suitable type of cellulosic based polymer or oligomer fabric treatment
material for use herein has an average molecular weight of from about 5,000 to
about 2,000,000, preferably from about 50,000 to about 1,000,000.
These cellulosic based compounds will generally be comprised at a level of
from
0.1 % to 5%, more preferably at a level of from 0.5% to 4%, more preferably at
a
level of from 0.75% to 3% by the weight of the detergent composition.
One suitable group of cellulosic based polymer or oligomer materials for use
herein is characterized by the following formula:
R
O R
O ~R
O
O O i 1
0 0 O
R R O
R
wherein each R is selected from the group consisting of R2, Rc, and
CH, CH O RH
1
R2 t
wherein:
- each R2 is independently selected from the group consisting of H and C1-C4
alkyl;
0
11
- each Rcis -(CH,)y-C-OZ
wherein each Z is independently selected from the group consisting of M, R2,
Rc, and RH;
- each RH is independently selected from the group consisting of C5 -C20
alkyl,
C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl,
hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-
hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2-hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-
2-hydroxyalkyl, C6-C12 aryloxy-2-hydroxyalkyl,
CA 02386914 2002-04-04
WO 01/32816 PCT/US00/28438
O R5 O R5 O R5 O
II 1 II 1 II 1 II
-C CH C CH2 -C CH, CH C-OM and
O R5 O
II 1 II
-C-CH-CH,-C-OM.
- each R4 is independently selected from the group consisting of H, C1-C20
alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl,
alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl,
cycloalkylaminoalkyl and hydroxyalkyl;
- each R5 is independently selected from the group consisting of H, C1 -C20
alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted
alkyl, hydroxyalkyl, (R4)2N-alkyl, and (R4)3 N-alkyl;
wherein:
M is a suitable cation selected from the group consisting of Na, K, 1/2Ca,
and 1/2Mg;
each x is from 0 to about 5;
each y is from about 1 to about 5; and
provided that:
- the Degree of Substitution for group RH is between about 0.001 and 0.1, more
preferably between about 0.005 and 0.05, and most preferably between
about 0.01 and 0.05;
- the Degree of Substitution for group Rc wherein Z is H or M is between about
0.2 and 2.0, more preferably between about 0.3 and 1.0, and most
preferably between about 0.4 and 0.7;
- if any RH bears a positive charge, it is balanced by a suitable anion; and
- two R4's on the same nitrogen can together form a ring structure selected
from the group consisting of piperidine and morpholine.
The "Degree of Substitution" for group RH, which is sometimes
abbreviated herein "DSRH", means the number of moles of group RH components
that are substituted per anhydrous glucose unit, wherein an anhydrous glucose
unit is a six membered ring as shown in the repeating unit of the general
structure above.
The "Degree of Substitution" for group Rc, which is sometimes
abbreviated herein "DSRC", means the number of moles of group Rc
components, wherein Z is H or M, that are substituted per anhydrous glucose
unit, wherein an anhydrous glucose unit is a six membered ring as shown in the
26
CA 02386914 2005-05-19
repeating unit of the general structure above. The requirement that Z be H or
M
is necessary to insure that there are a sufficient number of carboxy methyl
groups such that the resulting polymer is soluble. It is understood that in
addition
to the required number of Rc components wherein Z is H or M, there can be, and
most preferably are, additional Rc components wherein Z is a group other than
H
or M.
Detergent Builder
The laundry detergent compositions herein may also further comprise from 0.1 %
to 80% by weight of a detergent builder. Preferably such compositions in
liquid
form will comprise from about 1% to 10% by weight of the builder component.
Preferably such compositions in granular form will comprise from about 1% to
50% by weight of the builder component. Detergent builders are well known in
the art and can comprise, for example, phosphate salts as well as various
organic and inorganic nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include the
various alkali metal, ammonium and substituted ammonium polyacetates,
carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of
polyacetate and polycarboxylate builders are the sodium, potassium, lithium,
ammonium and substituted ammonium salts of ethylene diamine tetraacetic
acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic
acids, and citric acid. Other suitable polycarboxylates for use herein are the
polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13,
1979 to Crutchfield et al., and U.S. Patent 4,246,495, issued March 27, 1979
to
Crutchfield et al. Particularly preferred polycarboxylate builders are
the oxydisuccinates and the ether carboxylate builder compositions comprising
a
combination of tartrate monosuccinate and tartrate disuccinate described in
U.S.
Patent 4,663,071, Bush et al., issued May 5, 1987.
Examples of suitable nonphosphorus, inorganic builders include the
silicates, aluminosilicates, borates and carbonates. Particularly preferred
are
sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate
decahydrate, and silicates having a weight ratio of Si02 to alkali metal oxide
of
27
CA 02386914 2005-05-19
from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also
preferred are aluminosilicates including zeolites. Such materials and their
use as
detergent builders are more fully discussed in Corkill et al., U. S. Patent
No.
4,605,509. Also discussed in U.S. Patent No. 4,605,509 are crystalline layered
silicates which are suitable for use in the detergent compositions of this
invention.
Optional Detergent Ingredients
The laundry detergent compositions of the present invention can also include
any
number of additional optional ingredients. These include conventional
detergent
composition components such as enzymes and enzyme stabilizing agents, suds
boosters or suds suppressers, anti-tamish and anticorrosion agents, bleaching
agents, soil suspending agents, soil release agents, germicides, pH adjusting
agents, non-builder alkalinity sources, chelating agents, organic and
inorganic
fillers, solvents, hydrotropes, optical brighteners, dye transfer inhibition
agents,
dyes and perfumes.
pH adjusting agents may be necessary in certain applications where the pH of
the wash solution is greater than about 10.0 because the fabric integrity
benefits
of the defined compositions begin to diminish at a higher pH. Hence, if the
wash
solution is greater than about 10.0 after the addition of the cyclic amine
based
polymer, oligomer or copolymer materials of the present invention a pH
adjuster
should be used to reduce the pH of the washing solution to below about 10.0,
preferably to a pH of below about 9.5 and most preferably below about 7.5.
Suitable pH adjusters will be known to those skilled in the art.
A preferred optional ingredients for incorporation into the detergent
compositions
herein comprises a bleaching agent, e.g., a peroxygen bleach. Such peroxygen
bleaching agents may be organic or inorganic in nature. Inorganic peroxygen
bleaching agents are frequentily utilized in combination with a bleach
activator.
Useful organic peroxygen bleaching agents include percarboxylic acid
bleaching agents and salts thereof. Suitable examples of this class of agents
include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
28
CA 02386914 2005-05-19
diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent
4,483,781, Hartman, Issued November 20, 1984; European Patent Application
EP-A-133,354, Banks et al., Published February 20, 1985; and U.S. Patent
4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching
agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as
described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used, generally in
particulate form, in the detergent compositions herein. Inorganic bleaching
agents are in fact preferred. Such inorganic peroxygen compounds include
alkali
metal perborate and percarbonate materials. For example, sodium perborate
(e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleaching agents
can also include sodium or potassium carbonate peroxyhydrate and equivalent
"percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONETM,
manufactured commercially by DuPont) can also be used. Frequently inorganic
peroxygen bleaches will be coated with silicate, borate, sulfate or water-
soluble
surfactants. For example, coated percarbonate particles are available from
various commercial sources such as FMC, Solvay Interox, Tokai Denka and
Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the
percarbonates, etc., are preferably combined with bleach activators, which
lead
to the in situ production in aqueous solution (i.e., during use of the
compositions
herein for fabric laundering/bleaching) of the peroxy acid corresponding to
the
bleach activator. Various non-limiting examples of activators are disclosed in
U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent
4,412,934 Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene
sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are
typical
and preferred. Mixtures thereof can also be used. See also the hereinbefore
referenced U.S. 4,634,551 for other typical bleaches and activators useful
herein.
Other useful amido-derived bleach activators are those of the formulae:
R1 N(R5)C(O)R2C(O)L or R1 C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl,
aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is
any
suitable leaving group. A leaving group is any group that is displaced from
the
29
CA 02386914 2005-05-19
bleach activator as a consequence of the nucleophilic attack on the bleach
activator by the perhydrolysis anion. A preferred leaving group is phenol
sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene-
sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as
described in the hereinbefore referenced U.S. Patent 4,634,551.
Another class of useful bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October
30, 1990. A highly preferred activator of the benzoxazin-type is:
0
11
C'O
O i
~C O
N
Still another class of useful bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
0 0
O ~ -CH~-CH2 0 i -CH~CH2
R6 C -N R6-C -N
H2
\CH2-CH2 CH2 CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to
about 12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam,
nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyf valerolactam, nonanoyl valerolactam, decanoyl
valerolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam
and mixtures thereof. See also U.S. Patent 4,545,784, Issued to Sanderson,
October 8, 1985, which discloses acyl caprolactams, including benzoyl
caprolactam,
adsorbed into sodium perborate.
If utilized, peroxygen bleaching agent will generally comprise from about
2% to 30% by weight of the detergent compositions herein. More preferably,
peroxygen bleaching agent will comprise from about 2% to 20% by weight of the
compositions. Most preferably, peroxygen bleaching agent will be present to
the
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WO 01/32816 PCT/US00/28438
extent of from about 3% to 15% by weight of the compositions herein. If
utilized,
bleach activators can comprise from about 2% to 10% by weight of the detergent
compositions herein. Frequently, activators are employed such that the molar
ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more
preferably from about 1.5:1 to 5:1.
Another highly preferred optional ingredient in the detergent compositions
herein
is a detersive enzyme component. Enzymes can be included in the present
detergent compositions for a variety of purposes, including removal of protein-
based, carbohydrate-based, or triglyceride-based stains from substrates, for
the
prevention of refugee dye transfer in fabric laundering, and for fabric
restoration.
Suitable enzymes include proteases, amylases, lipases, cellulases,
peroxidases,
mannanases, and mixtures thereof of any suitable origin, such as vegetable,
animal, bacterial, fungal and yeast origin. Preferred selections are
influenced by
factors such as pH-activity and/or stability, optimal thermostability, and
stability
to active detergents, builders and the like. In this respect bacterial or
fungal
enzymes are preferred, such as bacterial amylases and proteases, and fungal
cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning,
stain removing or otherwise beneficial effect in a laundry detergent
composition.
Preferred enzymes for laundry purposes include, but are not limited to,
proteases, cellulases, lipases, amylases and peroxidases.
Enzymes are normally incorporated into detergent compositions at levels
sufficient to provide a "cleaning-effective amount". The term "cleaning-
effective
amount" refers to any amount capable of producing a cleaning, stain removal,
soil removal, whitening, deodorizing, or freshness improving effect on
substrates
such as fabrics. In practical terms for current commercial preparations,
typical
amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of
active enzyme per gram of the detergent composition. Stated otherwise, the
compositions herein will typically comprise from 0.001% to 5%, preferably
0.01 %-1 /a by weight of a commercial enzyme preparation. Protease enzymes
are usually present in such commercial preparations at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition.
Higher active levels may be desirable in highly concentrated detergent
formulations.
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Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniformis. One suitable protease
is
obtained from a strain of Bacillus, having maximum activity throughout the pH
range of 8-12, developed and sold as ESPERASEO by Novo Industries A/S of
Denmark, hereinafter "Novo". The preparation of this enzyme and analogous
enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include
ALCALASEO and SAVINASEO from Novo and MAXATASEO from International
Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in
EP
130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April
28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from
Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic
detergents comprising protease, one or more other enzymes, and a reversible
protease inhibitor are described in WO 9203529 A to Novo. Other preferred
proteases include those of WO 9510591 A to Procter & Gamble. When desired,
a protease having decreased adsorption and increased hydrolysis is available
as
described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like
protease for detergents suitable herein is described in WO 9425583 to Novo.
Cellulases usable herein include both bacterial and fungal types, preferably
having a pH optimum between 5 and 10. U.S. 4,435,307, Barbesgoard et al.,
March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or
Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the
genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine
mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed
in
GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME and
CELLUZYMEO (Novo) are especially useful. See also WO 9117243 to Novo.
Amylases (a and/or 13) can be included for removal of carbohydrate-based
stains. WO94/02597, Novo Nordisk A/S published February 03, 1994, describes
cleaning compositions which incorporate mutant amylases. See also
WO95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases
known for use in cleaning compositions include both a- and P-amylases. a-
Amylases are known in the art and include those disclosed in US Pat. no.
5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610;
EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other
suitable
amylases are stability-enhanced amylases described in WO94/18314, published
August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and
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amylase variants having additional modification in the immediate parent
available
from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also
suitable are amylases described in EP 277 216, W095/26397 and W096/23873
(all by Novo Nordisk). Examples of commercial a-amylases products are Purafect
Ox Am from Genencor and Termamyl , Ban Fungamyl and Duramyl , all
available from Novo Nordisk A/S Denmark. W095/26397 describes other
suitable amylases : a-amylases characterised by having a specific activity at
least 25% higher than the specific activity of Termamyl0 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. Suitable are variants of the above
enzymes, described in W096/23873 (Novo Nordisk). Other amylolytic enzymes
with improved properties with respect to the activity level and the
combination of
thermostability and a higher activity level are described in W095/35382.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri
ATCC 19.154, as disclosed in GB 1,372,034. See also, the lipase in Japanese
Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available
from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark
Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include
Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum
var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter
viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE enzyme
derived from Humicola lanuginosa and commercially available from Novo, see
also EP 341,947, is a preferred lipase for use herein.
Preferred enzyme for the compositions of the present invention is a mannanase
enzyme. Encompassed are the following three mannans-degrading enzymes :
EC 3.2.1.25 : R-mannosidase, EC 3.2.1.78 : Endo-1,4-0-mannosidase, referred
therein after as "mannanase" and EC 3.2.1.100 : 1,4-p-mannobiosidase (IUPAC
Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic
Press). Preferably, the detergent compositions of the present invention
comprise
a R-1,4-Mannosidase (E.C. 3.2.1.78) referred to as "Mannanase". Indeed, it has
been found that the compositions of the present invention comprising further a
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mannanase enzyme, provide excellent color care while maintaining superior
cleaning performance.
Preferably, the mannanase enzyme will be an alkaline mannanase as defined
below, more preferably, a mannanase originating from a bacterial source.
Especially, the compositions of the present invention will comprise an
alkaline
mannanase selected from the mannanase from the strain Bacillus
agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168,
gene yght; the mannanase from Bacillus sp. 1633; the mannanase from Bacillus
sp. AA112 and/or the mannanase from the strain Bacillus halodurans. Most
preferred mannanase for the inclusion in the detergent compositions of the
present invention is the mannanase enzyme originating from Bacillus sp. 1633
as
described in WO 99/64619. The terms "alkaline mannanase enzyme" is meant to
encompass an enzyme having an enzymatic activity of at least 10%, preferably
at least 25%, more preferably at least 40% of its maximum activity at a given
pH
ranging from 7 to 12, preferably 7.5 to 10.5.
A first more preferred mannanase for use in the present invention is the
alkaline
mannanase from Bacillus agaradhaerens NICMB 40482 which is described in
WO 99/64619. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482;
or
ii) a polypeptide comprising an amino acid sequence as shown in
positions 32-344 of SEQ ID NO:6 as shown in WO 99/64619; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least
70% homologous with said polypeptide, or is derived from said
polypeptide by substitution, deletion or addition of one or several
amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
Also encompassed is the corresponding isolated polypeptide having mannanase
activity selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as
shown in SEQ ID NO: 5 from nucleotide 94 to nucleotide 1032 as
shown in WO 99/64619;
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(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 70% identical to the amino acid
sequence of SEQ ID NO: 6 from amino acid residue 32 to amino
acid residue 344 as shown in WO 99/64619;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pSJ1678 comprising the polynucleotide molecule (the DNA
sequence) encoding said mannanase has been transformed into a strain of the
Escherichia coli which was deposited by the inventors according to the
Budapest
Treaty on the International Recognition of the Deposit of Microorganisms for
the
Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen
und Zelikulturen GmbH, Mascheroder Weg 1 b, D-38124 Braunschweig, Federal
Republic of Germany, on 18 May 1998 under the deposition number DSM
12180.
A second more preferred enzyme is the mannanase from the Bacillus subtilis
strain 168, which is described in U.S. Patent No. 6,060,299. More
specifically,
this mannanase is:
i) is encoded by the coding part of the DNA sequence shown in SEQ
ID No. 5 shown in the U.S. Patent No. 6,060,299 or an analogue
of said sequence; and/or
ii) a polypeptide comprising an amino acid sequence as shown SEQ
ID NO:6 shown in the U.S. Patent No. 6,060,299; or
iii) an analogue of the polypeptide defined in ii) which is at least 70%
homologous with said polypeptide, or is derived from said
polypeptide by substitution, deletion or addition of one or several
amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
Also encompassed in the corresponding isolated polypeptide having mannanase
activity selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as
shown in SEQ ID NO:5 as shown in the U.S. Patent No. 6,060,299
(b) species homologs of (a);
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(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 70% identical to the amino acid
sequence of SEQ ID NO: 6 as shown in U.S. Patent No.
6,060,299;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
A third more preferred mannanase is described in WO 99/64619. More
specifically, this mannanase is:
i) a polypeptide produced by Bacillus sp. 1633;
ii) a polypeptide comprising an amino acid sequence as shown in
positions 31-330 of SEQ ID NO:2 as shown in WO 99/64619; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least
65% homologous with said polypeptide, is derived from said
polypeptide by substitution, deletion or addition of one or several
amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule
selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as
shown in SEQ ID NO: 1 from nucleotide 94 to nucleotide 990 in
WO 99/64619;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 65% identical to the amino acid
sequence of SEQ ID NO: 2 from amino acid residue 31 to amino
acid residue 330 in WO 99/64619;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM3 comprising the polynucleotide molecule (the DNA
sequence) encoding a mannanase of the present invention has been
transformed into a strain of the Escherichia coli which was deposited by the
inventors according to the Budapest Treaty on the International Recognition of
the Deposit of Microorganisms for the Purposes of Patent Procedure at the
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Deutsche Sammlung von Mikroorganismen und Zelikulturen GmbH,
Mascheroder Weg 1 b, D-38124 Braunschweig, Federal Republic of Germany, on
29 May 1998 under the deposition number DSM 12197.
A fourth more preferred mannanase is described in WO 99/64619. More
specifically, this mannanase is:
i) a polypeptide produced by Bacillus sp. AAI 12;
ii) a polypeptide comprising an amino acid sequence as shown in
positions 32-362 of SEQ ID NO:10 as shown in WO 99/64619; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least
65% homologous with said polypeptide, is derived from said
polypeptide by substitution, deletion or addition of one or several
amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule
selected from the group consisting of
(a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as
shown in SEQ ID NO: 9 from nucleotide 94 to nucleotide 1086 as
shown in WO 99/64619;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 65% identical to the amino acid
sequence of SEQ ID NO: 10 from amino acid residue 32 to amino
acid residue 362 as shown in WO 99/64619;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM1 comprising the polynucleotide molecule (the DNA sequence)
encoding a mannanase of the present invention has been transformed into a
strain of the Escherichia coli which was deposited by the inventors according
to
the Budapest Treaty on the International Recognition of the Deposit of
Microorganisms for the Purposes of Patent Procedure at the Deutsche
Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1 b,
D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under
the deposition number DSM 12433.
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A fifth more preferred mannanase is described in WO 99/64619. More
specifically, this mannanase is :
i) a polypeptide produced by Bacillus halodurans,
ii) a polypeptide comprising an amino acid sequence as shown in positions
33-331 of SEQ ID NO:12 as shown in WO 99/64619, or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 65%
homologous with said polypeptide, is derived from said polypeptide by
substitution, deletion or addition of one or several amino acids, or is
immunologically reactive with a polyclonal antibody raised against said
polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule
selected from the group consisting of :
a) polynucleotide molecules encoding a polypeptide having mannanase
activity and comprising a sequence of nucleotides as shown in SEQ ID
NO: 11 from nucleotide 97 to nucleotide 993 as shown in WO
99/64619;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase
activity that is at least 65% identical to the amino acid sequence of SEQ
ID NO: 12 from amino acid residue 33 to amino acid residue 331 as
shown in WO 99/64619;
d) molecules complementary to (a), (b) or (c); and
e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM5 comprising the polynucleotide molecule (the DNA
sequence) encoding a mannanase of the present invention has been
transformed into a strain of the Escherichia coli which was deposited by the
inventors according to the Budapest Treaty on the International Recognition of
the Deposit of Microorganisms for the Purposes of Patent Procedure at the
Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH,
Mascheroder Weg 1 b, D-38124 Braunschweig, Federal Republic of Germany, on
9 October 1998 under the deposition number DSM 12441.
The enzyme-containing compositions herein may optionally also comprise
from about 0.001% to about 10%, preferably from about 0.005% to about 8%,
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most preferably from about 0.01% to about 6%, by weight of an enzyme
stabilizing system. The enzyme stabilizing system can be any stabilizing
system
which is compatible with the detersive enzyme. Such a system may be inherently
provided by other formulation actives, or be added separately, e.g., by the
formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing
systems can, for example, comprise calcium ion, boric acid, propylene glycol,
short chain carboxylic acids, boronic acids, and mixtures thereof, and are
designed to address different stabilization problems depending on the type and
physical form of the detergent composition.
The laundry detergent compositions of the present invention can also include
compounds for inhibiting dye transfer from one fabric to another of
solubilized
and suspended dyes encountered during fabric laundering operations involving
colored fabrics. These are generally comprised in the laundry detergent
compositions of the present invention at a level of from 0.001% to 10 %,
preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight.
Polymeric dye transfer inhibiting agents are used to inhibit the transfer of
dyes
from colored fabrics onto fabrics washed therewith. These polymers have the
ability to complex or adsorb the fugitive dyes washed out of dyed fabrics
before
the dyes have the opportunity to become attached to other articles in the
wash.Especially suitable polymeric dye transfer inhibiting agents are
polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles
or
mixtures thereof.
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use contain units having the
following structure formula :
P
1
(1) Ax
I
R
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wherein P is a polymerisable unit, whereto the R-N-O group can be attached to
or wherein the R-N-O group forms part of the polymerisable unit or a
combination of both.
O O O
II II II
A is NC, CO, C, -0-,-S-, -N- ; x is 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or
alicyclic groups or any combination thereof whereto the nitrogen of the
N-0 group can be attached or wherein the nitrogen of the N-0 group is
part of these groups.
The N-0 group can be represented by the following general structures
0 0
I I
(R1)x -N- (R2)y =N- (R1)x
(R3)z
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x or/and y or/and z is 0 or 1 and
wherein the nitrogen of the N-0 group can be attached or wherein the
nitrogen of the N-0 group forms part of these groups.
The N-0 group can be part of the polymerisable unit (P) or can be attached to
the
polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-0 group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected from
aliphatic, aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of polyamine N-
oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such
as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine
and
derivatives thereof.
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Another class of said polyamine N-oxides comprises the group of polyamine N-
oxides wherein the nitrogen of the N-O group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having
the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic
groups
wherein the nitrogen of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having
the general formula (I) wherein R are aromatic, heterocyclic or alicyclic
groups
wherein the nitrogen of the N-0 functional group is attached to said R groups.
Examples of these classes are polyamine oxides wherein R groups can be
aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed
is water-soluble and has dye transfer inhibiting properties. Examples of
suitable
polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers of the present invention typically have a ratio of
amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine
oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-oxidation.
Preferably,
the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably
from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of
the present invention actually encompass random or block copolymers where
one monomer type is an amine N-oxide and the other monomer type is either an
amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa
< 10, preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of polymerisation.
The degree of polymerisation is not critical provided the material has the
desired
water-solubility and dye-suspending power.
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Typically, the average molecular weight is within the range of 500 to
1000,000;
preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most
preferably from 3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention
have an average molecular weight range from 5,000-1,000,000, preferably from
5,000-200,000.
Highly preferred polymers for use in the laundry detergent compositions
according to the present invention comprise a polymer selected from N-
vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an
average molecular weight range from 5,000 to 50,000 more preferably from
8,000 to 30,000, most preferably from 10,000 to 20,000.
The average molecular weight range was determined by light scattering as
described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern
Methods of Polymer Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an
average
molecular weight range from 5,000 to 50,000; more preferably from 8,000 to
30,000; most preferably from 10,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having
said
average molecular weight range provide excellent dye transfer inhibiting
properties while not adversely affecting the cleaning performance of detergent
compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has
a
molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more
preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone
The laundry detergent compositions of the present invention may also utilize
polyvinylpyrrolidone ("PVP") having an average molecular weight of from about
2,500 to about 400,000, preferably from about 5,000 to about 200,000, more
preferably from about 5,000 to about 50,000, and most preferably from about
5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially
vailable
from ISP Corporation, New York, NY and Montreal, Canada under the product
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CA 02386914 2005-05-19
names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average
molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000),
and PVP K-90 (average molecular weight of 360,000). Other suitable
polyvinylpyrrolidones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to
persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-
256,696).
d) Polyvinyloxazolidone :
The laundry detergent compositions of the present invention may also utilize
polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said
polyvinyloxazolidones have an average molecular weight of from about 2,500 to
about 400,000, preferably from about 5,000 to about 200,000, more preferably
from about 5,000 to about 50,000, and most preferably from about 5,000 to
about 15,000.
e) Polyvinylimidazole :
The laundry detergent compositions of the present invention may also utilize
polyvinylimidazole as polymeric dye transfer inhibiting agent. Said
polyvinylimidazoles have an average about 2,500 to about 400,000, preferably
from about 5,000 to about 200,000, more preferably from about 5,000 to about
50,000, and most preferably from about 5,000 to about 15,000.
f) Cross-linked polymers :
Cross-linked polymers are polymers whose backbone are interconnected to a
certain degree; these links can be of chemical or physical nature, possibly
with
active groups n the backbone or on branches. In one embodiment, the cross-
linked
polymers are made in such a way that they form a three-dimensional rigid
structure,
which can entrap dyes in the pores formed by the three-dimensional structure.
In
another embodiment, the cross-linked polymers entrap the dyes by swelling.
Such
cross-linked polymers are described in U.S. 5,912,221.
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Further, the laundry detergent composition of the present invention can
optionally
comprise a peariescing agent to improve the aesthetic appearance of the
product. Suitable peariescing agents are those well known in the art to
provide
pearlescing effects in surfactant compositions. For instance, pearl lustre
mica
pigments such Iriodin ex Merck or equivalent e.g. Mearlin Magnapearl from the
Meare Corp., or organic compounds having the property to crystallise as
peariescent needles in the product. Typical compounds having this property are
polyol esters such as ethylene glycol mono- (EGMS) or di-stearate (EGDS), or
polyethyleneglycol mono- (PGMS) or distearate (PGDS). There are several
commercial sources for these materials. For instance but not exclusively
PEG6000MS ex Stepan, Empilan EGDS/A ex Albright & Wilson, are all suitable
pearlescing agents. Other suitable peariescing agents can be found in WO
99/09944." It is known in the art to further add to pearleacent agent-
containing
liquid products, a pearlescent crystallization enhancer. Suitable enhancers
are
the acids, salts, alcohols and esters having a hydrophobic moiety with at
least
16C, pref. at least 18C; as described EP 520 551 B. It has been surprisingly
found that the semi-polar nonionic surfactants of the present invention and
preferably the amine oxide compounds, can function as a crystallization
enhancer for organic pearlescent agents. Liquid detergent compositions
comprising an organic peariescent agent and a semi-polar nonionic surfactant,
preferably an amine oxide, demonstrate a very attractive peariescent
appearance. It has been further found that liquid laundry detergent
compositions
comprising the surfactant system of the present invention demonstrate a
particularly attractive pearleascent effect.
Detercient Composition Preparation
The laundry detergent compositions according to the present invention can be
prepared by combining the essential and optional components in the requisite
concentrations in any suitable order and by any conventional means.
Granular compositions, for example, are generally made by combining base
granule ingredients, e.g., surfactants, builders, water, etc., as a slurry,
and spray
drying the resulting slurry to a low level of residual moisture (5-12%). The
remaining dry ingredients, e.g., granules of the essential cyclic amine based
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fabric treatment materials, can be admixed in granular powder form with the
spray dried granules in a rotary mixing drum. The liquid ingredients, e.g.,
solutions of the essential cyclic amine based fabric treatment materials,
enzymes, binders and perfumes, can be sprayed onto the resulting granules to
form the finished detergent composition.
Liquid detergent compositions can be prepared by admixing the essential
and optional ingredients thereof in any desired order to provide compositions
containing components in the requisite concentrations. Liquid compositions
according to the present invention can also be in "compact form", in such
case,
the liquid detergent compositions according to the present invention will
contain a
lower amount of water, compared to conventional liquid detergents. Addition of
the cyclic amine based polymer, oligomer or copolymer materials to liquid
detergent or other aqueous compositions of this invention may be accomplished
by simply mixing into the liquid solutions the desired cyclic amine based
fabric
treatment materials.
Fabric Laundering Method
The present invention also provides a method for laundering fabrics in a
manner
which imparts fabric cleaning and fabric appearance benefits provided by the
combination of the semi-polar nonionic surfactant and the cyclic amine based
polymer, oligomer or copolymer materials used herein. Such a method employs
contacting these fabrics with an aqueous washing solution formed from an
effective amount of the detergent compositions hereinbefore described or
formed
from the individual components of such compositions. Contacting of fabrics
with
washing solution will generally occur under conditions of agitation although
the
compositions of the present invention may also be used to form aqueous
unagitated soaking solutions for fabric cleaning and treatment. As discussed
above, it is preferred that the washing solution have a pH of less than about
10.0,
preferably it has a pH of about 9.5 and most preferably it has a pH of about
7.5.
Agitation is preferably provided in a washing machine for good cleaning.
Washing is preferably followed by drying the wet fabric in a conventional
clothes
dryer. An effective amount of a high density liquid or granular detergent
composition in the aqueous wash solution in the washing machine is preferably
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from about 500 to about 7000 ppm, more preferably from about 1000 to about
3000 ppm.
Examples
The following examples illustrate the compositions and methods of the present
invention, but is not necessarily meant to limit or otherwise define the scope
of
the invention.
EXAMPLE 1
Synthesis of the adduct of imidazole and epichlorohydin (Ratio of
imidazole:epichlorohydrin 1:1):
The polycationic condensate is prepared by reacting imidazole and
epichlorohydrin. To a round bottomed flask equipped with a magnatic stirrer,
condenser and a thermometer are added imidazole (0.68 moles) and 95 mL
water. The solution is heated to 50 C followed by dropwise addition of
epichlorohydrin (0.68 moles). After all the epichlorohydrin is added, the
temperature is raised to 80 C until all the alkylating agent is consumed. The
condensate produced had molecular weight of about 12,500.
EXAMPLE 2
Synthesis of the adduct of imidazole and epichlorohydin (Ratio of
imidazole:epichlorohydrin 1.4:1)
To a round bottomed flask equipped with a magnatic stirrer, condenser and a
thermometer are added imidazole (0.68 moles) and 95 mL water. The solution is
heated to 50 C followed by dropwise addition of epichlorohydrin (0.50 moles).
After all the epichlorohydrin is added, the temperature is raised to 80 C
until all
the alkylating agent is consumed. The condensate produced had molecular
weight of about 2000.
EXAMPLE 3
Synthesis of the adduct of piperazine, morpholine and epichlorohydin (Ratio
1.8/0.8/2.0)
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Into a round bottom flask equipped with stirrer, thermometer, dropping funnel
and
reflux condenser were weighed 154.8 g (1.8 mole) of piperazine and 69.6 g (0.8
mole) of morpholine and 220 ml of water. After a clear solution at 40 C was
obtained, the solution was heated to 55-65 C and with vigorous stirring 185 g
(2
mole) of epichlorohydrin were added at such a rate, that the temperature did
not
exceed 80 C. After all the epichlorohydrin had been added the reaction mixture
was heated to 85 C until all of the alkylating agents had been consumed
(negative Preussmann test after 4 hours). 108.8 g (0.68 mole) of 25% NaOH and
40 g of water were added and the reaction mixture was stirred for another hour
at
85 C. Then additional 47 g of water were added and the mixture was allowed to
cool to room temperature.
EXAMPLE 4
Synthesis of the adduct of piperazine and epichlorohydin (Ratio of
imidazole:epichlorohydrin 1:1)
To a round bottomed flask equipped with a magnatic stirrer, condenser and a
thermometer are added piperazine (0.68 moles) and 95 mL water. The solution is
heated to 50 C followed by dropwise addition of epichlorohydrin (0.68 moles).
After all the epichlorohydrin is added, the temperature is raised to 80 C
until all
the alkylating agent is consumed
EXAMPLE 5
To the condensate in example 4 are added 1.4 mole equivalent of methyl
chloride based on piperazine and mixed until all the methyl chloride is
consumed.
EXAMPLE 6
Synthesis of the adduct of imidazole, piperazine and epichlorohydin (Ratio of
imidazole:piperazine:epichlorohydrin =1:3:4)
68.8 g (1.0 mole) of limidazole and 260.6 g (3.0 mole) of piperazine were
solved in 700.2 g of water and at a temperature of 50-60 C 370 g (4.0 mole) of
epichlorhydrin were added dropwise. After the addition was complete, the
reaction mixture was stirred for additional 5 hours at 80 C.
EXAMPLE 7
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(a) Reaction of bis(aminopropyl)piperazine with epichlorohydrin in a molar
ratio of 2 : 1
600 g (3 moles) of bis(aminopropyl)piperazine were dissolved in 750 g of
water. This solution was heated to 90 C. As soon as this temperature was
reached 140.1 g (1.5 moles) of epichlorohydrin were added within 60 minutes at
90 C. The reaction mixture was then stirred at 90 C for 150 minutes.
Thereafter
no epichlorohydrin could be detected. The condensation product contained NH
groups.
(b) Permethylation of the condensation product obtained under (a)
99.7 g (content of NH groups was 0.87 moles) of the condensation
product obtained according to (a) were mixed with 100.3 g (2.18 moles) of
formic
acid (99%) with stirring and cooling in an ice bath. 104.5 g (1.045 moles) of
formaldehyde in the form of a 30% strength by weight aqueous solution were
added in the course of 20 minutes at room temperature. The reaction mixture
was then cautiously heated to 60 C. At about 50 C the evolution of carbon
dioxide from the reaction mixture began and became vigorous at 60 C so that
the heating could be removed. After the evolution of carbon dioxide had slowed
down the reaction mixture was refluxed for 12 hours. After cooling 100 mi of
concentrated hydrochloric acid were added and the water removed from the
reaction mixture. 153.6 g of of solids were obtained and dissolved in water
forming a 50% strength by weight solution of a cyclic amine based polymer
substantially free of primary and secondary amino groups. As determined by
13C-NMR spectroscopy, more than 90% of the NH groups were converted into
tertiary nitrogen atoms. The amount of quaternary ammonium groups in the
polymer was below 5%. The aqueous polymer solution had a pH of 9.58. The k
value of the polymer was 8.6.
EXAMPLE 8
A solution of 92.6 g (1.36 moles) of imidazole in 140.5 g of water was heated
to
50 C and combined in the course of 10 minutes with an aqueous solution of 8.2
g (0.07 moles) of the sodium salt of 2-chloroacetic acid in 50 g of water. The
solution is then heated at 65 C until all of the sodium salt of 2-chloroacetic
acid
has reacted as can be analytically determined by the chloride ion content of
the
solution. 5.6 g (0.07 moles) of a 50% strength by weight aqueous solution of
sodium hydroxide were added and 89.7 g (0.97 moles) of epichlorohydrin were
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added while stirring within 30 minutes so that the temperature of the reaction
mixture could be kept in the range of from 55 to 65 C. After the addition of
epichlorohydrin the reaction mixture was heated to 80 C and stirred for 4
hours
at this temperature. After this period no more alkylating agent could be
detected.
377.7 g of a yellowish aqueous solution of an amphoteric amine based polymer
having a net cationic charge of 4.2 mequiv/g polymer were obtained. The
solution
had a pH of 6.97 and contained 50.3% of water, 0.06% of glycolic acid and less
than 0.05% of 2-chloroacetic acid. The molecular weight of the polymer was Mn
= 700, Mw = 1,460 and Mw/Mn = 2.1.
EXAMPLE 9
According to the procedure given in Example 8, 92.6 g (1.36 moles) of
imidazole,
16.3 g(0.14 moles) of the sodium salt of 2-chloroacetic acid, 11.2 g(0.14
moles)
of a 50% strength by weight aqueous solution of sodium hydroxide and 86.1 g
(0.93 moles) of epichlorohydrin were reacted. 386.3 g of a yellowish aqueous
solution of an amphoteric amine based polymer having a net cationic charge of
3.4 mequiv/g polymer were obtained. The solution had a pH of 7.10 and
contained 49.6% of water, 0.1% glycolic acid and less than 0.05% of 2-
chloroacetic acid. The molecular weight of the polymer was Mn = 650, Mw =
1,320 and Mw/Mn = 2Ø
EXAMPLE 10
According to the procedure given in Example 8, 92.6 g (1.36 moles) of
imidazole
dissolved in 122.6 g of water, 39.6 g (0.34 moles) of the sodium salt of 2-
chloroacetic acid dissolved in 100 g of water, 27.2 g (0.34 moles) of a
50%strength by weight aqueous solution of sodium hydroxide and 76.8 g (0.83
moles) of epichlorohydrin were reacted. 386.3 g of a yellowish aqueous
solution
of an amphoteric amine based polymer having a net cationic charge of 2.8
mequiv/g were obtained. The solution had a pH of 7.82 and contained 53.4% of
water, 0.2% of glycolic acid and less than 0.05% of 2-chloroacetic acid. The
molecular weight of the polymer was Mn = 540, Mw = 1,060 and Mw/Mn = 2Ø
EXAMPLE 11
Example 7 was repeated with the exceptions that 68.1 g(1.0 mole) of imidazole
dissolved in 54.9 g of water, 72.0 g (0.6 moles) of the sodium salt of 2-
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chloroacetic acid dissolved in 150 g of water, 48.0 g (0.6 moles) of a 50%
strength by weight solution of sodium hydroxide and 64.8 g(0./ moles) of
epichlorohydrin were reacted. 446.4 g of a dark yellow aqueous solution of an
amphoteric amine based polymer having a net cationic charge of 3.2 mequiv/g
were obtained. The solution had a pH of 12.29 and contained 48.2% of water,
0.5% of glycolic acid and less than 0.05% of 2-chloroacetic acid. The
molecular
weight of the polymer was Mn = 740, Mw = 1,690 and Mw/Mn = 2.3.
EXAMPLE 12
Example 8 was repeated with the exceptions that 71.5 g (1.05 moles) of
imidazole dissolved in 116.3 g of water, 40.8 g (0.34 moles) of the sodium
salt of
2-chloroacetic acid dissolved in 100 g of water, 27.2 g (0.24 moles) of a 50%
strength by weight solution of sodium hydroxide and 76.8 g (0.83 moles) of
epichlorohydrin were reacted. 427.6 g of a yellow aqueous solution of an
amphoteric amine based polymer having a net cationic charge of 3.7 mequiv/g
and a K value of 9.5 were obtained. The solution had a pH of 11.62 and
contained 54.2% of water, 0.3% of glycolic acid and less than 0.05% of 2-
chloroacetic acid. The molecular weight of the polymer was Mn = 1,050, Mw =
2,380 and Mw/Mn = 2.3.
EXAMPLE 13
68.1 g (1 mole) of imidazole were dissolved in 73.6 g of water and heated to a
temperature of 50 C. As soon as this temperature had been reached, a solution
of 73.5 g (0.34 moles) of the sodium salt of 3-chloro-2-hydroxypropanesulfonic
acid in 150 g of water and 27.2 g (0.34 moles) of a 50% strength by weight
aqueous solution of sodium hydroxide were simultaneously added with stirring
over a period of 25 minutes. The reaction mixture was then stirred at a
temperature of from 65 to 90 C until all of the sodium salt of 3-chloro-2-
hydroxypropanesulfonic acid had reacted as determined analytically by
measuring the concentration of chloride ions in the solution. The solution was
cooled to 55 C and 76.8 g (0.83 moles) of epichlorohydrin were introduced
within
30 minutes at such a rate that the temperature of the reaction mixture could
be
kept at 55 C. After completion of the epichlorohydrin addition the reaction
mixture was heated to 80 C and stirred for 4 hours at this temperature. After
this
period no more alkylating agent could be detected in the reaction mixture.
461.3
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g of a clear yellow aqueous solution of an amphoteric amine based polymer
having a net cationic charge of 2.9 mequiv/g polymer and a K value of 10.0
were
obtained. The solution had a pH of 11.55 and contained 52.4% of water. The
molecular weight of the polymer was Mn = 1,800, Mw = 3,490 and Mw/Mn =
1.95.
EXAMPLE 14
Example 13 was repeated with the exception that 34.1 g (0.5 moles) of
imidazole
dissolved in 31.3 g of water, 64.8 g (0.35 moles) of the sodium salt of 3-
chloro-2-
hydroxypropanesulfonic acid dissolved in 100 g of water, 24.0 g (0.3moles) of
a
50% strength by weight aqueous solution of sodium hydroxide and 32.4 g (0.35
moles) of epichlorohydrin were reacted. 284.1 g of a clear yellow aqueous
solution of an amphoteric amine based polymer having a net cationic charge of
3.3 mequiv/g polymer and a K value of 7.6 were obtained. The solution had a pH
of 11.92 and contained 51.7% of water. The molecular weight of the polymer was
Mn = 1,100, Mw = 1,990 and Mw/Mn = 1.80.
EXAMPLE 15
Synthesis of the adduct of imidazole/piperazine/epi, in a ratio 1.0/3.0/4.0
100% oxidized
68.8 g (1.0 mole) of limidazole and 260.6 g (3.0 mole) of piperazine were
solved
in 700.2 g of water and at a temperature of 50-60 C 370 g (4.0 mole) of
epichlorhydrin were added dropwise. After the addition was complete, the
reaction mixture was stirred for additional 5 hours at 80 C. To 237 g of this
product (equivalent to 1,022 mole of oxidizable nitrogen atoms) 80.7 g (1.12
mole) of a 47.2% solution of H202 in water were added over a period of 5 hours
at 40 C. After that the mixture was heated to 50-60 C until the theoretical
amount of H202 had been consumed. Unreacted H202 was destroyed by using
Pt/C and the solution then filtered.
The reaction product was characterized as follows:
water content: 58.6%
pH: 2.86
chloride content: 3.694 mmole/g
Mn (GPC): 340
Mw (GPC): 940
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Mn/Mw: 2.8+/-0.1
Example 16
The following 2 sets of liquid laundry detergent compositions were prepared in
accordance with the present invention :
1 II III IV
C12_18 Fatty acid 8.0 8.0 8.0 8.0
Citric acid 2.0 2.0 2.0 2.0
C12_14 alcohol ethoxylate 7E0 20.0 20.0 - 10.0
C12_13 alcohol ethoxylate 9E0 - - 20.0 -
C13_15 alcohol ethoxylate 5E0 - - - 10.0
C12_14 dimethylamine oxide 5.0 5.0 5.0 5.0
Ethanol 2.0 2.0 - -
Propanediol 7.0 7.0 9.0 7.0
Monoethanolamine 5.0 5.0 5.0 5.0
Dispersant polymer 3.0 3.0 2.5 2.5
Phosphonate 1.0 1.0 - 1.0
Chelant - - 1.0 1.0
Cyclic amine base polymer - compounds and levels as
shown in the table below
Enzyme 1.0 1.0 1.5 2.0
Ethylene glycol distearate 0.5 1.0 - -
Borate 2.0 2.0 3.0 2.0
Miscellaneous and water Up to 100%
V VI VII VIII IX
C12_18 Fatty acid - 8.0 8.0 8.0 -
Citric acid 7.0 2.0 2.0 2.0 6.0
C12_14 alcohol ethoxylate 7E0 22.0 20.0 - 15.0
C12_13 alcohol ethoxylate 9E0 - - 17.0 - -
C12_13 alcohol ethoxylate 5E0 - - - - 23.0
C12_14 dimethylamine oxide 3.0 3.0 5.0 4.0 2.5
C$_10 amido propyl - 1.5 - - -
dimethylamine
C12_15 alkyl sulfate - 2.0 - 2.0 -
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C12_15 alkyl ether 2.5EO sulfate - - 3.0 - -
C14-15 alkyl ether 0.35E0 - - - 1.0 -
sulfate
Linear alkyl benzene sulfonate - - - 2.0 -
Ethanol 1.0 - - - 1.0
Propanediol 7.0 9.0 9.0 9.0 12.0
Monoethanolamine 7.0 6.5 5.0 5.0 7.5
Dispersant polymer 2.5 2.0 2.5 2.5 3.0
Phosphonate 1.0 0.5 - - 1.0
Chelant - - 1.0 1.0 -
Cyclic amine base polymer Compounds and levels as shown in the
table below
Enzyme 0.8 2.0 1.5 1.5 1.0
Mannanase - - - - 0.3
Ethylene glycol distearate - 1.0 - 1.0 -
Borate 2.0 2.0 2.5 2.0 2.0
Miscellaneous and water Up to 100%
Wherein the components are defined as below :
1) The cyclic amine based polymer is selected from one or more compound(s)
illustrated in the table below
2) The chelant is selected from Ethylenediamine-N,N'-disuccinic acid, (S,S)
isomer in the form of its sodium salt and/or Diethylene triamine pentaacetic
acid.
3) The enzymes are selected from the conventional protease, amylase, lipase
and/or cellulase enzymes as described above. Mannanase is the mannanase
enzyme sold by Novo Nordisk A/S under the trademark Mannaway.
4) The dispersant polymer is a poly(ethyleneimine) ethoxylated polymer of a
molecular weight between 200 and 3000 and an EO between 7 and 30
EXAMPLE 17
The following granular laundry detergent compositions were prepared in
accordance with the present invention
I 11 III
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Na C12 Linear alkyl benzene sulfonate 3.0 3.0 5.0
Na C14-15 alkyl sulfonate 2.0 2.0 -
Zeolite Builder 27.8 27.8 27.8
Sodium Carbonate 27.3 27.3 27.3
PEG 4000 1.6 1.6 1.6
Dispersant, Na polyacrylate 2.3 2.3 2.3
C12-13 alkyl ethoxylate (E9) 15.0 15.0 10.0
C12-14 dimethylamine oxide 2.0 2.5 5.0
Polyvinylpyridine-N-Oxide, with an average 0.5 - -
molecular weight of 50,000
Cellulosic polymer 1.0 1.0 -
Sodium Perborate 1.03 1.03 1.03
Cyclic amine based polymer/oligomer level shown in the table below
Other Adjunct ingredient Up to 100%
Wherein the cellulosic polymer is a carbox meth Icellulose characterized by
Degree of DSRC= 0.3 - 2.0; preferred DSRC = 0.5 -
Carbox meth lation 0.70.
Distribution of Even and random distribution of
Carbox meth Is carbox Imeth Is along the backbone
Molecular Weight Mw: 5,000 - 2,000000. Preferred:
medium (approx 250,000 g/mol)
Type of Modification Ether modification (in addition to
carboxymethylation). Mixed cellulose
ether
Level of Modification DSRH = about 0.001 to about 0.1
Wherein the cyclic base amine polymer/oligomer are selected from one or more
of the compounds below. The chemical structures shown in the examples below
are idealized structures. Side reactions expected to occur during the
condensation are not shown.
Material Level
wt %
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Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1:1, Polymer from Example 1)
tv~! ~ OH
3.0
Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1.36:1, Polymer from Example
2)
0.8
L OH
Adduct of Imidazole-epichlorohydrin
0.8
(Ratio of imidazole:epichlorohydrin 1.75:1)
N~ R
L ''/ OH
Adduct of Imidazole-epichlorohydrin-trisglycidyl ether from
glycerine (Ratio of imidazole:epichlorohydrin: trisglycidylether
2.0:1.76:0.26)
H 0.C7
HO O OH
-O N
OH
Adduct of lmidazole-epichlorohydrin- -trisglycidyl ether from
glycerine(Ratio of imidazole:epichlorohydrin: -trisglycidyl ether
from glycerine 2.0:1.9:0.1) 0.8
H
HO O OH
N-"
~-j OH
Adduct of piperazine and epichlorohydrin (ratio 1:1) 0.8
N~ \V
d
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Adduct of piperazine and epichlorohydrin (ratio 1:1), benzyl quat 0$
OH
~O~d
Adduct of piperazine and epichlorohydrin (ratio 1:1) methyl quat 0$
CH3 OH
~N \_j N
Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0)
/--~ OH
O\ /N N\/ \/N N\~/0
a
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9: 0.8
0.4:1.0)
//D
N Adduct of piperazine, morpholine and epichlorohydrin (ratio 0.9: 0.8
0.4:1.0) methyl quat
CH30H
O~N N~O+ N/0
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9: 0.8
0.4:1.0) methyl quat
l-~
No
CN CH3
OH OH
Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9: 0.8
0.4:1.0) benzyl quat
O
O N N N N O
OH OH
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Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9: 0.8
0.4:1.0) benzyl quat
O
CNNCNQ
OH OH
Adduct of imidazole, piperazine and epichlorohydrin (ratio 2:1:3) 0.8
OH
N~~ N N~N
OH
Adduct of imidazole, piperazine and epichlorohydrin (ratio 1:1:2) 0.8
D
N~~ N N/ L ~ OH Adduct of imidazole, 1,6 diaminohexane and epichlorohydrin
(ratio
1:1:2)
NNH 0.8
OH OH
Adduct of imidazole, dimethylaminopropylamine and
epichlorohydrin (ratio 1.02:0.34:1.0)
OH
N/~~
~ OH 0.8
N
H3C/ \OH3
Adduct of imidazole-epichlorohydrin and chloroacetic acid (Ratio- 1.0
1.36:0.83:0.34)
HOOC,--~'J~ ' N~~ N~ N--COOH
OH ~ H \,--/
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Adduct of imidazole, piperazine and 0.5
epichlorohydrin (Ratio- 1.0:1.0:2.0) quat with 0.22 moles of
chloroacetate
Hooc
\ ~ ) OH OH
OH \---~
Adduct of imidazole, piperazine and epichlorohydrin (Ratio- 2.0
1.0:3.0:4.0) quat with 0.32 moles of chloroacetate
HOOC
OH OH
OH \~ v
Adduct of imidazole and epichlorohdrin, (ratio 1.75:1) oxidized 0.1
O-N 'N N 'N NO
OH
58
