Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY DETERGENT COMPOSITIONS WITH CERTAIN CATIONICALLY CHARGED
DYE MAINTENANCE POLYMERS
FIELD OF THE INVENTION
The present invention relates to compositions, in either liquid or granular
form, for use in
laundry applications, wherein the compositions comprise certain dye
maintenance polymers that
have a net positive charge. Compositions comprising the dye maintenance
polymers of this
invention impart appearance and integrity benefits to fabrics and textiles
laundered in washing
solutions formed from such compositions.
BACKGROUND OF THE INVENTION
It is, of course, well lrnown 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 lrnit 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, 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, there is clearly an ongoing need to identify materials
which could be
added to laundry products that would associate themselves with the fibers of
the fabrics and
textiles laundered using such products and thereby reduce or minimize the
tendency of the
laundered fabric/textiles to deteriorate in appearance. Any such detergent
product additive
CA 02365303 2004-08-06
material should, of course, be able to benefit fabric appearance and integrity
without unduly
interfering with the ability of the laundry product to perform its intended
function. The present
invention is directed to the use of dye maintenance polymers in laundry
applications that perform in
this desired manner.
SUMMARY OF TIC INVENTION
The present invention meets the aforementioned need in that it has been
surprisingly
discovered that fabric which is treated, and subsequently re-treated with the
compositions of the
present invention, will resist normal fading and color loss without regard to
the circumstances, inter
alia, due to mechanical wear and abrasion. In addition, fabric which has not
been treated can have
the loss of fabric dye attenuated by washing clothing with the laundry
detergent compositions of the
present invention. The compositions of the present invention can take any
form, inter alia, heavy
duty liquid (HDL), heavy duty granular (HDG), bars, pastes, thixotropic
compositions.
In one embodiment the present invention provides a detergent composition
comprising:
a) from 4% to 70% by weight, of a surfactant; b) from 0.01 % to 10% by weight,
of a dye
maintenance co-polymer, said copolymer having the general formula:
A
x has the value of from 10 to 100,000; y has the value of from 10 to 100,000;
the ratio of x to y is
from 9:1 to 1:9; each Z is independently (CH2)mCOR' wherein R' is selected
from: i) -OR3;
ii) -O(CHz)°N(R3h; iii) -0(CHz)r,N+(R3)3X ; iv) -NR3(CHZ)°N(R3~;
v) -NR3(CHZ~,N+(R3~X ;
vi) -(CHz)"N(R3)Z; vii) -(CHZ)"N+(R3)3X-; viii) or mixtures thereof; each R3
is independently
hydrogen, Cl-Cg alkyl, CZ-C$ hydroxyalkyl, and mixtures thereof; X is a water
soluble anion; the
index n is from 0 to 6; the index m is from 0 to 6; provided said co-polymer
has a net cationic
charge; and wherein said dye maintenance co-polymer is not an
polyethyleneimine or alkoxylated
derivative thereof; and c) the balance carriers and other adjunct ingredients.
Another aspect of the present invention relates to laundry detergent
compositions providing
dye protection benefits to fabric comprising:
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2a
a) from about 4% to about 70% by weight, of a surfactant selected from the
group
consisting of nonionic, anionic, cationic, amphoteric, zwitterionic
surfactants and
mixtures thereof, preferably at least one of said surfactants is an anionic
surfactant;
b) from about 0.01 %, preferably from about 0.1 %, more preferably from about
0.5%,
most preferably from about 0.8% to about 10%, preferably to about 8%, more
preferably to about 6%, most preferably to about 5% by weight, of a dye
maintenance polymer or oligomer, said polymer or copolymer comprising one or
more units having the formula:
I) linear polymer units having the formula:
R~ R2
I ~
C-C
R~ Z
wherein each R' is independently
a) hydrogen;
b) C1-C4 alkyl;
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3
c) substituted or unsubstituted
phenyl;
d) substituted or unsubstituted
benzyl;
e) carbocyclic;
f) heterocyclic;
g) and mixtures thereof;
eachRZ is independently
a) hydrogen;
b) halogen
c) C,-C4 alkyl;
d) C,-C4 alkoxy;
e) substituted or unsubstituted
phenyl;
f) substituted or unsubstituted
benzyl;
g) carbocyclic;
h) heterocyclic;
i) and mixtures thereof;
eachZ is independently
a) hydrogen;
b) hydroxyl;
c) halogen;
d) -(CHZ),"R;
wherein R is:
i) hydrogen;
ii) hydroxyl
iii) halogen;
iv) nitrilo;
v) -OR3;
vi) -O(CHZ)"N(R3)Z;
vii) -O(CHZ)"N+(R3)3X
;
viii) -OCO(CHZ)"N(R3)z;
ix) -OCO(CHZ)"N+(R3)3X
-;
x) -NHCO(CHZ)"N(R3)2;
xi) -NHCO(CHZ)"N+(R3)3X-;
xii) -(CHZ)"N(R3)z;
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4
xiii) -(CHz)oN+(R3)sX ;
xiv) carbocyclic;
xv) heterocyclic;
xvi) nitrogen heterocycle quaternary ammonium;
xvii) nitrogen heterocycle N-oxide;
xviii) aromatic N-heterocyclic quaternary ammonium;
xix) aromatic N-heterocyclic N-oxide;
xx) -NHCHO;
xxi) or mixtures thereof;
each R3 is independently hydrogen, C,-Cg alkyl, CZ-C8
hydroxyalkyl, and mixtures thereof; X is a water soluble anion;
the index n is from 0 to 6
e) -(CHZ)",COR'
wherein
R' is
i) -OR3;
ii) -O(CHZ)nN(R3)2;
iii) -O(CHz)"N+(R3)sX
-;
iv) -NR3(CHZ)"N(R3)z;
-NR3(CHz)nN+(R3)sX
v1) -(CHZ)nN(R3)2i
v11) -(CHZ)nN+(R3)sX
,
viii) or mixtures thereof;
each R3 is independently hydrogen, C,-Cg alkyl, CZ-C8
hydroxyalkyl, and mixtures thereof; X is a water soluble anion;
the index n is from 0 to 6;
f) and mixtures thereof;
the index m is from 0 to 6;
II) cyclic units derived from cyclically polymerizing monomers having the
formula:
Ra _
X
Ra-N~ Rs
Rs
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wherein each R4 is independently an olefin comprising unit which is
capable of propagating polymerization in addition to forming a cyclic
residue with an adjacent R4 unit; RS is C,-C,2 linear or branched alkyl,
benzyl, substituted benzyl, and mixtures thereof; X is a water soluble
anion; and
III) mixtures thereof;
provided said polymer or co-polymer has a net cationic charge; and wherein
said
dye maintenance polymer is not an polyethyleneimine or alkoxylated derivative
thereof; and
b) the balance carriers and other adjunct ingredients.
In addition to the surfactant and the dye maintenance polymer of this
invention, the
laundry detergent compositions herein comprise from about 0.01% to 80% by
weight of an
organic or inorganic detergency builder and other conventional laundry
detergent products.
In its method aspect, the present invention relates to the laundering or
treating of fabrics and
textiles in aqueous washing, rinsing, or treating solutions formed from
effective amounts of any
of the detergent compositions, fabric softener compositions, or aqueous
solution treatments
described herein, or formed from the individual components of such
compositions. Laundering
of fabrics and textiles in such washing, rinsing and/or treatment solutions,
followed by drying,
imparts fabric appearance benefits to the fabric and textile articles so
treated. Such benefits can
include improved overall appearance, pill/fuzz reduction, anti-fading,
improved abrasion
resistance, and/or enhanced softness. It has been surprisingly determined that
the dye
maintenance polymers of this invention impart fabric appearance and integrity
benefits that are
greater than the benefits achieved by a corresponding amount of either
component by itself.
These and other objects, features and advantages will become apparent to those
of
ordinary skill in the art from a reading of the following detailed description
and the appended
claims. All percentages, ratios and proportions herein are by weight, unless
otherwise specified.
All temperatures are in degrees Celsius (° C) unless otherwise
specified.
DETAILED DESCRIPTION OF THE INVENTION
As noted, when fabric or textiles are laundered in solutions which comprise
the dye
maintenance polymers of the present invention fabric appearance and integrity
are enhanced. The
dye maintenance polymers can be added to wash solutions by incorporating them
into a detergent
composition, a fabric softener or by adding them separately to the washing
solution. The dye
maintenance polymers are described herein primarily as liquid or granular
detergent additives but
CA 02365303 2004-08-06
6
the present invention is not meant to be so limited. The dye maintenance
polymers, detergent
composition components, optional ingredients for such compositions and methods
of using such
compositions, are described in detail below. All percentages are by weight
unless other specified.
Dve Maintenance Polymers
Compositions and systems of the present invention comprise from about 0.1 %,
preferably
for about 1%, more preferably from about 2%, most preferably from about 3% to
about 10%,
preferably to about 7%, more preferably to about 5% by weight, of a polymer,
co-polymer, or
mixture thereof, wherein said polymer or co-polymer comprises at least one
cationically charged
unit, inter alia, quaternary ammonium moiety or unit which can form a cationic
charge in situ,
inter alia, primary amine moiety. Stated in another way, the oligomer,
polymer, or co-polymer
resulting from the herein below described monomer units must have a net
cationic charge. The
charge can be distributed among any of the herein described units.
The dye maintenance polymers of this invention can be used in any fabric
laundering
process and provide certain appearance benefits to the fabrics laundered in
these processes. 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. The dye maintenance polymers used in the
compositions and
methods herein can provide such fabric appearance benefits when incorporated
in a wash or rinse
added products.
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 copolymerizing acrylamide with
dimethyldiallylammonium chloride, vinyl amine with vinyl alcohol, etc
Cationic polymers in general and their method of manufacture are know. For
example, a
detailed description of cationic polymers can be found in an article by M.
Fred Hoover that was
published in the Journal ofMacromolecular Science-Chemistry, A4(6), pp 1327-
1417, October,
1970. The dye maintenance polymers of this invention will be better understood
when read in light
of the Hoover article, the present disclosure and the Examples herein.
Linear Polymer Units
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7
The polymers or co-polymers of the present invention can comprise one or more
linear
polymer units having the formula:
R1 R2
C-C
RI Z
wherein R', RZ, and Z are defined herein below. Preferably, the linear polymer
units are formed
from linearly polymerizing monomers. Linearly polymerizing monomers are
defined herein as
monomers which under standard polymerizing conditions result in a linear
polymer chain or
alternatively which linearly propagate polymerization. The linearly
polymerizing monomers of
the present invention have the formula:
R1 R2
\C=C~
Rl~ Z .
however, those of skill in the art recognize that many useful linear monomer
units are introduced
indirectly, inter alia, vinyl amine units, vinyl alcohol units, and not by way
of linearly
polymerizing monomers. For example, vinyl acetate monomers once incorporated
into the
backbone are hydrolyzed to form vinyl alcohol units. For the purposes of the
present invention,
linear polymer units may be directly introduced, i.e. via linearly
polymerizing units, or indirectly,
i.e. via a precursor as in the case of vinyl alcohol cited herein above.
Each R' is independently hydrogen, C,-C4 alkyl, substituted or unsubstituted
phenyl,
substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures
thereof. Preferably
R' is hydrogen, C,-CQ alkyl, phenyl, and mixtures thereof, more preferably
hydrogen and methyl.
Each RZ is independently hydrogen, halogen, C,-C4 alkyl, C,-C4 alkoxy,
substituted or
unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic,
heterocyclic, and mixtures
thereof. Preferred Rz is hydrogen, C,-CQ alkyl, and mixtures thereof.
Each Z is independently hydrogen; hydroxyl; halogen; -(CHZ)mR, wherein R is
hydrogen,
hydroxyl, halogen, nitrilo, -OR3, -O(CHZ)"N(R3)2, -O(CHZ)"N+(R3)3X-, -
OCO(CHZ)~N(R3)z,
OCO(CHZ)nN+(R3)3X , -NHCO(CHZ)"N(R3)z, -NHCO(CHZ)~N+(R3)3X , -(CHZ)"N(R3)2, -
(CHZ)~N+(R3)3X-, a non-aromatic nitrogen heterocycle comprising a quaternary
ammonium ion, a
non-aromatic nitrogen heterocycle comprising an N-oxide moiety, an aromatic
nitrogen
containing heterocyclic wherein one or more or the nitrogen atoms is
quaternized; an aromatic
nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide; -
NHCHO
(formamide), -or mixtures thereof; wherein each R3 is independently hydrogen,
C,-C8 alkyl, C,-C8
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hydroxyalkyl, and mixtures thereof; X is a water soluble anion; the index n is
from 0 to 6;
carbocyclic, heterocyclic, or mixtures thereof; -(CHZ)mCOR' wherein R' is -
OR3, -O(CHz)nN(R3)z,
-O(CHz)nN+(R3)sX ~ -~3(CHz)~N(R3)z~ -~3(CHz)nN+(R3)sX ~ -(CHZ)nN(R3)2~ -
(CHz)aN+(R3)sX
or mixtures thereof, wherein R3, X, and n are the same as defined herein
above. A preferred Z is
-O(CHZ)nN+(R3)3X-, wherein the index n is 2 to 4. The index m is from 0 to 6,
preferably 0 to 2,
more preferably 0.
Non-limiting examples of linearly polymerizing monomers comprising a
heterocyclic Z
unit includes 1-vinyl-2-pyrrolidinone, 1-vinylimidazole, 2-vinyl-1,3-
dioxolane, 4-vinyl-1-
cyclohexenel,2-epoxide, and 2-vinylpyridine.
The polymers and co-polymers of the present invention comprise Z units which
have a
cationic charge or which result in a unit which forms a cationic charge in
situ. When the co-
polymers of the present invention comprise more than one Z unit, for example,
Z', ZZ,...Z° units,
at least about 1 % of the monomers which comprise the co-polymers will
comprise a cationic unit.
Preferred cationic units include -O(CHZ)"N+(R3)3X- and -(CHZ)oN+(R3)3X-. When
the co-
polymers of the present invention are formed from two monomers, Z' and ZZ, the
ratio of Z' to ZZ
is preferably from about 9:1 to about 1:9.
A non-limiting example of a Z unit which can be made to form a cationic charge
in situ is
the -NHCHO unit, formamide. The formulator can prepare a polymer or co-polymer
comprising
formamide units some of which are subsequently hydrolyzed to form vinyl amine
equivalents.
For example the formulator may prepare a co-polymer having the general
formula:
which comprises a formamide unit and then subsequently treat the co-polymer
such that some of
the formamide units are hydrolyzed to form a co-polymer comprising vinyl amine
units, said
polymer having the formula:
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wherein Z may be a cationic unit comprising or non-cationic unit comprising
moiety and x' + x" _
x.
Another class of preferred linearly polymerizable monomers comprise
canonically
charged heteroaromatic Z units having the formula:
R1 R2
/C=C
R
N+
6
R
an non-limiting example of which is 4-vinyl (N-alkyl)pyridine wherein R' and
RZ are each
hydrogen and R6 is methyl.
Another class of preferred linearly polymerizable monomers which comprises a
heterocyclic ring includes Z units comprising an N-oxide, for example, the N-
oxide having the
formula:
R' RZ
\C=C~
R~~
N/
~O
a non-limiting example of which is 4-vinyl pyridine N-oxide.
N-alkyl vinylpyridine monomers and N-oxide vinylpyridine monomers can be
suitably
combined with other non aromatic monomers, inter alia, vinyl amine. However,
preferred
polymers of the present invention include co-polymers derived from a
combination of
quaternized, N-oxide, and nitrogen containing heteroaromatic monomers, non-
limiting examples
of which includes a copolymer of N-methyl vinyl pyridine and vinyl pyridine in
a ratio of 4: l; a
copolymer of N-methyl vinyl pyridine and vinyl pyridine in a ratio of 4:6; a
co-polymer of
poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratio of polymer
to monomer of
4:1; poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratio of
polymer to monomer
of 4:6; and mixtures thereof.
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A preferred linear co-polymer according to the present has the formula:
Z~ Jx ~ ZZ J y
wherein Z' has the formula:
O NH2.
Z2 has the formula:
~H3 X_
N+_
O O~ ~ CH3
CH3
wherein X is chlorine; x has the value of from about 10 to about 100,000; y
has the value of from
about 10 to about 100,000; the ratio of x to y is from 9:1 to 1:9. Co-polymers
of this type are
available as, e.g., Sedipur~ CF104 ex BASF.
As described herein above, some preferred polymer residues may be formed by
treatment of the
resulting polymer. For example, vinyl amine residues are preferably introduced
via formamide
monomers which are subsequently hydrolyzed to the free amino unit. Also vinyl
alcohol units are
obtained by hydrolysis of residues formed form vinyl acetate monomers.
Likewise, acrylic acid
residues may be esterified after polymerization, for example, units having the
formula:
CH3 X -
N+_
O O~ ~ CH3
CH3
may be more conveniently formed after the backbone has been formed by
polymerization with
acrylic acid or acrylic acid precursor monomers.
II) Cyclic Units Derived from Cyclically Polymerizing Monomers
The polymers or co-polymers of the present invention can comprise one or more
cyclic
polymer units which are derived from cyclically polymerizing monomers.
Cyclically
polymerizing monomers are defined herein as monomers which under standard
polymerizing
conditions result in a cyclic polymer residue as well as serving to linearly
propagate
polymerization. Preferred cyclically polymerizing monomers of the present
invention have the
formula:
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11
Ra _
X
Ra-N~ Rs
Rs
wherein each R4 is independently an olefin comprising unit which is capable of
propagating
polymerization in addition to forming a cyclic residue with an adjacent R4
unit; RS is C,-C,2 linear
or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a
water soluble anion.
Non-limiting examples of R4 units include allyl and alkyl substituted allyl
units.
Preferably the resulting cyclic residue is a six-member ring comprising a
quaternary nitrogen
atom.
RS is preferably C,-C4 alkyl, preferably methyl.
An example of a cyclically polymerizing monomer is dimethyl diallyl ammonium
having
the formula:
N+
/\
H3C CH3
which results in a polymer or co-polymer having units with the formula:
N+ X-
H3C CH3
z
wherein preferably the index z is from about 10 to about 50,000.
III) Mixtures thereof.
The polymers or co-polymers of the present invention must retain a net
cationic charge,
whether the charged is developed in situ, or whether the polymer or co-polymer
itself has a
formal positive charge. Preferably the polymer or co-polymer has at least 10%,
more preferably
at least about 25%, more preferably at least about 35%, most preferably at
least about 50% of the
residues comprise a cationic charge.
The polymers or co-polymers of the present invention can comprise mixtures of
linearly
and cyclically polymerizing monomers, for example the poly(dimethyldiallyl-
ammonium
chloride/acrylamide) co-polymer having the formula:
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wherein Z', Z2, x, y, and z are the same as defined herein above and X is
chloride ion.
A particularly preferred embodiment of this invention is the composition
comprising a
polymer based on dimethyldiallylammonium chloride and a copolymer which is
based upon
acrylamide with a co-monomer selected from the group consisting of N, N
dialkylaminoalkyl(meth)acrylate, N, N dialkylaminoalkylacrylate, N,N
dialkylaminoalkylacrylamide, N,N dialkylaminoalkyl(meth)acrylamide, their
quaternized
derivatives and mixtures thereof.
Non-limiting examples of preferred polymers according to the present invention
include
dye maintenance copolymers comprising:
i) a first monomer selected from the group consisting of N, N
dialkylaminoalkyl(meth)acrylate, N, N dialkylaminoalkylacrylate, N,N
dialkylaminoalkylacrylamide, N,N dialkylaminoalkyl(meth)acrylamide, their
quaternized derivatives and mixtures thereof; and
ii) a second monomer selected from the group consisting of acrylic acid,
methacrylic
acid, C,-C6 alkylmethacrylate, C,-C6 alkyl acrylate, C,-C8
hydroxyalkylacrylate,
C,-C8 hydroxyalkylmethacrylate, acrylamide, C,-C,6 alkyl acrylamide, C,-C,6
dialkylacrylamide, 2-acrylamido-2-methylpropane sulfonic acid or its alkali
salt,
methacrylamide, C,-C,6 alkylmethacrylamide, C,-C,6 dialkylmethacrylamide,
vinyl formamide, vinylacetamide, vinyl alcohol, C,-C8 vinylalkylether, vinyl
pyridine, itaconic acid, vinyl acetate, vinyl propionate, vinyl butyrate and
mixtures thereof;
wherein the copolymer comprises at least 25 mole % of the first monomer.
ADJUNCT INGREDIENTS
The compositions of the present invention may also optionally comprise one or
more
adjunct ingredients. Non-limiting examples of adjunct ingredients are selected
from the group
consisting of detersive surfactants, electrolytes, stabilizers, low molecular
weight water soluble
solvents, chelating agents, dispersibility aids, soil release agents, nonionic
fabric softening agents,
CA 02365303 2005-08-03
13
concentration aid, perfume, preservatives, colorants, optical brighteners,
opacifiers, germicides,
fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof.
The following are applications which describe various detergent additive,
methods of
making these additives and methods of using them. WO 99/07813 A 1 Randall et
al.,
"Laundry Detergent Compositions with Amino Acid Based Polymers to Provide
Appearance and Integrity Benefits to Fabrics Laundered Therewith"; WO 99/07814
A 1
Randall et al., "Laundry Detergent Compositions with Amino Acid Based Polymers
to
Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith"; WO
99/14299 AI
Panandiker et al., "Laundry Detergent Compositions with Anionically Modified,
Cyclic Amine
Based Polymers; WO 99/14300 A1 Panandiker et al., "Laundry Detergent
Compositions with
Cyclic Amine-Based Polymers to Provide Appearance and Integrity Benefits to
Fabrics
Laundered Therewith"; WO 99/14301 A1 Panandiker et al., "Laundry Detergent
Compositions
and Fabric Conditioning Compositions with Oxidized Cyclic Amine-Based
Polymers"; and
WO 00/22078 Panandiker et al., "Laundry Detergent Compositions with A
Combination of Cyclic
Amine Based Polymers and Hydrophobically Modified Carboxy Methyl Cellulose".
SURFACTANT SYSTEM
The laundry detergent compositions of the present invention comprise a
surfactant
system. The surfactant systems of the present invention may comprise any type
of detersive
surfactant, non-limiting examples of which include one or more mid-chain
branched alkyl sulfate
surfactants, one or more mid-chain branched alkyl aIkoxy sulfate surfactants,
one or more mid-
chain branched aryl sulfonate surfactants, one or more non mid-chain branched
sulphonates,
sulphates, cationic surfactants, zwitterionic surfactants, ampholytic
surfactants, and mixtures
thereof.
The total amount of surfactant present in the compositions of the present
invention is
from about 4% by weight, preferably from about 10% more preferably from about
15% to about
60%, preferably to about 30% by weight, of said composition.
Nonlimiting examples of surfactants useful herein include:
a) C"-C,8 alkyl benzene sulfonates (LAS);
b) C6-C,8 mid-chain branched aryl sulfonates (BLAS);
c) C,°-CZO primary, a or cc~-branched, and random alkyl sulfates (AS);
d) C"-C~ mid-chain branched alkyl sulfates (BAS);
e) C,°-C,e secondary (2,3) alkyl sulfates as described in U.S.
3,234,258 Morris, issued
February 8, 1966; U.S. 5,075,041 Lutz, issued December 24, 1991; U.S.
5,349,101 Lutz
CA 02365303 2004-08-06
is
et al., issued September 20, 1994; and U.S. 5,389,277 Prieto, issued February
14, 1995;
f) C,o-C,8 alkyl alkoxy sulfates (AExS) wherein preferably x is from 1-7;
g) C"-C~ mid-chain branched alkyl alkoxy sulfates (BAE,S);
h) C,o-C,e alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units;
i) C,2-C,e alkyl.ethoxylabes, C6-C,i alkyl phenol alkoxylates wherein the
alkoxylate units
are a mixture of ethyleneoxy and propyltneoxy units, C,2-C,e alcohol and C6-
C,z alkyl
phenol condensates with ethylene oxide/propylene oxide block polymers inter
alia
Pluronic~ ex BASF which are disclosed in U.S. 3,929,678 Laughlin et al.,
issued
December 30, 1975;
j) C"-CZZ mid-chain branched alkyl alkoxylates, BAEx;
k) Alkylpolysaccharides as disclosed in U.S. 4;565,647 Llenado, issued January
26, 1986;
1) Polyhydroxy fatty acid' amides having the formula:
O R8
R~ C-N-Q
wherein R' is CS-C3, alkyl; R$ is selected from the group consisting of
hydrogen, C,-C, alkyl, C,-
C~ hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear alkyl chain
with at least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof; prefen ed alkoxy
is ethoxy or propoxy, and mixtures thereof; prefer ed Q is derived from a
reducing sugar in a
reductive amination reaction, more preferably Q is a glycityl moiety; Q is
more preferably
selected from the group consisting of -CHZ(CHOH)"CHZOH, -
CH(CHZOH)(CHOH)".,CH,OH, -
CHZ(CHOH)Z(CHOR')(CHOH) CHZ OH, and alkoxylated derivatives thereof, wherein n
is an
integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or aliphatic
monosaccharide, which
are described in U.S. 5,489,393 Connor et al., issued February 6, 1996; and
U.S. 5,45,982 Murch
et al., issued October 3, 1995.
A non-limiting example of a nonionic surfactant suitable for use in the
present invention
has the formula:
O
R-C-N-((R~O)x(RZO)yR3)m
~~n
wherein R is C,-C~, linear alkyl, C,-Ci, branched alkyl, CT-CZ, linear
alkenyl, C,-CZ, branched
alkenyl, and mixtures thereof.
CA 02365303 2001-09-13
WO 00/56849 PCT/US00/08031
R' is ethylene; RZis C3-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof;
preferably RZ is 1,2-propylene. Nonionic surfactants which comprise a mixture
of R' and RZUnits
preferably comprise from about 4 to about 12 ethylene units in combination
with from about 1 to
about 4 1,2-propylene units. The units may be alternating, or grouped together
in any
combination suitable to the formulator. Preferably the ratio of R' units to RZ
units is from about 4
1 to about 8 : 1. Preferably an RZ units (i.e. 1,2-propylene) is attached to
the nitrogen atom
followed by the balance of the chain comprising from 4 to 8 ethylene units.
R2 is hydrogen, C,-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof; preferably
hydrogen or methyl, more preferably hydrogen.
R4 is hydrogen, C,-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof; preferably
hydrogen. When the index m is equal to 2 the index n must be equal to 0 and
the R' unit is absent
and is instead replaced by a -[(R'O)X(RZO)yR3] unit.
The index m is 1 or 2, the index n is 0 or 1, provided that when m is equal to
1, n is equal
to 1; and when m is 2 n is 0; preferably m is equal to 1 and n is equal to
one, resulting in one -
[(R'O)X(RZO)S.R3] unit and R4 being present on the nitrogen. The index x is
from 0 to about 50,
preferably from about 3 to about 25, more preferably from about 3 to about 10.
The index y is
from 0 to about 10, preferably 0, however when the index y is not equal to 0,
y is from 1 to about
4. Preferably all of the alkyleneoxy units are ethyleneoxy units. Those
skilled in the art of
ethoxylated polyoxyalkylene alkyl amide surface active agents will recognized
that the values for
the indices x and y are average values and the true values may range over
several values
depending upon the process used to alkoxylate the amides.
The mid-chain branched alkyl sulfate surfactants of the present invention have
the
formula:
2
R R R
CH3CH2(CHZ)WCH(CH2),~CH(CH2)yCH(CHZ)ZOS03M
the alkyl alkoxy sulfates have the formula:
R R1 RZ
CH3CH2(CHZ)~,CH(CHZ)XCH(CH2)yCH(CH2)Z(OR3)",OS03M;
the alkyl alkoxylates have the formula:
CA 02365303 2004-08-06
16
R R1 R2
CH3CH~(CHI""CH(CH~,zCH(CH~yCH(CH~(OR3~pH
wherein R, R', and RZ are each independently hydrogen, C,-C3 alkyl, and
mixtures thereof;
provided at least one of R, R', and RZ is not hydrogen; preferably R, R', and
RZ are methyl;
preferably one of R, R', and Rs is methyl and the other units are hydrogen.
The total number of
carbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxy sulfate
surfactants is from
14 to 20; the index w is an integer from 0 to 13; x is an integer from 0 to
13; y is an integer from 0
to 13; z is an integer of at least 1; provided w + x + y + z is from 8 to 14
and the total number of
carbon atoms in a surfactant is from 14 to 20; R' is C,-C, linear or branched
alkylene, preferably
ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and
mixtures thereof.
However, a preferred embodiment of the present invention comprises from 1 to 3
units wherein
R' is 1,2-propylene, 1,3-propylene, or mixtures thereof followed by the
balance of the R' units
comprising ethylene units. Another preferred embodiment comprises R' units
which are
randomly ethylene and 1,2-propylene units. The average value of the index m is
at least about
0.01. When the index m has low values, the surfactant system comprises mostly
alkyl sulfates
with a small amount of alkyl alkoxy sulfate surfactant. Some tertiary carbon
atoms may be
present in the alkyl chain, however, this embodiment is not desired.
M denotes a cation, preferably hydrogen, a water soluble cation, and mixtures
thereof.
Non-limiting examples of water soluble cations include sodium, potassium,
lithium, ammonium,
alkyl ammonium, and mixtures thereof.
Detergent Builder
The detergent compositions herein may also comprise from about 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, anunonium and substituted ammonium polyacetates, carboxylates,
polycarboxylates and
polyhydroxy sulfonates. 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
CA 02365303 2004-08-06
17
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,
aluminosiIicates, 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 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
In addition to the surfactants, builders and dye maintenance polymers of the
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-
tarnish 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, 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
I0.0 after the addition of the dye maintenance polymers 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 frequently
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 diperoxydodecanedioic acid. Such
bleaching agents
CA 02365303 2004-08-06
18
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., OXONE~, 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, Solway 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.; slid
U.S. Patent 4,412,934
Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate
(HOBS) 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:
R1N(R5)C(O)R2C(O)Lor R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an alkylene
containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl
containing from
about 1 to about 10 carbon atoms, and L is any suitable leaving group. A
leaving group is any
group that is displaced from the bleach activator as a consequence of the
nucleophilic attack on
the bleach activator by the perhydrolysis anion. A preferred leaving group is
phenol sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene-
sulfonate, (6-
decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in
the hereinbefore
noted U.S. Patent 4,634,551.
CA 02365303 2004-08-06
19
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.
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 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, Iipases,
cellulases, peroxidases, 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
CA 02365303 2001-09-13
WO 00/56849 PCT/US00/08031
compositions herein will typically comprise from 0.001% to 5%, preferably
0.01%-1% by weight
of a commercial enzyme preparation. Protease enzymes are usually present in
such commercial
preparations at levels sufficient to provide from 0.005 to 0.1 Anson units
(AU) of activity per
gram of composition. Higher active levels may be desirable in highly
concentrated detergent
formulations.
Cellulases usable herein include those disclosed in U.S. Patent No. 4,435,307,
Barbesgoard et al., March 6, 1984, and GB-A-2.075.028; GB-A-2.095.275 and DE-
OS-
2.247.832. CAREZYME~ and CELLUZYME~ (Novo) are especially useful. See also WO
9117243 to Novo.
The enzyme-containing compositions herein may optionally also comprise from
about
0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably
from about
0.01% to about 6%, by weight of an enzyme stabilizing system. 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.
Detergent Composition Preparation
The detergent compositions according to the present invention can be in
liquid, paste or
granular form. Such compositions can be prepared by combining the essential
and optional
components in the requisite concentrations in any suitable order and by any
conventional means.
The forgoing description of uses for the dye maintenance polymers defined
herein are intended to
be exemplary and other uses will be apparent to those skilled in the art and
are intended to be
within the scope of the present invention.
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 dye maintenance polymers, 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 dye
maintenance polymers, enzymes, binders and perfumes, can be sprayed onto the
resulting
granules to form the finished detergent composition. Granular compositions
according to the
present invention can also be in "compact form", i.e. they may have a
relatively higher density
than conventional granular detergents, i.e. from 550 to 950 g/1. In such case,
the granular
CA 02365303 2004-08-06
21
detergent compositions according to the present invention will contain a lower
amount of
"inorganic filler salt", compared to conventional granular detergents; typical
filler salts are
alkaline earth metal salts of sulphates and chlorides, typically sodium
sulphate; "compact"
detergents typically comprise not more than 10% filler salt.
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 dye maintenance polymers to liquid detergent or other aqueous
compositions of
this invention may be accomplished by simply mixing into the liquid solutions
the desired dye
maintenance polymers.
Fabric Laundering_Method
The present invention also provides a method for laundering fabrics in a
manner which
imparts fabric appearance benefits provided by the dye maintenance polymers
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 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 are not necessarily meant to limit or otherwise define the scope of the
invention.
CA 02365303 2004-08-06
22
EXAMPLE I
TABLE I comprises numerous examples according to the present invention albng
with
some comparative examples of material known to the art of laundry detergents.
The chemical
structures shown in the examples below are idealized structures. Side
reactions expected to occur
during the condensation are not shown.
TABLEI
Ex.# Material
1 Poly(N, N dimethylaminoethyl methacrylate)
2 Poly(N, N dimethylaminoethyl methacryIate),
MW 9700
3 Poly(N,N dimethylaminoethyl methacrylate),
MW 15,700
4 Poly(N,N dimethylaminoethyl methacrylate),
MW 39,700
S Poly(N,N dimethylaminoethyl methacrylate-co-
dimethylacrylamide) ratiol:l MW 13670
6 Poly(N,N dimethylaminoethyl methacrylate-co-
dimethylacrylamide) ratio 2:1, MW =14,400
7 Poly(N, N dimethylaminoethyl methacrylate-co-
dimethylacrylamide) ratio 3:1 MW 16,300
8 Methyl quat of poly(N,N dimethylaminoethyl
methacrylate)
9 Amine oxide ofPoly(N, N dimethylaminoethyl
methacrylate)
Poly(N,N dimethylaminoethyl methacrylate-co-octylacrylamide)
ratio 3:1, MW = 6730
11 Poly(N,N dimethylaminoethyl methacrylate-co-acrylic
acid) ratio
1:1, MW = 14,950
12 Poly(N,N dimethylaminoethyl methacrylate-acrylamide)
ratio 1:1,
Poly(N,N dimethylaminoethyl methacrylate-propane
sultone)
ratio 1:1,
13 Poly(dimethyldiallylammonium chloride)
sold under the trade
mark Mer uat 100 b Cal on Co oration
Pittsbur PA.
14 Poly(dimethyldiallylammonium chloride
-co- acrylamide) sold
under the trade :mark Merquat Plus (Calgon
Corporation,
Pittsbur , PA .
Poly(dimethyldiallylammonium chloride
-co- acrylamide) sold
under the trade mark Merquat 550 (Calgon
Corporation,
Pittsbur PA .
16 Poly(dimethyldiallylammonium chloride
-co- acrylic acid) sold
under the trade mark Merquat 280 (Calgon
Corporation,
Pittsbur PA .
CA 02365303 2004-08-06
23
17 Poly(N methyl,N octadecyl aminoethyl methacrylate)
quaternized
with dimeth 1 sulfate CTFA nomenclature
of uaternium 8
18 Ionene polymer of N,N,N',N' tetramethyl
hexanediamine and 1,6
dibromohexane in the ratio 4'3
19 Polyvinylamine
20 Poly(vinylamine-co-vinylalcohol) ratio
1:1
21 Poly(vinylamine-co-acrylic acid) ratio
1: l
22 Polyallylamine
23 poly(vinylamine-co-vinyl formamide) ratio
1:1
24 polyvinylamine ethoxylated with 0.5 moles
of ethylene oxide per
N-H
25 polyvinylamine propoxylated with 0.5 moles
of propylene oxide
er N-H
26 Polyquaternium 2 (CTFA nomenclature) sold
under the trade
mark Mira of A15 b Rhone Poulenc Paris,
France.
27 Polyquaternium 17(CTFA nomenclature) sold
under the trade
mark Mira of AD-1 b Rhone Poulenc, Paris
France.
28 Copolymer of N methylvinyl pyridine co-vinyl
pyridine (ratio
4:1)
29 Copolymer of N methylvinyl pyridine co-vinyl
pyridine (ratio
4:6)
30 Poly(N methylvinyl pyridine co-vinyl pyridine
N oxide) ratio 4:1
31 Poly (N methylvinyl pyridine co-vinyl
pyridine N-oxide) ratio 4:6
EXAMPLE II
Granular Detereent Test Composition Preparation
Several heavy duty granular detergent compositions are prepared containing one
or more
dye maintenance polymer having a DMP according to this invention. These
granular detergent
compositions all have the following basic formula:
TABLE II
Com onent Wt.
C Linear alk 1 benzene sulfonate9.31
C a 1 ether 0.35 EO sulfate 12.74
Zeolite Builder 27.79
Sodium Carbonate 27.31
PEG 4000 1.60
Dis ersant 2.26
C Alcohol Ethoxvlate 9 EO 1.5
SodiumPerborate 1.03
Soft Release Polymer 0.41
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WO 00/56849 PCT/US00/08031
24
Enz mes 0.59
D a Maintenance Polymer 3.0
Perfume, Brightener, Suds Suppressor,Balance
Other
Minors, Moisture, Sulfate
100%
EXAMPLE III
Liquid Detergent Test Composition Preparation
Several heavy duty liquid detergent compositions are prepared containing one
or more
dye maintenance polymer having a DMP according to this invention. These liquid
detergent
compositions all have the following basic formula:
TABLE III
Com onent Wt
C _ alk 1 ether 2.5 sulfate 38
C lucose amide ~ 6.86
Citric Acid 4.75
C _ Fat Acid 2.00
E mes 1.02
MEA 1.0
Pro anediol 0.36
Borax 6.58
Dis ersant 1.48
Na Toluene Sulfonate 6.25
D a Maintenance Pol mer 1.0
Dye, Perfume, Brighteners, Preservatives,Balance
Suds
Su ressor, Other Minors, Water
100%
EXAMPLE IV
Granular Detergent Test Composition Preparation
Several granular detergent compositions are prepared containing one or more
dye
maintenance polymer having a DMP according to this invention. Such granular
detergent
compositions all have the following basic formula:
TABLE IV
Exam 1e Com arative
Com onent Wt. % Wt%
Na C Linear alk 1 benzene 9.40 9.40
sulfonate
Na C alk 1 sulfonate 11.26 11.26
Zeolite Builder 27.79 27.79
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WO 00/56849 PCT/US00/08031
Sodium Carbonate 27.31 27.31
PEG 4000 1.60 1.60
Dis ersant, Na of acr 2.26 2.26
late
C alk 1 ethox late 9 1.5 1.5
Sodium Perborate 1.03 1.03
D a Maintenance Pol mer 0.8 0
Other Ad'unct in redientsBalance Balance
100% 100%
