Amphiphilic polymer composition

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

Reexamination Certificate

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C526S210000, C526S318200, C526S318300, C526S318410, C526S225000, C526S229000, C526S932000

Reexamination Certificate

active

06569976

ABSTRACT:

BACKGROUND
The present invention relates to polymer compositions containing both hydrophobic and hydrophilic moieties. Polymer compositions of the present invention are useful as active ingredients in detergent and cleaning formulations; in particular, the polymer compositions of the present invention are useful in laundry detergent formulations.
In the absence of suitable dispersants, oily soil particles that are removed during the washing step of typical laundry processes may re-deposit onto the fabric being cleaned. Additives are used during the washing process to disperse and suspend the soil particles in the wash liquor so that the soil particles may be removed during the rinse portion of the cleaning process. Materials used to disperse and suspend soil particles in cleaning formulations must be compatible with other components of the cleaning formulation as well as provide satisfactory dispersing and suspending properties towards oil soil particles. Accordingly, there is a need for materials that can be used as compatible, effective oily soil dispersants in laundry detergent formulations.
A variety of copolymer compositions have been used as additives in cleaning formulations. For example, JP 7-216388 discloses detergent compositions for cleaning hard surfaces, in particular metal parts, where the components of the detergent composition are (1) copolymers of 1 to 50% acrylic or methacrylic acid monomer units and 50 to 99% of (meth)acrylic acid derivative monomer units, such as (C
1
-C
4
)alkyl (meth)acrylates and methoxy(meth)acrylate poly(ethyleneglycol) adducts; and (2) an anionic surfactant.
U.S. Pat. No. 4,384,096 discloses emulsion polymers containing 15 to 60% of (C
3
-C
8
) ethylenically unsaturated carboxylic acid monomer units, 15 to 80% of nonionic copolymerizable (C
2
-C
12
) ethylenically unsaturated monomer units, and 1 to 30% of certain vinyl surfactant esters, including (C
8
-C
20
)alkoxy(meth)acrylate poly(alkyleneglycol) and (C
8
-C
16
)alkylphenoxy(meth)acrylate poly(alkyleneglycol) adducts; these emulsion polymers are disclosed as being useful as thickeners in cosmetic products, drilling muds, and aqueous coating compositions, such as latex paint.
U.S. Pat. No. 4,797,223 discloses detergent compositions containing water-soluble polymers as builders, dispersants and anti-redeposition agents. The water-soluble polymers disclosed include those containing 20 to 95% of ethylenically unsaturated (C
3
-C
6
)monocarboxylic acid monomer units; 4 to 80% of (meth)acrylate esters of poly(alkyleneoxides), including (C
1
-C
18
)alkoxy(meth)acrylate poly(alky-lene glycol) and (C
1
-C
18
)alkaryloxy(meth)acrylate poly(alkyleneglycol) adducts; and 0 to 30% of noncarboxylate ethylenically unsaturated monomer units such as ethyl acrylate or methyl methacrylate.
European Patent Application EP 995,791 discloses hydrophobically-modified polycarboxylate polymers for promoting soil release from fabrics, where the polymers contain monomeric units of a first monomer selected from alkyl (meth)acrylates, ethoxylated alkyl (meth)acrylates and poly(alkylene glycol) (meth)acrylates and at least one of second monomer selected from unsaturated (C
3
-C
8
)carboxylic acids and/or other unsaturated monomers copolymerizable with the other monomers.
The present invention seeks to improve upon the prior detergent dispersant technology by identifying polymers that are compatible in the cleaning formulation and that provide enhanced cleaning and anti-redeposition properties when used in laundry detergent formulations.
SUMMARY OF INVENTION
The present invention provides a polymer comprising, as polymerized units: (a) 5 to 40 percent, based on weight of the polymer, of a monoethylenically unsaturated (C
3
-C
6
)carboxylic acid; (b) 35 to 65 percent, based on weight of the polymer, of a (C
1
-C
4
)alkyl (meth)acrylate ester; and (c) 20 to 60 percent, based on weight of the polymer, of an alkoxylated (meth)acrylate monomer having formula I:
wherein:
n is from 2 to 30;
R
1
is H or CH
3
;
R
2
is H or a (C
1
-C
6
)alkyl group; and
R
3
is H or CH
3
.
In another embodiment, the present invention provides a polymer comprising, as polymerized units: 10 to 30 percent of acrylic acid, 40 to 60 percent of butyl acrylate, and 30 to 50 percent of the alkoxylated (meth)acrylate monomer having formula I, wherein R
1
and R
2
are CH
3
, R
3
is H, and n is from 4 to 9.
DETAILED DESCRIPTION
We have discovered that polymer compositions based on selected alkyl (meth)acrylate ester monomers, carboxylic acid monomers and alkoxylated (meth)acrylate monomers, formed in selected weight ratios, can be designed to incorporate the beneficial hydrophilic and hydrophobic characteristics of each type of monomer, resulting in unexpectedly improved cleaning properties of fabric cleaning formulations containing the polymers, in particular liquid and solid laundry detergent formulations.
As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise. The term “alkyl (meth)acrylate” refers to either the corresponding acrylate or methacrylate ester; similarly, the term “(meth)acrylic” refers to either acrylic or methacrylic acid and the corresponding derivatives, such as esters or amides. All percentages referred to will be expressed in weight percent (%), based on total weight of polymer or composition involved, unless specified otherwise. The term “copolymer” refers to polymer compositions containing units of two or more different monomers. The following abbreviations are used herein: g=grams; ppm=parts per million by weight/volume. Unless otherwise specified, ranges listed are to be read as inclusive and combinable and temperatures are in degrees centigrade (° C.).
Polymers of the present invention typically have a weight average molecular weight (M
w
) for the backbone polymer of 1,000 to 100,000, preferably from 2,000 to 50,000 and more preferably from 3,000 to 20,000. Weight average molecular weights for the backbone polymer are based on aqueous phase gel permeation chromatography (GPC) analysis using known polymer standards appropriate for the polymer compositions involved; the polymers are subjected to hydrolysis (to the acid form) prior for determination of the backbone polymer molecular weight.
The polymers of the present invention contain, as polymerized units, from 5 to 40%, preferably from 10 to 30% and more preferably from 10 to 20%, of one or more monoethylenically unsaturated (C
3
-C
6
)carboxylic acid monomers. Suitable monoethylenically unsaturated (C
3
-C
6
)carboxylic acid monomers include monoethylenically unsaturated monocarboxylic acids and monoethylenically unsaturated dicarboxylic acid monomers. For example, monoethylenically unsaturated monocarboxylic acids include acrylic acid (AA), methacrylic acid (MAA), &agr;-ethacrylic acid, &bgr;,&bgr;-dimethylacrylic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, and alkali and metal salts thereof. Suitable monoethylenically unsaturated dicarboxylic acid monomers include, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, methylenemalonic acid, and alkali and metal salts thereof. Preferably, the monoethylenically unsaturated (C
3
-C
6
)carboxylic acid monomers are selected from one or more of acrylic acid and methacrylic acid.
The polymers of the present invention contain, as polymerized units, from 35 to 65%, preferably from 40 to 60% and more preferably from 40 to 50%, of one or more (C
1
-C
4
)alkyl (meth)acrylate ester monomers. Suitable (C
1
-C
4
)alkyl (meth)acrylate ester monomers include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, secondary butyl acrylate, tertiary-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate and isobutyl methacrylate. Preferred (meth)acrylate esters include methyl acrylate, ethyl acrylate and butyl acrylate.
T

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