Laundry detergent and cleaning compositions comprising polymers containing carboxyl groups

文档序号：802791 发布日期：2021-03-26 浏览：16次中文

阅读说明：本技术 包含含羧基基团的聚合物的衣物洗涤剂和清洁组合物 (Laundry detergent and cleaning compositions comprising polymers containing carboxyl groups ) 是由王晓利 B·J·罗内刘晓艳 J·S·杜邦米田淳郎道尭大祐于 2012-08-31 设计创作，主要内容包括：本发明涉及包含含羧基基团的聚合物的衣物洗涤剂或清洁组合物,优选颗粒状洗涤剂产品,其可用于改善白度和/或抗污垢再沉积性。本发明还包括所述衣物洗涤剂或清洁组合物的制备方法和使用方法。(The present invention relates to laundry detergent or cleaning compositions, preferably granular detergent products, comprising polymers containing carboxyl groups, which are useful for improving whiteness and/or resistance to soil redeposition. The invention also includes methods of making and methods of using the laundry detergent or cleaning compositions.)

1. A laundry detergent or cleaning composition comprising a carboxyl group-containing polymer comprising:

i. structural units (a) derived from an ether bond-containing monomer (A); wherein the structural unit (a) is represented by formula (1):

wherein R is⁰Represents a hydrogen atom or a methyl group; r¹Represents CH₂Radical, CH₂CH₂A group, or a direct bond; x represents a hydroxyl group or a group represented by formula (2) or (3):

wherein R, which may be the same or different, are²Represents C₂-C₄An alkylene group; n represents an oxyalkylene group (-O-R)²-) and is 0 to 5; and R is³、R⁴And R⁵Independently represent C₁-C₄An alkyl group;

y represents a hydroxyl group or a group represented by formula (2) or (3); and one of X and Y is a hydroxyl group and the other is a group represented by formula (2) or (3),

structural units (B) derived from sulfonic acid group-containing monomer (B); and

structural units (C) derived from acrylic-based monomers (C);

wherein:

the structural unit (a) is present at a content of 0.5 to 15% by mass based on 100% by mass of all structural units derived from all monomers in the carboxyl group-containing polymer; the structural unit (b) is present in a content of 5 to 23% by mass based on 100% by mass of all the structural units derived from all the monomers in the carboxyl group-containing polymer; and is

The structural unit (c) is present in a content of 55 to 99% by mass based on 100% by mass of all the structural units derived from all the monomers in the carboxyl group-containing polymer;

and the carboxyl group-containing polymer has a weight average molecular weight of more than 30,000 and less than 60,000.

2. The laundry detergent or cleaning composition according to claim 1, further comprising an adduct of a bisulfite salt with the acrylic-based monomer (C), wherein the adduct is present at a content of 0.01 to 1.5 mass% based on 100 mass% of a solid content of the carboxyl group-containing polymer composition.

3. The laundry detergent or cleaning composition according to any preceding claims, wherein the laundry detergent or cleaning composition is selected from the group consisting of a liquid laundry detergent composition, a solid laundry detergent composition, a hard surface cleaning composition, a liquid hand dishwashing composition, a solid automatic dishwashing composition, a liquid automatic dishwashing composition, and a tablet/unit dose type automatic dishwashing composition.

4. A laundry detergent or cleaning composition according to any preceding claim wherein the carboxyl group-containing polymer comprises:

(1)1 to 9 mass% of the structural unit (a);

(2)5 to 23 mass% of the structural unit (b); and

(3)68 to 98 mass% of the structural unit (c).

5. A laundry detergent or cleaning composition according to any preceding claim wherein the carboxyl group-containing polymer has a weight average molecular weight of greater than 30,000 and less than or equal to 50,000.

6. A laundry detergent or cleaning composition according to any preceding claim wherein the carboxyl group-containing polymer is selected from:

7. a laundry detergent or cleaning composition according to any preceding claim wherein the carboxyl group-containing polymer comprises:

i. a structural unit (a) represented by the formula (1) wherein R⁰Is a hydrogen atom; r¹Is CH₂A group; x is a hydroxyl group; and Y is formula (2); and in formula (2), n is 0; and R is³Is C₁-C₄An alkyl group;

a structural unit (b) represented by formula (5):

wherein R is⁶Represents a hydrogen atom or a methyl group; r⁷Represents CH₂Radical, CH₂CH₂A group, or a direct bond; r⁸And R⁹Independently represents a hydroxyl group or-SO₃Z; z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group; and R is⁸And R⁹At least one of which is-SO₃Z; and

a structural unit (c) represented by formula (8):

wherein R is¹⁰Represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.

8. A laundry detergent or cleaning composition according to claim 7 wherein the structural unit (b) is selected from vinylsulphonic acid, styrenesulphonic acid, (meth) propenesulphonic acid, 3- (meth) allyloxy-2-hydroxypropanesulphonic acid, 3- (meth) allyloxy-1-hydroxypropanesulphonic acid, 2- (meth) allyloxyethenesulphonic acid, or 2-acrylamido-2-methylpropanesulphonic acid.

9. A laundry detergent or cleaning composition according to any preceding claim, wherein the carboxyl group-containing polymer has an anti-soil redeposition ratio of from 37.0% to 46.0% according to the anti-soil redeposition test described herein.

10. The laundry detergent or cleaning composition according to any preceding claims, wherein the carboxyl group-containing polymer has a whiteness index measurement of 2.0 or greater according to the whiteness retention assay described herein.

11. The laundry detergent or cleaning composition of claim 1, wherein said carboxyl group-containing polymer has a Whiteness Maintenance Efficacy (WME) of at least 6%.

12. A laundry detergent or cleaning composition according to claim 9,10 or 11 wherein the wash solution comprises said carboxyl group containing polymer at a concentration of less than 40 ppm.

13. A laundry detergent or cleaning composition according to claim 1, wherein the laundry detergent or cleaning composition comprises a detersive surfactant, wherein the detersive surfactant comprises:

(i) an alkyl alkoxylated sulphate anionic detersive surfactant having an average degree of alkoxylation of from 0.5 to 5; and/or

(ii) Principal ground C₁₂An alkyl sulphate anionic detersive surfactant; and/or

(iii) Less than 25% of a non-ionic detersive surfactant.

14. A laundry detergent or cleaning composition according to claim 1, wherein the laundry detergent or cleaning composition comprises a clay and soil removal/anti-redeposition agent selected from the group consisting of:

(a) a random graft copolymer comprising:

(i) a hydrophilic backbone comprising polyethylene glycol; and

(ii) one or more hydrophobic side chains selected from: c₄-C₂₅Alkyl radical, polypropylene, polybutene, saturated C₁-C₆Vinyl esters of monocarboxylic acids, C of acrylic or methacrylic acid₁-C₆Alkyl esters, and mixtures thereof;

(b) a cellulose polymer having a mw of 0.01 to 0.99Degree of Substitution (DS) and a Degree of Blockiness (DB) such that DS + DB is at least 1.00 or DB +2DS-DS²Is at least 1.20;

(i) from 50 to less than 98 weight percent structural units derived from one or more monomers comprising a carboxyl group;

(ii) from 1 to less than 49 weight percent structural units derived from one or more monomers comprising a sulfonate moiety; and

(iii)1 to 49 wt% structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (VI) and (VII):

wherein in formula (VI), R₀Represents a hydrogen atom or CH₃Group, R represents CH₂Radical, CH₂CH₂A group or a single bond, X represents a number from 0 to5, with the proviso that when R is a single bond, X represents a number from 1 to5, and R₁Is a hydrogen atom or C₁-C₂₀An organic group;

in the formula (VII), R₀Represents a hydrogen atom or CH₃Group, R represents CH₂Radical, CH₂CH₂A group or a single bond, X represents a number from 0 to5, and R₁Is a hydrogen atom or C₁-C₂₀An organic group;

(d) a polyester soil release polymer having a structure according to one of the following structures (III), (IV) or (V):

(III)-[(OCHR¹-CHR²)_a-O-OC-Ar-CO-]_d

(IV)-[(OCHR³-CHR⁴)_b-O-OC-sAr-CO-]_e

(V)-[(OCHR⁵-CHR⁶)_c-OR⁷]_f

wherein:

a. b and c are 1 to 200;

d. e and f are 1 to 50;

ar is 1, 4-substituted phenylene;

sAr is SO substituted in the 5-position₃1, 3-substituted phenylene substituted with Me;

me is Li, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, where the alkyl group is C₁-C₁₈Alkyl, or C₂-C₁₀Hydroxyalkyl, or any mixture thereof;

R¹、R²、R³、R⁴、R⁵and R⁶Independently selected from H or C₁-C₁₈N-alkyl or iso-alkyl; and is

R⁷Is straight-chain or branched C₁-C₁₈Alkyl, or straight or branched C₂-C₃₀Alkenyl or cycloalkyl having 5 to 9 carbon atoms, or C₈-C₃₀Aryl radicals, or C₆-C₃₀An aralkyl group; and

(e) any combination thereof.

15. The laundry detergent or cleaning composition of claim 1, wherein the laundry detergent or cleaning composition comprises a peroxyimine positive ion-based bleach catalyst having the formula (IX):

wherein: r¹Selected from the group consisting of H, branched alkyl groups comprising 3 to 24 carbons, and straight chain alkyl groups comprising 1 to 24 carbons; r²Independently selected from H, a branched alkyl group comprising 3 to 12 carbons, and a straight chain alkyl group comprising 1 to 12 carbons; and n is an integer of 0 to 1.

16. A laundry detergent or cleaning composition according to claim 1, wherein the laundry detergent or cleaning composition comprises c.i. fluorescent brightener 260 having the following structure (X):

wherein the c.i. fluorescent brightener 260:

predominantly in the alpha-crystalline form; or

Predominantly in the form of beta crystals and having a weight average primary particle size of from 3 to 30 microns.

17. A laundry detergent or cleaning composition according to claim 1, wherein the laundry detergent or cleaning composition comprises an enzyme selected from the group consisting of:

(a) a variant of thermomyces lanuginosus lipase having > 90% identity to a wild-type amino acid and comprising one or more substituents at T231 and/or N233;

(b) a cleaning cellulase belonging to glycosyl hydrolase family 45;

(i) a mutation at one or more of the following positions: 9. 26, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345; and

(ii) one or more substitutions and/or deletions in the following positions: 118. 183, 184, 195, 320, and 458; and

(d) any combination thereof.

18. A laundry detergent or cleaning composition according to claim 1, wherein the laundry detergent or cleaning composition is substantially free of zeolite builder, and wherein the composition is substantially free of phosphate builder.

19. A laundry detergent or cleaning composition according to claim 1, wherein the laundry detergent or cleaning composition further comprises an adjunct selected from the group comprising: enzymes, alkali builders, chelant builders, bleaching agents, bleach aids, perfumes, defoamers, bactericides, resists, and mixtures thereof.

20. A cleaning implement comprising a nonwoven substrate and a laundry detergent or cleaning composition according to claim 1.

21. A laundry detergent or cleaning composition comprising a carboxyl group-containing polymer comprising:

i. structural units (a) derived from an ether bond-containing monomer (A); wherein the structural unit (a) is represented by formula (1):

y represents a hydroxyl group or a group represented by formula (2) or (3); and one of X and Y is a hydroxyl group and the other is a group represented by formula (2) or (3),

structural units (B) derived from sulfonic acid group-containing monomer (B); and

structural units (C) derived from acrylic-based monomers (C);

wherein:

the structural unit (a) is present at a content of 0.5 to 15% by mass based on 100% by mass of all structural units derived from all monomers in the carboxyl group-containing polymer;

the structural unit (b) is present in a content of 5 to 23% by mass based on 100% by mass of all the structural units derived from all the monomers in the carboxyl group-containing polymer;

the structural unit (c) is present in a content of 55 to 99% by mass based on 100% by mass of all the structural units derived from all the monomers in the carboxyl group-containing polymer;

and the carboxyl group-containing polymer has a weight average molecular weight of 20,000 to 60,000,

the laundry detergent or cleaning composition further comprises an adduct of a bisulfite salt with the acrylic acid based monomer (C), wherein the adduct is present at a content of 0.01 mass% to 1.5 mass% based on 100 mass% of the solid content of the carboxyl group-containing polymer composition.

22. The laundry detergent or cleaning composition of claim 21, wherein the laundry detergent or cleaning composition is selected from the group consisting of a liquid laundry detergent composition, a solid laundry detergent composition, a hard surface cleaning composition, a liquid hand dishwashing composition, a solid automatic dishwashing composition, a liquid automatic dishwashing composition, and a tablet/unit dose type automatic dishwashing composition.

23. A laundry detergent or cleaning composition according to claim 21 wherein the carboxyl group-containing polymer comprises:

(1)1 to 9 mass% of the structural unit (a);

(2)5 to 23 mass% of the structural unit (b); and

(3)68 to 98 mass% of the structural unit (c).

24. The laundry detergent or cleaning composition of claim 21, wherein said carboxyl group-containing polymer has a weight average molecular weight of 30,000 to 50,000.

25. A laundry detergent or cleaning composition according to claim 21 wherein the carboxyl group-containing polymer is selected from:

26. a laundry detergent or cleaning composition according to claim 21 wherein the carboxyl group-containing polymer comprises:

i. a structural unit (a) represented by the formula (1) wherein R⁰Is a hydrogen atom; r¹Is CH₂A group; x is a hydroxyl group; and Y is formula (2); and in formula (2), n is 0;

and R is³Is C₁-C₄An alkyl group;

a structural unit (b) represented by formula (5):

wherein R is⁶Represents a hydrogen atom or a methyl group; r⁷Represents CH₂Radical, CH₂CH₂A group, or a direct bond; r⁸And R⁹Independently represents a hydroxyl group or-SO₃Z; z represents a hydrogen atom, a metal atomAn ammonium group or an organic amine group; and R is⁸And R⁹At least one of which is-SO₃Z; and

a structural unit (c) represented by formula (8):

wherein R is¹⁰Represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.

27. A laundry detergent or cleaning composition according to claim 26 wherein the structural unit (b) is selected from vinylsulphonic acid, styrenesulphonic acid, (meth) propenesulphonic acid, 3- (meth) allyloxy-2-hydroxypropanesulphonic acid, 3- (meth) allyloxy-1-hydroxypropanesulphonic acid, 2- (meth) allyloxyethenesulphonic acid, or 2-acrylamido-2-methylpropanesulphonic acid.

28. The laundry detergent or cleaning composition according to claim 21, wherein said carboxyl group-containing polymer has an anti-soil redeposition ratio of from 37.0% to 46.0% according to the anti-soil redeposition test described herein.

29. The laundry detergent or cleaning composition of claim 21, wherein said carboxyl group-containing polymer has a whiteness index measurement of 2.0 or greater according to the whiteness retention assay described herein.

30. The laundry detergent or cleaning composition of claim 21, wherein said carboxyl group-containing polymer has a Whiteness Maintenance Efficacy (WME) of at least 6%.

31. A laundry detergent or cleaning composition according to claim 28, 29 or 30 wherein the wash solution comprises said carboxyl group containing polymer at a concentration of less than 40 ppm.

32. A laundry detergent or cleaning composition according to claim 21, wherein the laundry detergent or cleaning composition comprises a detersive surfactant, wherein the detersive surfactant comprises:

(i) an alkyl alkoxylated sulphate anionic detersive surfactant having an average degree of alkoxylation of from 0.5 to 5; and/or

(ii) Principal ground C₁₂An alkyl sulphate anionic detersive surfactant; and/or

(iii) Less than 25% of a non-ionic detersive surfactant.

33. A laundry detergent or cleaning composition according to claim 21, wherein the laundry detergent or cleaning composition comprises a clay and soil removal/anti-redeposition agent selected from the group consisting of:

(a) a random graft copolymer comprising:

(i) a hydrophilic backbone comprising polyethylene glycol; and

(b) a cellulose polymer having a Degree of Substitution (DS) of from 0.01 to 0.99 and a Degree of Blockiness (DB) such that DS + DB is at least 1.00 or DB +2DS-DS²Is at least 1.20;

(i) from 50 to less than 98 weight percent structural units derived from one or more monomers comprising a carboxyl group;

(ii) from 1 to less than 49 weight percent structural units derived from one or more monomers comprising a sulfonate moiety; and

(iii)1 to 49 wt% structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (VI) and (VII):

(d) a polyester soil release polymer having a structure according to one of the following structures (III), (IV) or (V):

(III)-[(OCHR¹-CHR²)_a-O-OC-Ar-CO-]_d

(IV)-[(OCHR³-CHR⁴)_b-O-OC-sAr-CO-]_e

(V)-[(OCHR⁵-CHR⁶)_c-OR⁷]_f

wherein:

a. b and c are 1 to 200;

d. e and f are 1 to 50;

ar is 1, 4-substituted phenylene;

sAr is SO substituted in the 5-position₃1, 3-substituted phenylene substituted with Me;

R¹、R²、R³、R⁴、R⁵and R⁶Independently selected from H or C₁-C₁₈N-alkyl or iso-alkyl; and is

(e) any combination thereof.

34. The laundry detergent or cleaning composition of claim 21, wherein the laundry detergent or cleaning composition comprises a peroxyimine positive ion-based bleach catalyst having the formula (IX):

35. The laundry detergent or cleaning composition according to claim 21, wherein the laundry detergent or cleaning composition comprises c.i. fluorescent brightener 260 having the following structure (X):

wherein the c.i. fluorescent brightener 260:

predominantly in the alpha-crystalline form; or

Predominantly in the form of beta crystals and having a weight average primary particle size of from 3 to 30 microns.

36. A laundry detergent or cleaning composition according to claim 21, wherein the laundry detergent or cleaning composition comprises an enzyme selected from the group consisting of:

(a) a variant of thermomyces lanuginosus lipase having > 90% identity to a wild-type amino acid and comprising one or more substituents at T231 and/or N233;

(b) a cleaning cellulase belonging to glycosyl hydrolase family 45;

(i) a mutation at one or more of the following positions: 9. 26, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345; and

(ii) one or more substitutions and/or deletions in the following positions: 118. 183, 184, 195, 320, and 458; and

(d) any combination thereof.

37. The laundry detergent or cleaning composition of claim 21, wherein said laundry detergent or cleaning composition is substantially free of zeolite builder, and wherein said composition is substantially free of phosphate builder.

38. A laundry detergent or cleaning composition according to claim 21, wherein the laundry detergent or cleaning composition further comprises an adjunct selected from the group comprising: enzymes, alkali builders, chelant builders, bleaching agents, bleach aids, perfumes, defoamers, bactericides, resists, and mixtures thereof.

39. A cleaning implement comprising a nonwoven substrate and a laundry detergent or cleaning composition according to claim 21.

Technical Field

The present invention is in the field of laundry detergents or cleaning compositions. In particular, it relates to a particulate detergent product comprising a polymer containing carboxyl groups, the polymer comprising a specific ratio of structural units derived from; (i) ether bond-containing monomers, (ii) sulfonic acid group-containing monomers, and (iii) acrylic acid group monomers; and has a specific weight average molecular weight of about 20,000 to about 60,000; to improve and/or enhance cleaning performance, preferably whiteness maintenance and soil redeposition resistance. The invention also includes methods of making and using the laundry detergent and cleaning compositions.

Background

Improved soil and/or stain (e.g., organic stain) removal/reduction, whiteness maintenance, and/or clay suspension are desirable laundry detergent and cleaning composition properties. Generally, the wash water used in laundry detergents or cleaning compositions may contain naturally occurring impurities (e.g., calcium, iron, barium, bicarbonate, carbonate, oxide, oxalate, sulfate, phosphate, zinc, etc.) that chemically bind in the wash water to form insoluble precipitates. Additionally, the wash water may contain insoluble impurities (e.g., clay, silica, iron oxides, etc.) that precipitate out of the water during washing and onto the fabric articles and/or various cleaned material surfaces. These deposits and inert materials can accumulate on the fabric and material surfaces to form residues and/or deposits, thus adversely affecting its whiteness appearance, thereby affecting overall cleaning performance.

In addition, there is a need in the market today for laundry washing products and cleaning compositions with improved environmental sustainability (e.g. elimination of phosphate builders) and/or energy savings (e.g. formulation for reuse of wash water, such as in bathtubs) without adversely affecting cleaning performance (e.g. whiteness maintenance, stain removal, anti-soil redeposition, etc.). This, of course, presents additional challenges as the reclaimed wash water tends to have drawbacks such as increased soil components of the fabrics/materials in the reclaimed wash water, and increased water hardness due to, for example, repeated heating.

At high water hardness, anionic surfactants combine with the more readily available calcium and/or magnesium ions to reduce cleaning performance (i.e., reduce deposit inhibition and stain removal). Under high water hardness conditions, soil particle flocculation also tends to occur easily and causes the fabric/material to greying out due to soil redeposition. Specifically, the whiteness degradation will become more significant through a plurality of cycles of washing.

In addition, there are practical challenges to providing adequate cleaning performance for certain consumer wash behaviors such as dilute wash conditions due to insufficient amounts of laundry detergent or cleaning composition and/or excessive water volume usage. Both cost and load capacity limitations mean that increasing the amount of detergent ingredients or cleaning actives in a formulated laundry product or cleaning composition is not a viable option, but rather further improvements are needed to meet these needs.

Generally, acrylate polymers have been used as effective dispersants for suspending and removing particles. For example, Acusol 445^TM(Rohm and Haas) (a homopolymer of acrylic acid having a molecular weight of 4,500 g/mol) adsorbs via its acrylate functionality to the charged soil surface, removing the soil from the wash water, delivering a cleaning benefit. However, Acusol 445^TMIs not high enough to impart any significant steric stabilization to the main soil particles in the wash water to prevent the soil particles from aggregating.

One way of improving the acrylate functionality is by modification with nonionic monomers to ensure sufficient steric stability, while sulfonation is another way of imparting greater electrostatic stability after adsorption of the polymer onto the soil surface. PCT publications WO2010/024448 to Yoneda, a. et al and WO2010/04468 to Dupont, j.s. et al describe carboxyl group-containing polymers as hydrophobic group-containing copolymers comprising, in a molar ratio: (i) ether bond-containing monomers, (ii) carboxyl group-containing monomers, and (iii) sulfonic acid group-containing monomers; and has an average molecular weight range of 2,000-200,000 to reduce/prevent precipitation of the surfactant. However, none of the patent applications disclose any preferred molecular weight range for polymers useful for improving soil and stain removal, whiteness maintenance, and/or clay suspension, preferably when formulated in products for use in dilute and high water hardness wash conditions.

Thus, not all conventional carboxyl group-containing polymers and compositions comprising these polymers meet the current need, i.e. high enough performance in aqueous environments. Thus, further improvements are needed to provide laundry detergents and cleaning compositions comprising polymers that are suitable to meet the challenges of environmental sustainability and/or energy efficiency.

Therefore, there is a need for laundry detergents or cleaning compositions that have superior cleaning performance to those already present. In particular, laundry detergents or cleaning compositions with improved anti-soil redeposition and/or whiteness maintenance are sufficient to prevent soil particles and/or aggregates from re-adhering to the surface of the fabrics/materials being washed, preferably hard water wash conditions and/or undergoing multiple cycles of washing.

There is also a need for laundry detergents or cleaning compositions having improved soil or stain removal benefits, preferably effective on organic stains.

It is also desirable that laundry detergents or cleaning compositions have adequate cleaning performance within the consumer's washing habits, such as dilute wash conditions and/or the use of recyclable wash water.

Disclosure of Invention

In a first aspect, the present invention relates to laundry detergent or cleaning compositions comprising carboxyl group containing polymers which exhibit improved anti-soil redeposition ability when formulated in products, preferably laundry detergent products for fabric washing. The present inventors have identified carboxyl group-containing polymers comprising a specific ratio of structural units derived from: (i) an ether bond-containing monomer (A), (ii) a structural unit derived from a sulfonic acid group-containing monomer (B), and a structural unit derived from an acrylic acid group-containing monomer (C); and has a specific weight average molecular weight of about 20,000 to about 60,000; such that when formulated in the laundry detergent or cleaning composition, its cleaning performance, such as whiteness maintenance, soil and stain removal, and clay suspension, is improved.

In one embodiment, the laundry detergent or cleaning composition further comprises an adduct of bisulfite and acrylic-based monomer (C), which is useful as a modifier to adjust the molecular weight of the polymer to a desired degree to improve cleaning performance.

In another aspect, a method of efficiently preparing a laundry detergent or cleaning composition comprising a carboxyl group-containing polymer is disclosed.

These and other features of the present invention will become apparent to those skilled in the art upon review of the following detailed description when taken in conjunction with the appended claims.

Drawings

While the specification concludes with claims particularly pointing out and distinctly claiming the present invention, it is believed that the present invention will be better understood from the following description taken in conjunction with the accompanying drawings, in which:

figure 1 shows the effect of weight average molecular weight from example 4 on whiteness retention.

Detailed Description

As used herein, the articles "a" and "an" when used in a claim are understood to mean one or more and one or more as claimed or described.

As used herein, the term "cleaning composition" refers to a liquid or solid composition, and includes, inter alia: a hard surface cleaning composition; hand dishwashing detergents or light duty dishwashing detergents, especially those of the high sudsing type; machine dishwashing detergent; a personal care composition; a pet care composition; an automotive care composition; and a home care composition. In one embodiment, the cleaning composition of the present invention is a hard surface cleaning composition, preferably wherein the hard surface cleaning composition impregnates a nonwoven substrate.

As used herein, the term "laundry detergent" refers to liquid or solid compositions and, unless otherwise indicated, includes multipurpose or "heavy duty" detergents, especially cleaning detergents, in granular or powder form as well as cleaning adjuncts such as bleach additives or pretreatment types. In one embodiment, the laundry detergent is a solid laundry detergent composition, and preferably a free-flowing particulate laundry detergent composition (i.e. a particulate detergent product).

As used herein, the term "water hardness" or "hardness resistance" relates to uncomplexed calcium (i.e., Ca) from water and/or soil on soiled fabrics/materials²⁺) (ii) a More generally and more typically, "water hardness" also includes other uncomplexed cations (e.g., Mg) that have the potential to precipitate under alkaline conditions and tend to diminish the surfactant's surface activity and cleaning performance²⁺). Additionally, the terms "high water hardness" or "elevated water hardness" are used interchangeably and for purposes of the present invention are relative terms and are intended to mean at least "12 grams of calcium ions per gallon of water (gpg, 'american grain hardness' units)".

As used herein, the term "average molecular weight" refers to the average molecular weight of the polymer chains in the polymer composition. Further, "weight average molecular weight" ("M)_w") can be calculated using the formula:

M_w＝(Σ_iN_iM_i ²)/(Σ_iN_iM_i ²)

wherein N is_iTo have a molecular weight M_iThe number of molecules of (c). The weight average molecular weight must be measured by the method described in the test methods section.

As used herein, the term "whiteness maintenance" refers to the ability of a carboxyl group-containing polymer or a laundry detergent or cleaning composition comprising the polymer of the present invention to prevent or reduce the loss of whiteness of a clean fabric/material surface associated with laundering.

As used herein, the term "anti-soil redeposition" refers to the ability of the polymer to prevent soil components from reattaching to the fibers or material in a washing process using water. The anti-soil redeposition ability preferably needs to be better than existing polyacrylate polymers with lower molecular weight ranges in the context of high hardness water conditions to obtain improved cleaning performance, e.g. enhanced whiteness maintenance, which has to be determined by the method described in the test methods section.

As used herein, the term "organic stain" refers to stains derived from clay, proteinaceous soils and oxidizable soils, preferably in the presence of transition metal impurities.

It should be understood that when the invention is described herein and claimed, the test methods disclosed in the test methods section of this patent application must be used to determine the values of the various parameters of the invention.

In particular, the present invention provides a laundry detergent or cleaning composition comprising a carboxyl group-containing polymer comprising: a structural unit (a) derived from an ether bond-containing monomer (A) represented by formula (1) shown below; structural units (B) derived from a sulfonic acid group-containing monomer (B); and a structural unit (C) derived from an acrylic acid based monomer (C). The structural unit (a) is present at a content of about 0.5% by mass to about 10% by mass based on 100% by mass of all structural units derived from all monomers in the carboxyl group-containing polymer; the structural unit (b) is present at a content of about 0.5% by mass to about 30% by mass based on 100% by mass of all structural units derived from all monomers in the carboxyl group-containing polymer; and the structural unit (c) is present in an amount of about 55 to about 99 mass% based on 100 mass% of all structural units derived from all monomers in the carboxyl group-containing polymer. The carboxyl group-containing polymer has a weight average molecular weight of about 20,000 to about 60,000.

y represents a hydroxyl group or a group represented by formula (2) or (3); and one of X and Y is a hydroxyl group, and the other is a group represented by formula (2) or (3).

The present invention also provides a laundry detergent or cleaning composition comprising the carboxyl group-containing polymer composition as described above and an adduct of bisulfite and acrylic acid based monomer (C). The adduct is present in an amount of about 0.01% to about 1.5% by mass based on 100% by mass of the solids content of the carboxyl group-containing polymer composition.

Polymers containing carboxyl groups

The carboxyl group-containing polymer (hereinafter may also be referred to as "polymer") contains the structural unit (a) in an amount of about 0.5 to about 15 mass%, the structural unit (b) in an amount of about 0.5 to about 30 mass%, and the structural unit (c) in an amount of about 55 to about 99 mass%, based on 100 mass% of all the structural units (hereinafter also referred to as "all the structural units") derived from all the monomers in the carboxyl group-containing polymer. The structural unit (a) is derived from an ether bond-containing monomer (a), the structural unit (B) is derived from a sulfonic acid group-containing monomer (B), and the structural unit (C) is derived from an acrylic acid-based monomer (C). The weight average molecular weight of the carboxyl group-containing polymer is 20,000 to 60,000.

Ether bond-containing monomer (A)

The carboxyl group-containing polymer of the present invention is a polymer (hereinafter also referred to as "monomer (a)") substantially comprising a structural unit (a) derived from an ether bond-containing monomer (a).

The structural unit (a) derived from the ether bond-containing monomer (a) is represented by formula (1), and corresponds to a structural unit derived from an ether bond-containing monomer (a) represented by formula (4) described later, in which a carbon-carbon double bond is converted into a single bond.

In the formula (1), R⁰Represents a hydrogen atom or a methyl group; r¹Represents CH₂Radical, CH₂CH₂A group, or a direct bond; x represents a hydroxyl group or a group represented by formula (2) or (3); y represents a hydroxyl group or a group represented by formula (2) or (3); and one of X and Y is a hydroxyl group, and the other is a group represented by formula (2) or (3).

In the formulae (2) and (3), R, which may be the same or different, are²Represents C₂-C₄An alkylene group; n represents an oxyalkylene group (-O-R)²-) and is 0 to 5; and R is³、R⁴And R⁵Independently represent C₁-C₄An alkyl group.

The structural unit (a) has an adsorptive force for dirt attached to fibers and the like due to the presence of the hydrophobic group represented by formula (2) or (3). In addition, the carboxyl group-containing polymer has an adsorptive power to hydrophobic soils due to the presence of the structural unit (a), and exhibits a significant anti-soil redeposition ability to hydrophobic soils.

Examples of the ether bond-containing monomer (a) include monomers represented by formula (4).

In the formula (4), R⁰、R¹X and Y are as defined above for formula (1). When R in the formula (4)¹H in formula (4) when represents a direct bond₂C＝C(R⁰)-R¹-O-is H₂C＝C(R⁰) -O-. The same applies to formula (1).

When R is⁰And R¹Are each a methyl group and CH₂When radical, H₂C＝C(R⁰)-R¹-is a methallyl group. When R is⁰And R¹Are each a methyl group and CH₂CH₂When radical, H₂C＝C(R⁰)-R¹Is an isopentenyl group. When R is⁰And R¹When each is a methyl group and a direct bond, H₂C＝C(R⁰)-R¹-is an isopropenyl group. When R is⁰And R¹Are each a hydrogen atom and CH₂When radical, H₂C＝C(R⁰)-R¹-is an allyl group. When R is⁰And R¹Are each a hydrogen atom and CH₂CH₂When radical, H₂C＝C(R⁰)-R¹-is a butenyl group. When R is⁰And R¹When each is a hydrogen atom and a direct bond, H₂C＝C(R⁰)-R¹-is a vinyl group.

H₂C＝C(R⁰)-R¹Preferably an isopentenyl group, a methallyl group, an allyl group, or a vinyl group. In terms of improving polymerizability, H₂C＝C(R⁰)-R¹More preferably an isopentenyl group, a methallyl group, or an allyl group, and still more preferably an isopentenyl group or a methallyl group.

X and Y in the formulae (1) and (4) independently represent a hydroxyl group or a group represented by the formula (2) or (3). One of X and Y is a hydroxyl group, and the other is a group represented by formula (2) or (3).

R in the formulae (2) and (3)²May be the same or different and represents a C2-C4 alkylene group. C₂-C₄Examples of alkylene groups include ethylene, propylene, and the like,Propylene, and butylene groups. From the viewpoint of improving polymerizability of the ether bond-containing monomer (A), C is preferable₂-C₃Alkylene groups such as ethylene and propylene groups. One or more of the alkylene groups may be included.

The number n in the formulae (2) and (3) represents an oxyalkylene group (-O-R)²-) and is from 0 to 5. In terms of detergency and/or cleaning performance against slime soils, n is preferably from 0 to 4, more preferably from 0 to 3, still more preferably from 0 to 2, especially preferably 0 or 1, and most preferably 0.

R in the formulae (2) and (3)³、R⁴And R⁵Independently represent C₁-C₄An alkyl group. C₁-C₄Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups. These C₁-C₄The alkyl group may have one or more substituents. Examples of substituents include amino and hydroxyl groups. In particular, from the viewpoint of improving the anti-soil redeposition ability and whiteness maintenance of the polymer, methyl, ethyl, and butyl groups are preferable, and butyl groups are more preferable.

R in the formula (3)⁴And R⁵May be connected to each other to form a ring. In this case, the nitrogen atom and R are bonded to stabilize the ring structure⁴And R⁵The ring structure formed is preferably a3 to 7 membered ring, i.e. R⁴And R⁵The total number of carbon atoms of (a) is preferably 2 to 6.

Examples of the combination of X and Y (written in this order) include a hydroxyl group and a group represented by formula (2); a hydroxyl group and a group represented by formula (3); a group represented by formula (2) and a hydroxyl group; and a group represented by formula (3) and a hydroxyl group. In terms of improving the anti-soil redeposition ability of the polymer, X and Y are preferably a hydroxyl group and a group represented by formula (2), or a hydroxyl group and a group represented by formula (3), respectively, and more preferably a hydroxyl group and a group represented by formula (2), respectively.

As used herein, the phrase "carboxyl group-containing polymer comprising structural units (a) derived from ether bond-containing monomer (a)" means that the resulting polymer comprises structural units represented by formula (1). Specifically, the "structural unit (a) derived from the ether bond-containing monomer (a)" herein is intended to include a structural unit introduced in a step before the polymerization reaction and a structural unit introduced in a step after the polymerization reaction, and relates to a structural unit introduced in a polymer, for example, by synthesizing the ether bond-containing monomer (a) and then copolymerizing the ether bond-containing monomer (a) with another monomer, or a structural unit completed by copolymerizing to form a polymer main chain containing a carboxyl group and then introducing a side chain having a specific structure thereto.

The carboxyl group-containing polymer of the present invention may contain only one structural unit (a) or may contain two or more structural units (a).

The content of the structural unit (a) is about 0.5 to about 10% by mass based on 100% by mass of all the structural units derived from all the monomers in the carboxyl group-containing polymer, that is, the total amount of the structural unit (a) and the structural units (b), (c), and (e) described above. The polymer of the present invention containing the structural unit (a) in an amount within this range can successfully interact with soil components when used as a detergent builder or the like. Thus, the polymers can disperse soil particles by interaction and exhibit improved soil redeposition resistance and whiteness maintenance, preferably for multi-cycle washing. In addition, the polymers may have improved surfactant compatibility.

The content of the structural unit (a) is preferably from about 1% to about 9% by mass, more preferably from about 2% to about 8% by mass, and still more preferably from about 3% to about 7% by mass.

The method for preparing the ether bond-containing monomer (a) is not particularly limited, and can be prepared using any suitable method. Description of the epoxy ring of a Compound having a carbon-carbon double bond and an epoxy Ring with C₁-C₄A preparation method in which a hydroxyl group and/or an amino group of a compound of an alkyl group and a hydroxyl group and/or an amino group are reacted is exemplified as a simple preparation method. Examples of the compound having a carbon-carbon double bond and an epoxy ring include (meth) allyl glycidyl ether and glycidyl vinyl ether. Having a structure of C₁-C₄Alkyl radicalExamples of compounds having groups and hydroxyl groups and/or amino groups include methanol, ethanol, isopropanol, n-butanol, di-n-isopropylamine, and di-n-butylamine. The reaction may be carried out in the absence of a catalyst, or may be carried out in the presence of an acidic catalyst such as boron trifluoride or a basic catalyst such as sodium hydroxide or potassium hydroxide.

Monomer (B) containing sulfonic acid group

The carboxyl group-containing polymer of the present invention is a polymer further substantially comprising a structural unit (B) derived from a sulfonic acid group-containing monomer (B) (hereinafter also referred to as "monomer (B)").

Examples of the sulfonic acid group-containing monomer (B) include compounds having a carbon-carbon double bond and a sulfonic acid (salt) group. Specific examples thereof include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 3- (meth) allyloxy-2-hydroxypropanesulfonic acid, 3- (meth) allyloxy-1-hydroxypropanesulfonic acid, 2- (meth) allyloxyethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts of these. In order to more favorably ensure the sufficient effect of the present invention, 3- (meth) allyloxy-2-hydroxypropanesulfonic acid and salts thereof are preferable, and 3-allyloxy-2-hydroxypropanesulfonic acid and sodium salts thereof are more preferable.

Examples of the structural unit (B) include a structure derived from the monomer (B) in which a carbon-carbon double bond is converted into a single bond (if two or more double bonds are present, at least one carbon-carbon double bond is converted into a single bond). Preferred examples of the monomer (B) include those represented by the following formula (5), and preferred examples of the structural unit (B) include those represented by the following formula (6).

In the formula, R⁶Represents a hydrogen atom or a methyl group; r⁷Represents CH₂Radical, CH₂CH₂A group, or a direct bond; r⁸And R⁹Independently represents a hydroxyl group or-SO₃Z; z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group; and R is⁸And R⁹At least one of which is-SO₃Z。

In the formula, R⁶、R⁷、R⁸And R⁹As defined above. Due to the presence of structural unit (b), the carboxyl group-containing polymer can act as a high performance dispersant for stubborn soils, and exhibits enhanced anti-soil redeposition ability on hydrophobic soils, and has improved whiteness maintenance.

R in the formulae (3) and (4)⁶Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

R⁷Represents CH₂Radical, CH₂CH₂A radical, or a direct bond, and is preferably CH₂A group.

R⁸And R⁹Independently represents a hydroxyl group or-SO₃Z, and R⁸And R⁹At least one of which is-SO₃And Z. In a preferred embodiment, R⁴And R⁵Only one of them is-SO₃Z。

Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.

In case Z is a metal atom, an ammonium group or an organic amine group, -SO₃Z is a metal salt, ammonium salt, or organic amine salt of a sulfonic acid.

Examples of the metal atom and the organic amine for Z include R as described below¹⁰The same metal atoms and organic amines listed in (a). Z is preferably a hydrogen atom, an alkali metal atom, or an ammonium group, more preferably a hydrogen atom, sodium, or potassium, and still more preferably a hydrogen atom or sodium.

As used herein, the phrase "carboxyl group-containing polymer comprising structural unit (B) derived from sulfonic acid group-containing monomer (B)" means that the resulting polymer comprises structural unit represented by formula (6). Specifically, the "structural unit (B) derived from the sulfonic acid group-containing monomer (B)" herein is intended to include a structural unit introduced in a step before the polymerization reaction and a structural unit introduced in a step after the polymerization reaction, and relates to a structural unit introduced in a polymer, for example, by synthesizing the sulfonic acid group-containing monomer (B) and then copolymerizing the sulfonic acid group-containing monomer (B) with another monomer, or a structural unit completed by copolymerizing to form a polymer main chain containing a carboxyl group and then introducing a side chain having a specific structure thereto.

The carboxyl group-containing polymer of the present invention may contain only one structural unit (b), or two or more structural units (b).

The content of the structural unit (b) is about 0.5 to about 25% by mass based on 100% by mass of all the structural units derived from all the monomers in the carboxyl group-containing polymer, that is, the total amount of the structural units (a) and (b) and the structural units (c) and (e) as described above. The polymer of the present invention containing the structural unit (b) in an amount within this range can successfully interact with soil components when used as a detergent builder or the like. Thus, the polymers can disperse soil particles by interaction and exhibit enhanced anti-soil redeposition ability and whiteness maintenance, preferably for multi-cycle washing.

The content of the structural unit (b) is preferably from about 1% to about 23% by mass, more preferably from about 3% to about 22% by mass, and still more preferably from about 5% to about 21% by mass.

In the present invention, when the mass ratio (% by mass) of the structural unit (b) to all structural units derived from all monomers in the carboxyl group-containing polymer is calculated, the structural unit (b) is treated as its corresponding acid. For the structural unit derived from sodium 3-allyloxy-2-hydroxypropanesulfonate, the mass ratio (% by mass) of the structural unit derived from the corresponding acid (3-allyloxy-2-hydroxypropanesulfonic acid) was calculated. Also, when the mass ratio (% by mass) of the sulfonic acid group-containing monomer (B) to all monomers is calculated, the sulfonic acid group-containing monomer (B) is treated as its corresponding acid. For example, to determine the mass ratio of sodium 3-allyloxy-2-hydroxypropanesulfonate, the corresponding mass ratio (% by mass) of (3-allyloxy-2-hydroxypropanesulfonic acid) was calculated.

The method for preparing the sulfonic acid group-containing monomer (B) is not particularly limited, and can be prepared using any suitable method. For example, a method of adding a bisulfite to a glycidyl group of (meth) allyl glycidyl ether is described as an example of a simple preparation method.

Acrylic acid based monomer (C)

The carboxyl group-containing polymer herein is a polymer further substantially comprising a structural unit (C) derived from an acrylic acid-based monomer (C) (hereinafter also simply referred to as "monomer (C)").

Examples of the acrylic acid based monomer (C) herein include monomers represented by formula (7):

wherein R is¹⁰Represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.

Examples of the structural unit (C) derived from the acrylic-based monomer (C) include a structure derived from the monomer (C) in which a carbon-carbon double bond is converted into a single bond. Specific examples thereof are those represented by formula (8):

wherein R is¹⁰As defined above. Due to the presence of the structural unit (c), the carboxyl group-containing polymer can act as a high performance dispersant and exhibit enhanced anti-soil redeposition ability on hydrophobic soils, and whiteness maintenance, preferably for multi-cycle washing.

When R in the formulae (7) and (8)¹⁰In the case of a metal atom, an ammonium group, or an organic amine group, the acrylic acid based monomer (C) is a metal salt, an ammonium salt, or an organic amine salt of acrylic acid.

For R in formulae (7) and (8)¹⁰Examples of the metal atom of (a) include alkali metal atoms such as lithium, sodium and potassium; and alkaline earth metal atoms such as magnesium and calcium; and aluminum and iron.

For R¹⁰Of (2) aExamples of the amine include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as monoethylamine, diethylamine and triethylamine; and polyamines such as ethylenediamine and triethylenediamine.

R¹⁰Hydrogen atoms, alkali metal, or ammonium groups are preferred because of their greater efficacy in improving the polymer's resistance to soil redeposition. R¹⁰More preferably a hydrogen atom, sodium, potassium, or ammonium group, and still more preferably a hydrogen atom or sodium.

Specific examples of the acrylic-based monomer (C) include acrylic acid and salts thereof. The acrylic acid-based monomer (C) is preferably acrylic acid or a sodium salt thereof.

The phrase "carboxyl group-containing polymer comprising structural unit (C) derived from acrylic acid based monomer (C)" means that the resulting polymer comprises structural unit represented by formula (8). Specifically, the "structural unit (C) derived from an acrylic acid-based monomer (C)" herein is intended to include a structural unit introduced in a step before polymerization and a structural unit introduced in a step after polymerization, and relates to a structural unit introduced in a polymer, for example, by synthesizing an acrylic acid-based monomer (C) and then copolymerizing the acrylic acid-based monomer (C) with another monomer, or a structural unit completed by copolymerizing to form a polymer main chain containing a carboxyl group and then introducing a side chain having a specific structure thereto.

The carboxyl group-containing polymer of the present invention may contain only one structural unit (c) or may contain two or more structural units (c).

The structural unit (c) is contained in an amount of about 55 to about 99 mass% based on 100 mass% of all structural units derived from all monomers in the carboxyl group-containing polymer, that is, the total amount of the structural units (a), (b), and (c) and the structural unit (e) as described above. The polymer of the present invention containing the structural unit (c) in an amount within this range can successfully interact with soil components when used as a detergent builder or the like. Thus, the polymers can disperse soil particles by interaction and exhibit improved soil redeposition resistance and whiteness maintenance, preferably for multi-cycle washing.

The content of the structural unit (c) is preferably about 68% by mass to about 98% by mass, more preferably about 70% by mass to about 95% by mass, and still more preferably about 72% by mass to about 92% by mass.

In the present invention, when the mass ratio (% by mass) of the structural unit (c) to all structural units derived from all monomers in the carboxyl group-containing polymer is calculated, the structural unit (c) is treated as its corresponding acid. Is derived from the structural unit-CH of sodium acrylate₂-CH (COONa) -calculating the mass ratio (% by mass) of the structural unit derived from the corresponding acid (acrylic acid), i.e., the structural unit-CH₂Mass ratio (mass%) of-CH (COOH) -. Also, when the mass ratio (% by mass) of the acrylic acid based monomer (C) to all the monomers is calculated, the acrylic acid based monomer (C) is treated as a corresponding acid. For example, to determine the mass ratio of sodium acrylate, the mass ratio (% by mass) of the corresponding acid (acrylic acid) is calculated instead.

The method for preparing the acrylic acid based monomer (C) is not particularly limited.

Other monomers

The carboxyl group-containing polymer of the present invention may comprise one or more structural units (E) derived from one or more other monomers (E) (one or more monomers other than the ether bond-containing monomer (a), the sulfonic acid group-containing monomer (B) and the acrylic acid group-containing monomer (C)). The carboxyl group-containing polymer may contain only one structural unit (e), or two or more structural units (e).

The other monomer(s) (hereinafter also referred to as monomer(s) (E)) is not particularly limited, provided that they are copolymerizable with the monomers (a), (B) and (C). Suitable further monomers can be selected by taking into account the desired effect.

Specific examples of the other monomer (E) include carboxyl group-containing monomers other than the monomer (C), such as methacrylic acid, maleic acid, crotonic acid, itaconic acid, 2-methyleneglutaric acid, and salts of these; monomers containing a polyalkylene glycol chain such as monomers obtained by adding an alkylene oxide to an unsaturated alcohol (e.g., (meth) allyl alcohol, isoprenol) and (meth) acrylates of alkoxyalkylene glycols; based on vinyl groupsMonomers having a heterocyclic aromatic hydrocarbon group of aromatic compounds such as vinylpyridine and vinylimidazole; amino group-containing monomers such as dialkylaminoalkyl (meth) acrylates (e.g., dimethylaminopropyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate), dialkylaminoalkyl (meth) acrylamides (e.g., dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide), allylamines (including diallylamine and diallylalkylamines) (e.g., diallyldimethylamine), and quaternized compounds of these; n-vinyl monomers, e.g. N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide and N-vinylAn oxazolidinone; amide group monomers such as (meth) acrylamide, N-dimethylacrylamide, and N-isopropylacrylamide; monomers containing a hydroxyl group such as (meth) allyl alcohol and prenyl alcohol; alkyl (meth) acrylate-based monomers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and dodecyl (meth) acrylate; hydroxyalkyl (meth) acrylate-based monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-hydroxyhexyl (meth) acrylate; vinyl aryl monomers such as styrene, indene and vinyl aniline; and isobutylene and vinyl acetate.

Quaternized compounds can be obtained by reaction between amino group-containing monomers and customary quaternizing agents. Examples of quaternizing agents include alkyl halides and dialkyl sulfates.

The structural unit (E) derived from the other monomer (E) means a structural unit derived from the monomer (E) in which each carbon-carbon double bond is converted into a single bond (if two or more double bonds are present, at least one carbon-carbon double bond is converted into a single bond).

As used herein, the phrase "carboxyl group-containing polymer comprising one or more structural units (E) derived from one or more other monomers (E)" means that the resulting polymer comprises one or more structural units in which the unsaturated double bond in one or more monomers (E) is converted to a single bond.

The content of the structural unit(s) (E) derived from the other monomer(s) (E) as an optional component is preferably from about 0 to about 34% by mass based on 100% by mass of all the structural units derived from all the monomers in the carboxyl group-containing polymer, i.e., the total amount of the structural units (a), (b), (c) and (E). The content is more preferably about 0 to 10 mass%, still more preferably about 0 to about 5 mass%, and particularly preferably 0 mass%.

With respect to the structural unit (e) being a structural unit derived from an amino group-containing monomer, the mass ratio of this structural unit to all structural units derived from all monomers, and the mass ratio of the amino group-containing monomer to all monomers are calculated by treating the structural unit and the monomer as corresponding unneutralized amines. For example, in the case where the other monomer (E) is vinylamine hydrochloride, the mass ratio (% by mass) of its corresponding unneutralized amine is calculated instead, i.e., the mass ratio of vinylamine.

The mass of the counter anions is not calculated and the mass ratio (% by mass) of the monomer containing the quaternized amino group to the structural units derived from these is calculated.

In the case where the structural unit (e) is a structural unit derived from a monomer containing an acidic group, the mass ratio (% by mass) of the structural unit to all structural units derived from all monomers is calculated by treating the structural unit as its corresponding acid. The mass ratio (% by mass) of the monomer containing an acidic group to all monomers was calculated by treating the monomers as their corresponding acids as well.

Physical Properties of carboxyl group-containing Polymer

The laundry detergent or cleaning compositions of the present invention comprise a carboxyl group-containing polymer, wherein the polymer comprises the structural units (a), (b) and (c) in the amounts specified above, and optionally comprises one or more structural units (e) in the amounts specified above. These structural units may be arranged in a block or random manner.

Molecular weight is one of the most important factors in regulating polymer identification and adsorption behavior on specific fouling surfaces. Generally, increasing the molecular weight, especially above 60,000, will tend to increase the polymer/soil complex and/or polymer/Ca²⁺Deposition of deposits on the fabric/material surface, causing residue problems. Since the number average-weight average molecular weight is too high, the carboxyl group-containing polymer will have a high viscosity and will therefore be difficult to handle. Conversely, a number average-weight average molecular weight that is too low may not provide anti-soil redeposition capability, particularly for high hardness aqueous cleaning conditions.

In this context, the inventors have unexpectedly recognized that increasing the molecular weight of a carboxyl group-containing polymer within certain ranges does not adversely affect the residue deposition characteristics of the polymer. In addition, the present inventors have found that the molecular weight of the carboxyl group containing polymer is increased compared to a similar polyacrylate polymer having a lower molecular weight range, resulting in improved soil dispersability and delivering enhanced whiteness maintenance when formulated in laundry detergents or cleaning compositions.

Without being bound by theory, it is expected that highly water-soluble low molecular weight carboxyl group containing polymers have low interaction energy and poor adsorption at the soil-polymer surface interface compared to highly water-soluble high molecular weight carboxyl group containing polymers. In addition, high molecular weight carboxyl group-containing polymers that effectively adsorb and immobilize on the soil surface electrostatically and sterically stabilize soil/detergent residues. Redeposition on clean fabrics is prevented when the soil is stabilized in the wash solution.

Although the carboxyl group-containing polymer has a weight average molecular weight range of about 20,000 to about 60,000, the molecular weight in this range is not particularly limited, and an appropriate molecular weight may be appropriately determined in consideration of the desired cleaning performance of the laundry detergent or cleaning composition of the present invention, such as having improved anti-soil redeposition properties, clay-suspending properties, whiteness maintenance properties and/or stain-removing effects.

If the weight average molecular weight is within this range, the soil redeposition resistance is improved and whiteness maintenance is enhanced when the polymer is formulated in a laundry detergent or cleaning composition. The weight average molecular weight is preferably from about 30,000 to about 50,000, more preferably from about 33,000 to about 42,000, even more preferably from about 35,000 to about 40,000, and most preferably from about 36,000 to about 39,000.

In addition, the present inventors have found that carboxyl group-containing polymers having too high a weight average molecular weight (i.e., > 60,000) tend to have too high a viscosity to be handled under many manufacturing conditions. However, the present inventors have found that laundry detergent or cleaning compositions comprising those carboxyl group containing polymers do not provide sufficient, preferably enhanced/improved, anti-soil redeposition and whiteness maintenance benefits due to having a weight average molecular weight that is too low (i.e. <19,000).

The weight average molecular weight of the carboxyl group-containing polymers herein is determined according to the methods and conditions described in the assays of the test methods section.

The carboxyl group-containing polymers and laundry detergent or cleaning compositions comprising the polymers of the present invention have improved anti-soil redeposition ability and preferably have an anti-soil redeposition rate of from about 37.0% to about 46.0%, preferably from about 37.5% to about 45.0%, and more preferably from about 37.5% to about 39.0%. Anti-soil redeposition rates can be measured by the methods described in the anti-soil redeposition ability test described herein.

In addition, the carboxyl group-containing polymers and laundry detergents or cleaning compositions comprising the polymers of the present invention have improved whiteness maintenance performance as measured by a whiteness index measurement of 2.0 or greater, preferably 3.0 or greater, more preferably 4.0 or greater, and even more preferably 5.0 or greater, as measured by whiteness maintenance as described herein.

Alternatively, the carboxyl group containing polymer and laundry detergent or cleaning compositions comprising the polymer of the present invention have a Whiteness Maintenance Efficacy (WME) of at least 6%, preferably at least 8% WME, more preferably at least 10% WME, even more preferably 12% WME, and most preferably at least 20% WME, wherein% WME is as defined herein.

Given enhanced anti-soil redeposition ability, carboxyl group-containing polymers and laundry detergents or cleaning compositions comprising the polymers of the present invention can deliver sufficient whiteness maintenance performance when used in a wash solution comprising the carboxyl group-containing polymers at a concentration of less than about 40ppm, preferably less than about 30ppm, more preferably less than about 20ppm, and even more preferably less than about 10 ppm.

Method for producing carboxyl group-containing polymers

The carboxyl group-containing polymer of the present invention can be produced by copolymerizing a monomer material essentially comprising ether bond-containing monomer (a) represented by formula (4), sulfonic acid group-containing monomer (B) represented by formula (5), and acrylic acid group-containing monomer (C) represented by formula (7) in specific amounts, and optionally comprising one or more other monomers (E) in specific amounts.

In the process for preparing the carboxyl group-containing polymer of the present invention, the amounts of the respective monomers used in the polymerization reaction are specifically as follows: the amount of the monomer (a) is about 0.5 to about 15 mass%, the amount of the monomer (B) is about 0.5 to 30 mass%, and the amount of the monomer (C) is about 55 to about 99 mass%, based on 100 mass% of all the monomers (a), (B), (C), and (E)).

Use of monomer (a) in an amount of less than about 0.5 mass% can result in reduced adsorption to hydrophobic soils, which can result in reduced anti-soil redeposition ability, whiteness maintenance (especially through multiple wash cycles), and detergency to hydrophobic soils. The use of the monomer (B) in an amount of less than about 0.5 mass% may result in poor anti-soil redeposition ability against hydrophilic soils, resulting in increased gray deposits on the washed surface. The use of the monomer (C) in an amount of less than about 55 mass% may result in a decrease in anti-soil redeposition ability and detergency to hydrophilic soils.

The amounts of the monomers (a), (B), and (C) are preferably about 1 to about 9 mass%, about 1 to about 23 mass%, and about 68 to about 98 mass%, respectively, more preferably about 2 to about 8 mass%, about 3 to about 22 mass%, and about 70 to about 95 mass%, respectively, and still more preferably about 3 to about 7 mass%, about 5 to about 21 mass%, and about 72 to about 92 mass%, respectively.

Further, the monomer(s) (E) may be used in an amount of about 0 to about 34% by mass based on 100% by mass of all the monomers (a), (B), (C), and (E)). The amount is more preferably from about 0% to about 10% by mass, still more preferably from about 0% to about 5% by mass, and particularly preferably 0% by mass.

The polymerization method for obtaining the carboxyl group-containing polymer of the present invention is not particularly limited, and a common polymerization method or a modification thereof may be used. Examples of polymerization methods include radical polymerization. Specific examples thereof include oil-in-water emulsion polymerization, water-in-oil emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, solution polymerization, aqueous solution polymerization, and bulk polymerization. Among these polymerization methods, solution polymerization is preferable because it is a highly safe method and provides production (polymerization) cost savings.

For solution polymerization, the monomers are polymerized in a solvent. The solvent may be a solvent composed of an organic solvent, but is preferably an aqueous solvent. The solvent preferably contains water in an amount of at least 50 mass% based on the total amount of the solvent (100 mass%), and the amount of water is more preferably at least 80 mass%. Specifically, 100 mass% of water is preferred. Examples of the organic solvent that can be used alone or in combination with water include aqueous organic solvents such as lower alcohols (e.g., ethanol, isopropanol), amides (e.g., N-dimethylformamide), ethers (e.g., diethyl ether, dioxane), ethylene glycol, glycerol, and polyethylene glycol.

Only one solvent may be used alone, or two or more solvents may be used in combination. The amount of the solvent is preferably 40 to 300 parts by mass, more preferably 45 to 200 parts by mass, and still more preferably 50 to 150 parts by mass per 100 parts by mass of all the monomers (a), (B), (C), and (E)). The use of the solvent in an amount of less than 40 parts by mass per 100 parts by mass of all the monomers may result in the formation of a polymer having a high molecular weight. The use of the solvent in an amount of more than 300 parts by mass per 100 parts by mass of all the monomers makes it possible to obtain the resulting polymer in a low concentration, so that a step of removing the solvent may be required in some cases.

In the initial stage of the polymerization, a part or all of the solvent is added to the reaction vessel, and the remaining part of the solvent may be added to the reaction system during the polymerization (e.g., dropwise). Alternatively, the monomer and a reagent such as a polymerization initiator may be dissolved in a solvent, and a solution containing these components may be added (e.g., dropwise) to the reaction system.

The reaction via solution polymerization is not particularly limited and may be carried out in a usual manner. The reaction is usually carried out by, for example, adding a solvent to the reaction system, and dropping a monomer and a polymerization initiator (hereinafter also referred to as "initiator"). In this case, the concentration of each solution to be dropped is not particularly limited and can be appropriately determined.

For example, in the case of dropping the monomer and the initiator into the solvent group within the reaction system, the monomer (a), the monomer (B), the monomer (C), the monomer(s) (E) if necessary, the initiator, and other additives if necessary may be dissolved in the solvent separately, or they may be used as they are without being dissolved in the solvent, and the polymerization reaction may be carried out by adding (dropping) the solution into the reaction system in an appropriate manner during the polymerization. In this case, a part or all of the monomer (A) may be added to the reaction system before the polymerization is started.

Polymerization initiator: in the preparation process, the usual polymerization initiators can be used. Specifically, suitable examples thereof include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; azo compounds such as 2,2' -azobis (2-amidinopropane) hydrochloride, 4' -azobis-4-cyanovaleric acid, azobisisobutyronitrile, and 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, and cumene hydroperoxide. Among these polymerization initiators, hydrogen peroxide, persulfates, and 2,2 '-azobis (2-amidinopropane) hydrochloride are preferable, and persulfates and 2,2' -azobis (2-amidinopropane) hydrochloride are still more preferable. These polymerization initiators may be used aloneEither one of them, or two or more of them may be used in combination.

Chain transfer agent: in the production method, a chain transfer agent is preferably used as a molecular weight controlling agent for the polymer. The use of a chain transfer agent advantageously prevents the molecular weight of the resulting polymer from increasing beyond a certain level, thereby resulting in more efficient production of a polymer having a carboxyl group-containing group of low molecular weight.

Bisulfite and/or compounds capable of forming bisulfite are preferably used as one or more chain transfer agents in the preparation process. In this case, it is preferable to use a polymerization initiator in addition to the bisulfite and/or the compound capable of generating bisulfite. In addition, heavy metal ions may be used in combination as a reaction accelerator as described below.

If bisulfite and/or a compound capable of generating bisulfite is used as one or more chain transfer agents, the resulting polymer is end-capped at one or both ends of its backbone with sulfonic acid (salt) groups.

Examples of the compound capable of generating a bisulfite include pyrosulfite, dithionite, and sulfite. Pyrosulfurous acid (salt) is particularly preferable.

The salts are preferably salts with metal atoms, ammonium and organic amines. Examples of the metal atom include monovalent alkali metal atoms such as lithium, sodium and potassium; divalent alkaline earth metal atoms such as calcium and magnesium; and trivalent metal atoms such as aluminum and iron.

Examples of the organic amine include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and triethylamine.

Among the bisulfite and the compound capable of generating bisulfite, the bisulfite is preferred.

Examples of the bisulfite include sodium bisulfite, potassium bisulfite, and ammonium bisulfite. Sodium bisulfite is particularly more preferred.

Specific examples of the bisulfite-generating compound include sodium metabisulfite and potassium metabisulfite; sodium dithionite and potassium dithionite; and sodium sulfite, potassium sulfite, and sodium ammonium sulfite. Sodium metabisulfite is especially more preferred.

Any of these bisulfite salts and compounds capable of generating bisulfite salts may be used alone, or two or more of these may be used in combination.

In addition to the bisulfite and/or the compound capable of generating bisulfite, any of the following compounds may be used as a chain transfer agent. Examples of such chain transfer agents include thiol group chain transfer agents such as mercaptoethanol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, and n-dodecanethiol; halides such as carbon tetrachloride, dichloromethane, bromoform, and trichlorobromoethane; secondary alcohols such as isopropanol and glycerol; and suboxides such as phosphorous acid, hypophosphorous acid, and salts of these (e.g., sodium hypophosphite, potassium hypophosphite). Any of these chain transfer agents may be used alone, or two or more of these may be used in combination.

Reaction accelerator: in the preparation method, a reaction accelerator may be added to reduce the amount of a reagent used in the reaction, such as a polymerization initiator. Examples of the reaction accelerator include heavy metal ions.

The term "heavy metal ion" as used herein is intended to include ions having a concentration of not less than 4g/cm³Specific gravity of metal ions. Preferred examples of the heavy metal for the heavy metal ion include iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, and ruthenium. Any of these heavy metals may be used alone, or two or more of these may be used in combination. Of these, iron is more preferable.

The ion valence of the heavy metal ion is not particularly limited. For example, when iron is used as the heavy metal, the reaction promoter may comprise Fe²⁺Form or Fe³⁺Form(s) of iron ion, or may comprise both forms of iron ion.

These heavy metal ions may be used in any form, provided that they are present in an ionic form. From the viewpoint of handleability, these heavy metal ions are preferably used in the form of a solution obtained by dissolving a heavy metal compound. The heavy metal compounds are any compounds, provided that they each contain the desired heavy metal to be captured in the polymerization initiator. The heavy metal may be suitably selected depending on the polymerization initiator used in combination.

When iron ions are used as the heavy metal ions, preferable examples of the heavy metal compounds include ferrous ammonium sulfate (Fe (NH)₄)₂(SO₄)₂·6H₂O), ferrous sulfate heptahydrate, ferrous chloride, and ferric chloride. When manganese is used as the heavy metal ion, manganese chloride and the like are suitable. All of these are water soluble compounds and are therefore used in aqueous solution and are easy to handle. The solvents used for preparing the heavy metal compound solution are not limited to water, provided that they dissolve the heavy metal compound and do not inhibit the polymerization reaction in the preparation of the carboxyl group-containing polymer of the present invention.

The heavy metal ions may be added in any manner. Preferably, all heavy metal ions are added after the monomer addition is complete. More preferably, all the heavy metal ions are added at once at the beginning of the reaction.

The amount of the heavy metal ion is preferably 0.1 to 10ppm, based on the total amount of the polymerization reaction solution at the time of completion of the polymerization reaction. If the amount of the heavy metal ion is less than 0.1ppm, the efficacy of the heavy metal ion may not be sufficiently provided. If the amount of the heavy metal ion is more than 10ppm, the color tone of the resulting polymer may be deteriorated. In addition, polymers made with excess heavy metal ions can cause colored soils when used as detergent builders.

The term "at the completion of the polymerization reaction" refers to the time at which the polymerization reaction in the polymerization reaction solution is substantially completed so as to provide the desired polymer. For example, in the case where the polymer produced in the polymerization reaction solution is neutralized with an acid component, the amount of the heavy metal ion is determined based on the total amount of the polymerization reaction solution after the neutralization. In the case of containing two or more heavy metal ions, the total amount of the heavy metal ions is within the above range.

In the preparation method, other compounds such as a catalyst for decomposing the polymerization initiator and reducing the compound may be added to the reaction system at the time of polymerization in addition to the above-mentioned compounds.

Examples of the catalyst for decomposing the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; metal salts of inorganic acids such as hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid and nitric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid and benzoic acid, and esters and metal salts thereof; and heterocyclic amines such as pyridine, indole, imidazole and carbazole, and derivatives thereof. Any of these decomposition catalysts may be used alone, or two or more of these may be used in combination.

Examples of the reducing compound include organometallic compounds such as ferrocene; inorganic compounds capable of generating metal ions (e.g., iron, copper, nickel, cobalt, manganese ions), such as iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, and manganese naphthenate; inorganic compounds such as boron trifluoride ether adducts, potassium permanganate and perchloric acid; sulfur-containing compounds such as sulfur dioxide, sulfates, thiosulfates, sulfites, benzene sulfinic acid and substituted compounds thereof, and analogs of cyclic sulfinic acids such as p-methyl benzene sulfinic acid; nitrogen-containing compounds such as hydrazine, β -hydroxyethylhydrazine and hydroxylamine; aldehydes such as formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, and isovaleraldehyde; and ascorbic acid. Any of these reducing compounds may be used alone, or two or more of these may be used in combination.

The combination of the chain transfer agent, the polymerization initiator and the reaction accelerator is not particularly limited, and each of them may be appropriately selected from the above examples. A polymerization initiator or a reaction accelerator may not be used. Preferable examples of the combination of the chain transfer agent, the polymerization initiator and the reaction accelerator (written in this order) include sodium hydrogen sulfite/hydrogen peroxide/none, sodium hydrogen sulfite/sodium persulfate/none, sodium hydrogen sulfite/no/Fe (ion), sodium hydrogen sulfite/hydrogen peroxide/Fe (ion), sodium hydrogen sulfite/sodium persulfate/Fe (ion), and sodium hydrogen sulfite/sodium persulfate and hydrogen peroxide/Fe (ion). More preferably sodium bisulfite/sodium persulfate/nil in combination with sodium bisulfite/sodium persulfate/Fe (ions), and still more preferably sodium bisulfite/sodium persulfate/Fe (ions). Here, "none" means that nothing is used as a corresponding agent.

Amounts of polymerization initiators and other reagents: the amount of the polymerization initiator is not particularly limited, provided that it is sufficient to initiate copolymerization of the monomers. The amount of the polymerization initiator per mole of all the monomers (A), (B), (C) and (E)) is preferably not more than 15g, and more preferably 1g to 12 g.

In the case of using hydrogen peroxide as a polymerization initiator, the amount of hydrogen peroxide is 1.0g to 10.0g, and more preferably 2.0g to 8.0g, per mole of all the monomers. If the amount of hydrogen peroxide is less than 1.0g, the resulting polymer tends to have a high weight average molecular weight. On the other hand, addition of more than 10.0g of hydrogen peroxide may not produce an effect in proportion to the amount added and cause disadvantages such as leaving a large amount of hydrogen peroxide unreacted.

When a persulfate is used as the polymerization initiator, the amount of the persulfate is preferably from 1.0g to 5.0g, and more preferably from 2.0g to 4.0g, per mole of all the monomers. If the amount of the persulfate is less than 1.0g, the resulting polymer tends to have a high molecular weight. On the other hand, the addition of more than 5.0g of the persulfate may not produce an effect in proportion to the amount added, and causes disadvantages such as low purity of the resulting polymer.

In the case of using hydrogen peroxide and a persulfate in combination as a polymerization initiator, the mass ratio of the persulfate to the hydrogen peroxide is preferably 0.1 to 5.0, and more preferably 0.2 to 2.0. If the persulfate mass ratio is less than 0.1g, the resulting copolymer tends to have a high molecular weight. On the other hand, the addition of a persulfate having a mass ratio of more than 5.0 may not produce a lowering effect of the molecular weight in proportion to the amount added, so that the persulfate in the polymerization reaction system may be wasted.

As for the addition of hydrogen peroxide, it is preferable to almost continuously drop hydrogen peroxide in an amount of not less than 85 mass% of the predetermined required amount. The amount is more preferably not less than 90% by mass, and still more preferably 100% by mass (i.e., all hydrogen peroxide is preferably added dropwise). In the case of continuous dropping of hydrogen peroxide, the dropping rate may be changed.

When the reaction is carried out under suitable reaction conditions (e.g., temperature, pressure, pH) described below, it is preferable to start dropping hydrogen peroxide after starting dropping the monomer (not the monomer added at the start of the reaction) for a while. Specifically, it is preferable that the dropping of hydrogen peroxide is started not less than one minute after the start of the dropping of the monomer (C), more preferably not less than three minutes after the start, still more preferably not less than five minutes after the start, and particularly preferably not less than ten minutes after the start. The period of time before the start of dropping of hydrogen peroxide enables the polymerization reaction in the initial stage to be smoothly initiated, which in turn enables a narrow molecular weight distribution to be obtained. The time period before the start of the dropping of hydrogen peroxide is preferably not longer than 60 minutes after the start of the dropping of the monomer, and more preferably not longer than 30 minutes.

However, the dropwise addition of hydrogen peroxide may be started simultaneously with the dropwise addition of the monomer, or a part of hydrogen peroxide may be added to the reaction system and then the dropwise addition of the monomer may be started. The amount is preferably not more than 10% by mass, more preferably not more than 7% by mass, still more preferably not more than 5% by mass, and particularly more preferably not more than 3% by mass of the predetermined amount of hydrogen peroxide to be added to the reaction system in advance.

For example, in the case of using hydrogen peroxide together with a persulfate, the polymerization reaction can be terminated because the hydrogen peroxide concentration relative to the persulfate is high by adding hydrogen peroxide in an amount of 10 mass% larger than the predetermined required amount before starting dropping of the monomer. If hydrogen peroxide is added 60 minutes after the start of dropping the monomer, a reaction such as a chain transfer reaction by hydrogen peroxide may not start. Therefore, the polymer produced at the initial stage of polymerization may have a high molecular weight.

Preferably, when the reaction is carried out under suitable reaction conditions (e.g., temperature, pressure, pH) as described below, the dropwise addition of hydrogen peroxide is completed simultaneously with the completion of the dropwise addition of the monomer. The completion of the hydrogen peroxide addition is more preferably not less than 10 minutes ahead of the completion of the monomer dropping, and still more preferably not less than 30 minutes ahead of the completion of the monomer dropping. Even if the completion of the hydrogen peroxide dropping lags behind the completion of the monomer dropping, the polymerization system is not affected at all adversely. However, at the end of the polymerization, a portion of the added hydrogen peroxide remains undecomposed. Unreacted hydrogen peroxide does not produce efficacy and is used inefficiently. In addition, if a large amount of hydrogen peroxide remains, the remaining hydrogen peroxide adversely affects the thermal stability of the resulting polymer.

As for the use of the persulfate, the method of adding the persulfate is not particularly limited. However, it is preferable to almost continuously dropwise add at least 50 mass% of a predetermined required amount of the persulfate in consideration of its decomposition ability and the like. The amount is more preferably at least 80% by mass, and still more preferably 100% by mass (i.e., it is preferable to dropwise add all the persulfate). In the case of continuously dropping the persulfate, the dropping rate may be changed.

The dropping time is also not particularly limited. Since the persulfate is an initiator to be decomposed in a relatively short time when the reaction is carried out under suitable reaction conditions (e.g., temperature, pressure, pH) described below, it is preferable to continuously add the persulfate until the monomer addition is completed. The persulfate dropping is more preferably completed within 30 minutes after the completion of the monomer dropping, and the addition is particularly preferably completed within 5 to 20 minutes after the completion of the monomer dropping. By this method, the amount of residual monomer in the resulting polymer solution can be significantly reduced.

Even if the initiator dropping is completed prior to the monomer dropping, the polymerization reaction is not affected at all. The time for completion of the dropping of the initiator can be determined according to the amount of the residual monomer in the resulting polymer solution.

The dropping start time of the polymerization initiator is not particularly limited and is appropriately determined. For example, the dropping of the initiator may be started before the dropping of the monomer. When two or more initiators are used in combination, the dropping of the other one or more initiators may be started a certain time after the dropping of one of the initiators is started or a certain time after the dropping of the initiator is completed. In each case, the dropping start time of the one or more initiators may be appropriately determined depending on the decomposition rate of the one or more initiators and the reactivity of the monomer.

The concentration of the initiator solution is not particularly limited in terms of the dropwise addition of the polymerization initiator, and is preferably 5% to 60% by mass, and more preferably 10% to 50% by mass. In the polymerization reaction, when the initiator concentration is less than 5% by mass, the initiator solution contains a solvent at a high concentration, resulting in a low monomer concentration. In this case, the monomer polymerizability may be significantly low, and a substantial portion of the monomer may remain in the resulting polymer solution. Such concentrations are disadvantageous in terms of cost due to low transport efficiency and yield. A concentration of more than 60 mass% is disadvantageous in terms of safety and handleability upon dropping.

The amount of the chain transfer agent is not particularly limited, provided that the amount is determined so that the monomers (A), (B), (C) and (E) can be sufficiently polymerized. The amount of the chain transfer agent is preferably 1g to 20g, and more preferably 2g to 15g, per mole of all the monomers (A), (B), (C) and (E)). If the amount of the chain transfer agent is less than 1g, the molecular weight of the resulting polymer may not be controlled. On the other hand, the use of more than 20g of chain transfer agent may cause a large amount of impurities, resulting in low purity of the resulting polymer. Especially when more than 20g of the bisulfite is used, the excess bisulfite in the reaction system is decomposed, which may disadvantageously result in generation of sulfur dioxide gas. Furthermore, the use of more than 20g of chain transfer agent may be disadvantageous in terms of cost.

The preferred combination of initiator and chain transfer agent is one or more of persulfate and one or more of bisulfite.

In this case, the blending ratio between the one or more persulfate salts and the one or more bisulfite salts is not particularly limited. Preferably, 0.5 to5 parts by mass of one or more bisulfite is used relative to 1 part by mass of one or more persulfate. The lower limit of the amount of the one or more bisulfite is more preferably 1 part by mass, and still more preferably 2 parts by mass, relative to 1 part by mass of the one or more persulfate. The upper limit of the amount of the one or more bisulfite is more preferably 4 parts by mass, and still more preferably 3 parts by mass, relative to 1 part by mass of the one or more persulfate. If less than 0.5 parts by mass of one or more bisulfite is used relative to 1 part by mass of one or more persulfate, the total amount of initiator required to prepare a lower molecular weight polymer may increase. On the other hand, the use of more than 5 parts by mass of one or more bisulfite may increase side reactions, thereby increasing impurities generated by the side reactions.

The total amount of the chain transfer agent, the initiator, and the reaction accelerator is preferably 2g to 20g per mole of all the monomers (A), (B), (C), and (E). If the amount of these agents is within this range, the carboxyl group-containing polymer of the present invention can be efficiently produced, and the molecular weight distribution of the polymer can be controlled within a desired range. Their total amount is more preferably 4g to 18g, and still more preferably 6g to 15 g.

In the production method, the monomer, the polymerization initiator and the chain transfer agent may be added to the reaction vessel by continuous addition such as dropwise addition and batchwise addition. Each of them may be added to the reaction vessel separately, or they may be mixed with other materials in advance or mixed in a solvent or the like.

Specifically, these materials may be added by a method such as a method including adding all the monomers to a reaction vessel and adding a polymerization initiator to the reaction vessel to copolymerize the monomers; a method comprising adding a part of the monomer to a reaction vessel, and continuously or batchwise (preferably continuously) adding a polymerization initiator and the remaining monomer to the reaction vessel to copolymerize the monomer; and a method comprising adding a polymerization solvent to the reaction vessel, and adding all of the monomer and the polymerization initiator. Among these methods, a method comprising continuously dropwise adding a polymerization initiator and a monomer into a reaction vessel to copolymerize the monomer is preferable, because this provides a polymer having a narrow (i.e., sharp) molecular weight distribution, and when the polymer is formulated in a product, soil dispersibility and anti-soil redeposition ability are improved, thereby enhancing whiteness maintenance. The polymerization may be a batch polymerization or a continuous polymerization.

Polymerization conditions: in the preparation method, the polymerization temperature is appropriately determined depending on factors such as the polymerization method, the solvent, and the polymerization initiator. The polymerization temperature is preferably from 25 ℃ to 200 ℃, more preferably from 50 ℃ to 150 ℃, still more preferably from 60 ℃ to 120 ℃, and particularly preferably from 80 ℃ to 110 ℃. At polymerization temperatures below 25 ℃, the resulting polymer may have an excessively high weight average molecular weight and may generate a relatively large amount of impurities.

The polymerization temperature need not be kept substantially constant throughout the polymerization reaction. For example, the temperature at the start of polymerization may be set to room temperature and raised to a target temperature at an appropriate temperature raising rate or for an appropriate temperature raising time, and then maintained at the target temperature. Alternatively, the temperature may be changed (i.e., increased or decreased) over a period of time during the polymerization reaction according to the dropping method of the monomer, the initiator, and the like.

The term "polymerization temperature" as used herein refers to the temperature of the reaction solution during the polymerization reaction. The method of measuring the polymerization temperature and the apparatus for controlling the polymerization temperature may be appropriately selected from any method and control apparatus. For example, the polymerization temperature can be measured by a conventional apparatus.

In the preparation method, the pressure during the polymerization is not particularly limited and may be appropriately determined. For example, the pressure may be any of ambient pressure (e.g., atmospheric pressure), reduced pressure, and increased pressure. The atmosphere in the reaction system may be an air atmosphere or an inert atmosphere. In order to create an inert atmosphere in the reaction system, the air in the system is replaced with an inert gas such as nitrogen, for example, before the polymerization starts. In this atmosphere, atmospheric gas (such as oxygen) in the reaction system is dissolved in the liquid phase, and functions as a polymerization inhibitor.

In the production method, the solid content of the reaction solution (polymer solution) at the time of completion of the addition of the monomer, the polymerization initiator and the chain transfer agent is preferably not less than 35% by mass. The yield of the obtained polymer may not be significantly improved in terms of the solid content of less than 35 mass%. The solid content is more preferably 40 to 70 mass%, and still more preferably 45 to 65 mass%. When the solid content is not less than 35% by mass at the time of completion of the monomer, polymerization initiator and chain transfer agent addition, the polymerization can be carried out in one step in a high-concentration reaction solution. I.e. the polymer can be efficiently produced. In this case, steps such as a concentration step can be omitted, which in turn leads to a significant improvement in polymer yield and suppresses an increase in production cost.

The solid content can be calculated by sampling a part of the reaction solution after completion of the dropwise addition and quantifying the nonvolatile matter after one hour of treatment at 130 ℃ with a hot air dryer.

In the preparation method, a curing step may be performed to improve the polymerization rate of monomers and the like after all the raw materials are added. The aging time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes, and still more preferably 10 to 30 minutes. The curing of less than one minute is insufficient, so that a part of the monomer may remain. Therefore, impurities derived from the remaining monomers may be detrimental to the properties of the product. Aging for more than 120 minutes may result in a colored polymer solution.

In the production method, the polymerization time is not particularly limited, and is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and still more preferably 90 to 300 minutes. The term "polymerization time" as used herein refers to the time during which the monomer is added, i.e., the time from the beginning to the end of the addition of the monomer.

Use of polymers containing carboxyl groups

The carboxyl group-containing polymers and compositions comprising the polymers of the invention are useful as coagulants, printing inks, adhesives, soil control (i.e., modification) agents, fire retardants, skin care agents, hair care agents, additives for shampoos, hair sprays, soaps, and cosmetics, anion exchange resins, dye mordants and adjuvants for fiber and film, pigment dispersants for papermaking, paper strength agents, emulsifiers, preservatives, softeners for textiles and paper, additives for lubricants, water treatment agents, fiber treatment agents, dispersants, plate-like deposit control agents (plate-like deposit inhibitors), scale control agents (i.e., scale inhibitors), metal ion adhesives, viscosity modifiers, adhesives of any type, emulsifiers, and the like.

In a preferred modification, the carboxyl group-containing polymer composition comprises from about 40% to about 60% by mass of the carboxyl group-containing polymer and from about 38.5% to about 59.99% by mass of water.

Water treatment agent

Carboxyl group-containing polymers and compositions comprising the polymers of the invention are useful in water treatment agents. In these water treatment agents, other additives such as polyphosphates, phosphonates, corrosion inhibitors, slimicides, and chelating agents may be added if necessary.

Such a water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digesting tank, a black liquor concentrating tank, and the like. In addition, any suitable water-soluble polymer may be included within a range that does not affect the performance or efficacy of the composition.

Fiber treatment agent

Polymers containing carboxyl groups and compositions comprising the polymers of the invention are useful in fiber treatment agents. Such a fiber treatment agent contains at least one selected from a coloring agent, a peroxide and a surfactant, in addition to the carboxyl group-containing polymer or the composition containing the polymer of the present invention.

In these fiber-treating agents, the carboxyl group-containing polymer of the present invention preferably accounts for about 1% by mass to about 100% by mass of the total amount, and more preferably about 5% by mass to about 100% by mass. In addition, any suitable water-soluble polymer may be included within a range that does not affect the performance or efficacy of the composition.

Examples of the amounts of the components in these fiber treatment agents are described below. The fiber treatment agent can be used in scouring, dyeing, bleaching and soaking steps in fiber treatment. Examples of the coloring agent, peroxide, and surfactant include those commonly used in fiber treatment agents.

In terms of the blending ratio (in terms of solid content) between the carboxyl group-containing polymer composition of the present invention and at least one member selected from the group consisting of a coloring agent, a peroxide and a surfactant, for example, in order to improve whiteness, color uniformity, and color fastness of a fiber, it is preferable that the composition of the present invention contains at least one member selected from the group consisting of a coloring agent, a peroxide and a surfactant in an amount of 0.1 to 100 parts by mass per part by mass of the composition as a fiber treatment agent.

Such fiber treatment agents may be used for any suitable fiber, including cellulosic fibers such as cotton and hemp, synthetic fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as rayon, and textiles, and mixed products of these.

For the fiber treatment agent used in the scouring step, it is preferable to use an alkaline agent and a surfactant together with the polymer of the present invention. For the fiber treatment agent used in the bleaching step, it is preferable to use a peroxide and a silicic acid-based agent (e.g., sodium silicate) which acts as an alkaline bleach decomposition inhibitor together with the composition of the present invention.

Inorganic pigment dispersant

Carboxyl group-containing polymers and compositions comprising the polymers of the invention are useful in inorganic pigment dispersants. In these inorganic pigment dispersants, if necessary, other additives such as condensed phosphoric acid and salts thereof, phosphonic acid and salts thereof, and polyvinyl alcohol may be added.

Of these inorganic pigment dispersants, the carboxyl group-containing polymer of the present invention preferably accounts for about 5 to about 100 mass% of the total amount. In addition, any suitable water-soluble polymer may be included within a range that does not affect the performance or efficacy of the composition.

These inorganic pigment dispersants exhibit good performance as inorganic pigment dispersants for heavy or light calcium carbonate and clay used for paper coating. For example, by adding a small amount of such inorganic pigment dispersing agents to inorganic pigments and dispersing them in water, highly concentrated inorganic pigment slurries such as highly concentrated calcium carbonate slurries can be produced, which have low viscosity, high fluidity and excellent stability with time of these properties.

When such an inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant is preferably 0.05 to 2.0 parts by mass per 100 parts by mass of the pigment. Using the inorganic pigment dispersant in an amount within this range provides a sufficient dispersing effect in proportion to the added amount, and is advantageous in terms of cost.

Detergent builder

Polymers containing carboxyl groups and compositions comprising the polymers of the invention are also useful as detergent builders. These detergent builders can be incorporated into detergents for a variety of purposes, such as detergents for laundry, dishwashing, cleaning, hair, body, tooth brushing, and vehicles.

Laundry detergent or cleaning composition

In a preferred embodiment, polymers containing carboxyl groups can be added to the laundry detergent or cleaning compositions of the present invention. The content of the carboxyl group-containing polymer in the laundry detergent or cleaning composition is not particularly limited, but may further contain one or more components other than the carboxyl group-containing polymer and the bisulfite adduct. Examples of the other components include, but are not particularly limited to, residual polymerization initiator, residual monomer, by-products of polymerization reaction, and water.

From the viewpoint of exhibiting improved anti-soil redeposition and whiteness maintenance properties, the content of the adduct of bisulfite and acrylic-based monomer (C) is preferably from about 0.01 to about 1.5 mass% based on the total content of 100 mass% of the adduct of carboxyl-group-containing polymer and bisulfite and acrylic-based monomer (C). The bisulfite adduct in the above-mentioned range improves detergency to soil. The content is preferably about 0.02 to about 1.0 mass%, and more preferably about 0.03 to about 0.8 mass%.

The adduct of bisulfite with acrylic acid based monomer (C) (hereinafter also referred to as "bisulfite adduct") in the polymer is an impurity derived from acrylic acid based monomer (C) which remains unpolymerized, but to which the above-mentioned bisulfite and/or a compound capable of generating bisulfite as a chain transfer agent are added. Specific examples thereof include 3-sulfopropionic acid (salt) and the like.

Although the content of the polymer in the laundry detergent or cleaning composition is not particularly limited, the content of the carboxyl group-containing polymer is about 1% by mass to about 99.99% by mass based on 100% by mass of the total laundry detergent or cleaning composition in terms of improvement of anti-soil redeposition ability and whiteness maintenance. The polymer is preferably present in an amount of from about 0.1% to about 20%, or from about 0.2% to about 18%, or from about 0.3% to about 12%, or from about 0.4% to about 5% of the carboxyl group-containing polymer.

Laundry detergents and cleaning compositions comprising said polymers

The laundry detergent or cleaning compositions of the present invention comprise a carboxyl group-containing polymer and optionally other adjunct ingredients. The laundry detergent or cleaning composition may be in any form, i.e. liquid form; solid forms such as powders, granules, agglomerates, pastes, tablets, sachets, bars, gels; in the form of an emulsion; in the form of a dual or multi-compartment container or pouch; spray or foam detergent forms; pre-moistened wipe forms (i.e., a combination of a cleaning composition and a nonwoven material as described by Mackey et al in U.S. patent 6,121,165); a consumer water activated dry wipe form (i.e., a combination of a cleaning composition and a nonwoven material, as described in U.S. patent 5,980,931 to Fowler et al); and other homogeneous or heterogeneous consumer cleansing product forms.

Examples of laundry detergents and cleaning compositions

Of the various aspects of the invention shown in the summary above, certain embodiments are preferred.

In one embodiment of the invention is a laundry detergent or cleaning composition as set forth in the summary, the composition comprising a carboxyl group-containing polymer, wherein the polymer comprises:

a structural unit (b) represented by formula (5):

a structural unit (c) represented by formula (8):

wherein R is¹⁰Represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.

One aspect of this embodiment is a laundry detergent or cleaning composition, wherein the carboxyl group-containing polymer comprises structural units (b) selected from the group comprising: vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 3- (meth) allyloxy-2-hydroxypropanesulfonic acid, 3- (meth) allyloxy-1-hydroxypropanesulfonic acid, 2- (meth) allyloxyethenesulfonic acid, and 2-acrylamido-2-methylpropanesulfonic acid, with 3- (meth) allyloxy-2-hydroxypropanesulfonic acid being preferred as structural unit (b).

Another embodiment of the present invention is a laundry detergent or cleaning composition as described in the summary, wherein the carboxyl group-containing polymer comprises:

i. preferably from about 1 to about 9 mass%, more preferably from about 2 to about 8 mass%, and even more preferably from about 3 to about 7 mass% of structural unit (a);

preferably from about 1 to about 23 mass%, more preferably from about 3 to about 22 mass%, and even more preferably from about 5 to about 21 mass% of structural units (b); and

preferably from about 68 to about 98 mass%, more preferably from about 70 to about 95 mass%, and even more preferably from about 72 to about 92 mass% of structural units (c).

One aspect of this embodiment is a laundry detergent or cleaning composition, wherein the carboxyl group-containing polymer comprises:

i. even more preferably from about 3 to about 7 mass% of structural unit (a);

even more preferably from about 5 to about 21 mass% of structural units (b); and

even more preferably from about 72 to about 92 mass% of structural units (c).

In another embodiment, the laundry detergent or cleaning compositions of the present invention comprising a carboxyl group-containing polymer have high performance when used in an aqueous environment. In addition, the carboxyl group-containing polymer has improved high hard water resistance, anti-soil redeposition ability, clay dispersibility, detergency, and interaction with a surfactant, thereby exhibiting better performance when used in the laundry detergent or cleaning composition of the present invention.

In another embodiment, the laundry detergent or cleaning composition is a liquid or solid composition.

In another embodiment, the laundry detergents of the invention comprise multipurpose or "heavy duty" detergents, especially cleaning detergents, in granular or powder form, and cleaning auxiliaries, such as bleach additives, fabric softeners and fabric treatment liquors, or pre-or post-treatment types. In one aspect, the laundry detergent is, for example, a solid laundry detergent composition, and preferably a free-flowing particulate laundry detergent composition (i.e., a particulate detergent product). In another aspect, the laundry detergent comprises synthetic and soap-based laundry bars.

In another embodiment, the laundry detergent of the present invention relates to a gel detergent composition comprising an organic solvent selected from the group consisting of low molecular weight aliphatic or aromatic alcohols, low molecular weight alkylene glycols, low molecular weight alkylene glycol ethers, low molecular weight esters, low molecular weight alkyleneamines, low molecular weight alkanolamines, and mixtures thereof.

In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition, preferably wherein the hard surface cleaning composition impregnates a nonwoven substrate. As used herein, "saturated" means that the hard surface cleaning composition is placed in contact with a nonwoven substrate such that the hard surface cleaning composition penetrates into at least a portion of the nonwoven substrate. Preferably, the hard surface cleaning composition saturates the nonwoven substrate.

In another embodiment, the cleaning composition may also be used in automotive care compositions for cleaning various surfaces, such as, for example, hardwood, tile, ceramic, plastic, leather, metal, or glass.

In another embodiment, the cleaning composition of the present invention is a dishwashing cleaning composition, such as a liquid hand dishwashing composition, a solid automatic dishwashing composition, a liquid automatic dishwashing composition, or a tablet/unit dosage form automatic dishwashing composition.

In another embodiment, the cleansing composition of the present invention is a personal care composition or a pet care composition, such as a shampoo composition, a hair rinse, a mouthwash, a denture cleanser, a body wash (e.g., shower gel and foam bath), or a liquid or solid soap.

In another embodiment, the cleaning compositions of the present invention are compositions that come into contact with free hardness and/or require a hardness tolerant surfactant system, such as compositions comprising metal cleaners, oil cleaners, corrosion inhibitors or discoloration prevention aids.

In another embodiment, the cleansing composition of the present invention is an automotive care composition, such as an automotive shampoo.

In another embodiment, the cleaning composition of the present invention is a home care composition, such as a bathroom cleaner or carpet shampoo.

Specific embodiments of the present invention are described in more detail in the examples section below.

Preparation of a laundry detergent or cleaning composition comprising said polymer

In one embodiment, all types of cleaning compositions require several adjuncts. Common cleaning adjuncts include builders, enzymes, polymers not discussed above, bleaches, bleach activators, catalytic materials, and the like. Other cleaning adjuncts herein may include suds boosters, suds suppressors (defoamers), and the like, various active ingredients or specialty materials other than those described above, such as dispersant polymers (e.g., available from BASF corp. or Rohm & Haas), stain repellents, silverware care agents, rust and/or corrosion inhibitors, dyes, fillers, bactericides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizers, pro-perfumes, solubilizers, carriers, processing aids, pigments, and for liquid formulations, solvents, chelants, dye transfer inhibitors, dispersants, brighteners, suds suppressors, dyes, structure elasticizing agents, fabric softeners, anti-abrasion agents, hydrotropes, processing aids, and other fabric care agents, surface and skin care agents. Suitable examples of such other cleaning aids and amounts can be found in U.S. patents: 5,576,282; 6,306,812Bl and 6,326,348B 1.

In another embodiment, the finished detergent product in particulate form is prepared by mixing the carboxyl group-containing polymer with optional dry mix ingredients and/or optional liquid spray ingredients. Finished granular detergents are typically formulated such that the wash water will have a pH of between about 6.5 and about 12, or between about 7.5 and 10.5, during use in an aqueous cleaning operation. Techniques for adjusting the pH to a desirable use level include, but are not limited to, the use of buffers, bases, acids, and the like, and are well known to those skilled in the art. Sample formulations see example 5.

Typically, the laundry detergent is a fully formulated laundry detergent composition, not a part thereof, such as a spray-dried or agglomerated particle that forms only a part of the laundry detergent composition. However, it is within the scope of the present invention that additional rinse additive compositions (e.g., fabric conditioners or enhancers) or primary wash additive compositions (e.g., bleach additives) may also be used in combination with the laundry detergent composition during the present method. Preferably, however, a bleach-free additive composition is used in combination with the laundry detergent composition during the process of the present invention.

Typically, the laundry detergent composition comprises a plurality of chemically different particles, such as spray-dried base detergent particles and/or agglomerated base detergent particles and/or extruded base detergent particles in combination with one or more, typically two or more, or three or more, or four or more, or five or more, or six or more, or even ten or more particles selected from: surfactant granules, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant noodles, surfactant flakes; polymer particles such as cellulosic polymer particles, polyester particles, polyamine particles, terephthalic acid polymer particles, polyethylene glycol polymer particles; builder particles, such as sodium carbonate and sodium silicate co-builder particles, phosphate particles, zeolite particles, silicate particles, carbonate particles; filler particles such as sulfate particles; dye transfer inhibitor particles; dye fixative particles; bleach particles, such as percarbonate particles, in particular coated percarbonate particles, such as carbonate, sulphate, silicate, borosilicate, or any combination thereof coated percarbonate; perborate particles; bleach catalyst particles, such as transition metal bleach catalyst particles, or peroxyimine cation-based bleach catalyst particles; preformed peracid particles, particularly coated preformed peracid particles; and a bleach activator; a source of hydrogen peroxide and optionally a bleach catalyst; bleach activator particles such as sodium oxybenzenesulfonate bleach activator particles and tetraacetylethylenediamine bleach activator particles; chelant particles such as chelant agglomerates; a hueing dye particle; a brightener particle; enzyme granules such as protease granules, lipase granules, cellulase granules, amylase granules, mannanase granules, pectate lyase granules, xyloglucanase granules, bleaching enzyme granules, cutinase granules and co-granulation of any of them; clay particles such as montmorillonite particles or clay and silicone particles; flocculant particles such as polyethylene oxide particles; wax particles such as waxy agglomerates; perfume particles such as perfume microcapsules, in particular melamine formaldehyde based perfume microcapsules, starch encapsulated perfume accord particles, and pro-perfume particles such as schiff base reaction product particles; aesthetic particles such as colored bar-like or needle-like or flake-like particles, and soap rings including colored soap rings; and any combination thereof.

The components of the detergent are as follows: the compositions typically comprise detergent ingredients. Suitable detergent ingredients include: detersive surfactants including anionic detersive surfactant, nonionic detersive surfactant, cationic detersive surfactant, zwitterionic detersive surfactant, amphoteric detersive surfactant, and any combination thereof. Polymers including carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulose polymers, dye transfer inhibitor polymers, dye locking polymers such as condensation oligomers resulting from the condensation of imidazole and epichlorohydrin, optionally in a 1:4:1 ratio, hexamethylenediamine derivative polymers, and any combination thereof; builders including zeolites, phosphates, citrates, and any combinations thereof; buffers and alkalinity sources including carbonates and/or silicates; fillers, including sulfate and bio-filler materials; bleaching agents, including bleach activators, available oxygen sources, preformed peracids, bleach catalysts, reducing bleaches, and any combination thereof; a chelating agent; a photo-bleaching agent; a toner; a whitening agent; enzymes, including proteases, amylases, cellulases, lipases, xyloglucanases, pectate lyases, mannanases, bleaches, cutinases, and any combination thereof; fabric softeners including clays, silicones, quaternary ammonium salt fabric softeners, flocculants such as polyethylene oxide; perfumes including starch encapsulated perfume accords, perfume microcapsules, perfume loaded zeolites, schiff base reaction products of ketone perfume raw materials and polyamines, blooming perfumes, and any combination thereof; aesthetics including soap rings, lamellar aesthetic particles, gelatin beads, carbonate and/or sulfate speckles, colored clays, and any combination thereof; and any combination thereof.

Detersive surfactant: the composition typically comprises a detersive surfactant. Suitable detersive surfactants include anionic detersive surfactants, nonionic detersive surfactants, cationic detersive surfactants, zwitterionic cleaning surfactants, amphoteric detersive surfactants, and any combination thereof.

Anionic detersive surfactant: suitable anionic detersive surfactants include sulphate and sulphonate detersive surfactants.

Preferably, the amount of anionic detersive surfactant is in the range of from 5% to 50% by weight of the total composition. More preferably, the amount of anionic surfactant ranges from about 8% to about 35% by weight.

Suitable sulphonate detersive surfactants include alkyl benzene sulphonates, such as C_10-13An alkylbenzene sulfonate. Suitable alkyl benzene sulfonates (LAS) are available or even obtained by sulfonating commercially available Linear Alkyl Benzenes (LAB); suitable LAB include low 2-phenyl LAB, such as that sold under the trade name SasolOr by Petresa under the trade nameThose provided; other suitable LAB include high 2-phenyl LAB, such as that sold under the trade name SasolThose provided. Another suitable anionic detersive surfactant is alkyl benzene sulphonate, obtainable by DETAL catalysed processes, although other synthetic routes such as HF may also be suitable.

Suitable sulphate detersive surfactants include alkyl sulphates such as C_8-18Alkyl sulfates, or predominantly C₁₂An alkyl sulfate. The alkyl sulfates may be derived from natural sources, such as coconut oil and/or tallow. Alternatively, the alkyl sulfates may be derived from synthetic sources, such as C_12-15An alkyl sulfate.

Another suitable sulphate detersive surfactant is an alkyl alkoxylated sulphate, such as alkyl ethoxylated sulphate, or C_8-18Alkyl alkoxylated sulfates, or C_8-18Alkyl ethoxylated sulfates. The alkyl alkoxylated sulfates mayHas an average degree of alkoxylation of from 0.5 to 20, or from 0.5 to 10. The alkyl alkoxylated sulfate may be C_8-18Alkyl ethoxylated sulfates, which typically have an average degree of ethoxylation of from 0.5 to 10, or from 0.5 to 7, or from 0.5 to5, or from 0.5 to 3.

The alkyl sulfates, alkyl alkoxylated sulfates and alkylbenzene sulfonates may be linear or branched, substituted or unsubstituted.

The anionic detersive surfactant may be a mid-chain branched anionic detersive surfactant, such as a mid-chain branched alkyl sulphate and/or a mid-chain branched alkyl benzene sulphonate. The mid-chain branch is typically C_1-4Alkyl groups, such as methyl and/or ethyl.

Another suitable anionic detersive surfactant is an alkyl ethoxy carboxylate.

The anionic detersive surfactants are typically present in their salt form, usually complexed with a suitable cation. Suitable counterions include Na⁺And K⁺Substituted ammonium, e.g. C₁-C₆Alkanolammonium, such as Monoethanolamine (MEA), Triethanolamine (TEA), Diethanolamine (DEA), and any mixture thereof.

Nonionic detersive surfactant: suitable nonionic detersive surfactants are selected from: c₈-C₁₈Alkyl ethoxylates, e.g. from ShellA nonionic surfactant; c₆-C₁₂An alkylphenol alkoxylate, wherein optionally the alkoxylate unit is an ethyleneoxy unit, a propyleneoxy unit, or a mixture thereof; c₁₂-C₁₈Alcohol and C₆-C₁₂Condensates of alkylphenols with ethylene oxide/propylene oxide block polymers, e.g. from BASFC₁₄-C₂₂Mid-chain branched alcohols; c₁₄-C₂₂Mid-chain branched alkyl alkoxylates, which generally have 1An average degree of alkoxylation to 30; alkyl polysaccharides such as alkyl polyglycosides; polyhydroxy fatty acid amides; ether-terminated polyalkoxy alcohol surfactants; and mixtures thereof.

Suitable nonionic detersive surfactants are alkyl polyglucosides and/or alkyl alkoxylated alcohols.

The amount of nonionic detersive surfactant, if present, is preferably in the range of from about 1% to about 20% by weight.

Suitable nonionic detersive surfactants include alkyl alkoxylated alcohols, such as C_8-18Alkyl alkoxylated alcohols, or C_8-18An alkyl ethoxylated alcohol. The alkyl alkoxylated alcohol may have an average degree of alkoxylation of from 0.5 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10. The alkyl alkoxylated alcohol may be C_8-18An alkyl ethoxylated alcohol, typically having an average degree of ethoxylation of from 1 to 10, or from 1 to 7, or from 1 to5, or from 3 to 7. The alkyl alkoxylated alcohol may be linear or branched and substituted or unsubstituted.

Suitable nonionic detersive surfactants include secondary alcohol-based detersive surfactants having the formula (I):

wherein R is¹Linear or branched, substituted or unsubstituted, saturated or unsaturated C_2-8An alkyl group;

wherein R is²Linear or branched, substituted or unsubstituted, saturated or unsaturated C_2-8An alkyl group, a carboxyl group,

wherein R is¹+R²The total number of carbon atoms present in the moiety is in the range of 7 to 13;

wherein EO/PO are alkoxy moieties selected from ethoxy, propoxy, or mixtures thereof, optionally the EO/PO alkoxy moieties are in a random or block configuration;

wherein n is the average degree of alkoxylation and is in the range of 4 to 10.

Other suitable nonionic detersive surfactants include EO/PO block copolymer surfactants, such as those available from BASFA series of surfactants, and sugar derived surfactants such as alkyl N-methyl glucamides.

Suitable nonionic detersive surfactants which can be used include primary and secondary alcohol ethoxylates, especially C ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol₈-C₂₀Aliphatic alcohols, and more particularly C ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol₁₀-C₁₅Primary and secondary aliphatic alcohols. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxy amides (e.g., glucamide).

Cationic detersive surfactant: suitable cationic detersive surfactants include alkyl pyridinesCompound, alkyl quaternary ammonium compound, alkyl quaternary phosphonium compoundA compound, an alkyl ternary sulfonium compound, and mixtures thereof.

Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula (II):

(II)

(R)(R₁)(R₂)(R₃)N⁺X^-

wherein R is a linear or branched, substituted or unsubstituted C_6-18Alkyl or alkenyl moieties, R₁And R₂Independently selected from methyl or ethyl moieties, R₃Is a hydroxy, hydroxymethyl or hydroxyethyl moiety, X is an anion providing electrical neutrality, andthe anion includes: halides, such as chloride; a sulfate salt; and a sulfonate salt. Suitable cationic detersive surfactants are mono C_6-18Alkyl monohydroxyethyl dimethyl ammonium chloride. Suitable cationic detersive surfactants are mono C_8-10Alkyl monohydroxyethyl dimethyl ammonium chloride, mono C_10-12Alkyl monohydroxyethyl dimethyl ammonium chloride and mono C₁₀Alkyl monohydroxyethyl dimethyl ammonium chloride.

Zwitterionic and/or amphoteric detersive surfactants: suitable zwitterionic and/or amphoteric detersive surfactants include amine oxides such as dodecyl dimethyl amine oxide, alkanolamine sulfobetaines, cocamidopropyl betaine, based on HN⁺-R-CO₂ ^-Wherein R may be any bridging group such as alkyl, alkoxy, aryl or amino acid. Many suitable detergent-Active compounds are available and are well described in the literature, for example in "Surface-Active Agents and Detergents" volumes I and II of Schwartz, Perry and Berch.

Chelating agent: suitable chelating agents may also include: diethylene triamine pentaacetate, diethylene triamine penta (methyl phosphonic acid), ethylene diamine-N' -disuccinic acid, ethylene diamine tetraacetate, ethylene diamine tetra (methylene phosphonic acid), hydroxyethane di (methylene phosphonic acid), and any combination thereof. Suitable chelating agents are ethylenediamine-N' -disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP). The cleaning composition may comprise ethylenediamine-N' -disuccinic acid or salts thereof. ethylenediamine-N' -disuccinic acid can be in the form of the S, S enantiomer. The cleaning composition may comprise disodium 4, 5-dihydroxyisophthalate. Suitable chelating agents may also be calcium crystal growth inhibitors.

Polymer (b): suitable polymers include carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibiting polymers, dye fixing polymers such as condensation oligomers formed by the condensation of imidazole and epichlorohydrin, optionally in a 1:4:1 ratio, hexamethylenediamine derivative polymers, and any combination thereof.

Carboxylate polymer: suitable carboxylate polymers include maleate/acrylate random copolymers or polyacrylate homopolymers. The carboxylate polymer may be a polyacrylate homopolymer having a molecular weight of 4,000Da to 9,000Da, or 6,000Da to 9,000 Da. Other suitable carboxylate polymers are copolymers of maleic and acrylic acids and may have molecular weights in the range of 4,000Da to 90,000 Da.

Polymer (b): preferably, the polymer is a polyethylene glycol polymer. Suitable polyethylene glycol polymers include random graft copolymers comprising: (i) a hydrophilic backbone comprising polyethylene glycol; and (ii) one or more hydrophobic side chains selected from: c_4-C₂₅Alkyl radical, polypropylene, polybutene, saturated C₁-C₆Vinyl esters of monocarboxylic acids, C of acrylic or methacrylic acid_1-6Alkyl esters, and mixtures thereof; suitable polyethylene glycol polymers have a polyethylene glycol backbone and randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone may be in the range of 2,000Da to 20,000Da, or 4,000Da to 8,000 Da. The molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can range from 1:1 to 1:5, or from 1:1.2 to 1: 2. The average number of grafting sites per ethylene oxide unit may be less than 1, or less than 0.8, the average number of grafting sites per ethylene oxide unit may be in the range of 0.5 to 0.9, or the average number of grafting sites per ethylene oxide unit may be in the range of 0.1 to 0.5, or 0.2 to 0.4. Suitable polyethylene glycol polymers areHP22。

Polyester soil release polymers: suitable polyester soil release polymers have a structure defined by one of the following structures (III), (IV), or (V):

(III)-[(OCHR¹-CHR²)_a-O-OC-Ar-CO-]_d

(IV)-[(OCHR³-CHR⁴)_b-O-OC-sAr-CO-]_e

(V)-[(OCHR⁵-CHR⁶)_c-OR⁷]_f

wherein:

a. b and c are 1 to 200;

d. e and f are 1 to 50;

ar is 1, 4-substituted phenylene;

sAr is SO substituted in the 5-position₃1, 3-substituted phenylene substituted with Me;

me is H, Na, Li, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, where the alkyl group is C₁-C₁₈Alkyl, or C₂-C₁₀Hydroxyalkyl, or any mixture thereof;

R¹、R²、R³、R⁴、R⁵and R⁶Independently selected from H or C₁-C₁₈N-alkyl or iso-alkyl; and is

R⁷Is straight-chain or branched C₁-C₁₈Alkyl, or straight or branched C₂-C₃₀Alkenyl, or cycloalkyl having 5 to 9 carbon atoms, or C₈-C₃₀Aryl radicals, or C₆-C₃₀An aralkyl group.

Suitable polyester soil release polymers are terephthalate polymers having the above structure (III) or (IV).

Suitable polyester soil release polymers includeSeries of polymers such as Rebel-O-SF2(Rhodia), and/orPolymers of the series e.g.SRA300(Clariant)。

Other suitable soil release polymers may include, for example, end-capped and non-end-capped sulfonated and non-sulfonated PET/POET polymers, and oil-based ethylene glycol/polyvinyl alcohol graft copolymers such asHP222。

A particularly preferred soil release polymer is the non-end-capped sulfonated polyester described and claimed in PCT publication WO 95/32997A (Rhodia Chimie).

Amine polymer: suitable amine polymers include polyethyleneimine polymers, such as alkoxylated polyalkyleneimines, optionally comprising polyethylene oxide and/or polypropylene oxide blocks.

Cellulose polymer: the cleaning composition may comprise a cellulosic polymer, such as a polymer selected from the group consisting of alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses, and any combination thereof. Suitable cellulosic polymers are selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methylcarboxymethyl cellulose, and mixtures thereof. The carboxymethyl cellulose may have a degree of substitution of carboxymethyl groups of 0.5 to 0.9 and a molecular weight of 100,000Da to 300,000 Da. Another suitable cellulose polymer is hydrophobically modified carboxymethyl cellulose, e.g. carboxymethyl celluloseSH-1(CP Kelco)。

Other suitable cellulosic polymers may have a Degree of Substitution (DS) of from 0.01 to 0.99 and a Degree of Blockiness (DB) such that either DS + DB is at least 1.00 or DB +2DS-DS2 is at least 1.20. The substituted cellulosic polymer may have a Degree of Substitution (DS) of at least 0.55. The substituted cellulose polymer may have a blockiness (DB) of at least 0.35. The substituted cellulose polymer may have a DS + DB of 1.05 to 2.00. A suitable substituted cellulose polymer is carboxymethyl cellulose.

Another suitable cellulose polymer is cationically modified hydroxyethyl cellulose. Random graft copolymer suitable random graft copolymers generally comprise: (i) from 50 to less than 98 weight percent structural units derived from one or more monomers comprising a carboxyl group; (ii) from 1 wt% to less than 49 wt% structural units derived from one or more monomers comprising a sulfonate moiety; and (iii)1 to 49 wt% of structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (VI) and (VII):

In the formula (VII), R₀Represents a hydrogen atom or CH₃Group, R represents CH₂Radical, CH₂CH₂A group or a single bond, X represents a number from 0 to5, and R₁Is a hydrogen atom or C₁-C₂₀An organic group.

Dye transfer inhibitor polymer: suitable dye transfer inhibiting agent (DTI) polymers include polyvinylpyrrolidone (PVP), vinylpyrrolidone and imidazoline copolymers (pvpvpvi), polyethylene N-oxide (PVNO), and any mixtures thereof.

Hexamethylenediamine derivative polymer: suitable polymers include hexamethylenediamine derivative polymers, typically of the formula (VIII):

(VIII)

R₂(CH₃)N⁺(CH₂)6N⁺(CH₃)R₂.2X^-

wherein X^-Is a suitable counterion, such as chloride, and R is a poly (ethylene glycol) chain having an average degree of ethoxylation of from 20 to 30. Optionally, the poly (ethylene glycol) chains can be independently capped with sulfate and/or sulfonate groups, typically by reducing X^-Number of counterions, or (in the case of an average sulphation degree per molecule greater than two) introduction of Y⁺A counter ion such as a sodium cation to balance the charge.

In another aspect, the laundry detergent comprises citrate. A suitable citrate salt is sodium citrate. However, citric acid may also be incorporated into the laundry detergent, which may form citrate in the wash liquor.

In another aspect, the laundry detergent comprises a bleaching agent. Alternatively, the laundry detergent may be substantially free of bleach; substantially free means "not intentionally added". Suitable bleaching agents include bleach activators, available sources of oxygen, preformed peracids, bleach catalysts, reducing bleaches, and any combination thereof. If present, the bleaching agent or any of its components, e.g., a preformed peracid, can be coated, e.g., encapsulated or included, with, e.g., urea or cyclodextrin.

In another aspect, the laundry detergent comprises a bleach activator. Suitable bleach activators include: tetraacetylethylenediamine (TAED); phenolsulfonate salts such as nonanoyl phenolsulfonate (NOBS), acrylamide nonanoyl phenolsulfonate (NACA-OBS), 3,5, 5-trimethylhexanoyl phenolsulfonate (Iso-NOBS), dodecylphenolsulfonate (LOBS), and any mixtures thereof; caprolactam; pentaacetate glucose (PAG); a quaternary ammonium nitrile; imide bleach activators such as N-nonanoyl-N-methylacetamide; and any mixtures thereof.

In another aspect, the laundry detergent comprises a source of available oxygen. Suitable available oxygen sources (AvOx) are sources of hydrogen peroxide, such as percarbonate and/or perborate salts, such as sodium percarbonate. The peroxygen source may be at least partially coated, or even completely coated, with a coating ingredient such as a carbonate, sulfate, silicate, borosilicate, or any mixture thereof, including mixed salts thereof. Suitable percarbonates may be prepared by a fluid bed process or by a crystallisation process. Suitable perborates include sodium perborate monohydrate (PB1), sodium perborate tetrahydrate (PB4), and anhydrous sodium perborate known as foamed sodium perborate. Other suitable sources of AvOx include persulfates such as oxone. Another suitable AvOx source is hydrogen peroxide.

In another aspect, the laundry detergent comprises a preformed peracid. A suitable pre-formed peracid is N, N-phthalaminohexaperoxyacid (PAP).

In another aspect, the laundry detergent comprises a bleach catalyst. Suitable bleach catalysts include peroxyimine cation based bleach catalysts, transition metal bleach catalysts and bleaching enzymes.

In another aspect, the laundry detergent comprises a peroxyimine cation based bleach catalyst. Suitable peroxyimine cation based bleach catalysts have the formula (IX):

wherein: r¹Selected from: H. a branched alkyl group comprising 3 to 24 carbons and a linear alkyl group comprising 1 to 24 carbons; r¹May be a branched alkyl group comprising 6 to 18 carbons, or a straight alkyl group comprising 5 to 18 carbons; r¹Can be selected from: 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, isononyl, isodecyl, isotridecyl and isotentadecyl; r²Independently selected from: H. a branched alkyl group comprising 3 to 12 carbons, and a linear alkyl group comprising 1 to 12 carbons; optionally, R²Independently selected from H, methyl, a branched alkyl group containing 3 to 12 carbons, and a branched alkyl group containing 1 to 12 carbonsA 12 carbon straight chain alkyl group; and n is an integer of 0 to 1. Bleach boosters based on peroxyimine cations can be made according to U.S. patent publication 2006/0089284 Al.

In another aspect, the laundry detergent comprises a transition metal bleach catalyst. The laundry detergent composition may comprise a transition metal bleach catalyst, typically comprising copper, iron, titanium, ruthenium, tungsten, molybdenum and/or manganese cations. Suitable transition metal bleach catalysts are manganese-based transition metal bleach catalysts.

In another aspect, the laundry detergent comprises a reduction catalyst. The cleaning composition may comprise a reducing bleach. However, the laundry detergent composition may be substantially free of reducing bleach; substantially free means "not intentionally added". Suitable reducing bleaches include sodium sulfite and/or Thiourea Dioxide (TDO).

In another aspect, the laundry detergent comprises a co-bleach particle. The cleaning composition may comprise a co-bleach particle. Typically, the co-bleach particle comprises a bleach activator and a peroxide source. In co-bleach particles, the presence of a large amount of bleach activator relative to the source of hydrogen peroxide is highly desirable. The weight ratio of bleach activator to hydrogen peroxide source present in the co-bleach particle may be at least 0.3:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1.0:1.0, or even at least 1.2:1 or higher.

The co-bleach particle may comprise: (i) bleach activators, such as TAED; and (ii) a source of hydrogen peroxide, such as sodium percarbonate. The bleach activator may at least partially encapsulate, or even completely encapsulate, the source of hydrogen peroxide.

The co-bleach particle may comprise a binder. Suitable binders are carboxylate polymers, such as polyacrylate polymers, and/or surfactants, including nonionic and/or anionic detersive surfactants, such as linear C₁₁-C₁₃An alkylbenzene sulfonate.

In another aspect, the laundry detergent comprises a bleach stabilizer (heavy metal sequestrant). Suitable bleach stabilizationThe fixative includes ethylenediaminetetraacetic acid (EDTA) and polyphosphonates such asEDTMP。

In another aspect, the laundry detergent comprises a photo-bleach. Suitable photobleaches are sulfonated zinc phthalocyanines and/or sulfonated aluminum phthalocyanines.

In another aspect, the laundry detergent comprises a brightener. The cleaning composition may preferably comprise a fluorescent whitening agent such as disodium 4,4' -bis (2-sulphostyryl) biphenyl (c.l. fluorescent whitening agent 351); c.i. fluorescent brightener 260, or its phenylamino-or morpholino-substituted analogs with other groups. Suitable c.i. fluorescent whitening agents 260 may have the following structure (X):

wherein the c.i. fluorescent brightener 260:

predominantly in the alpha-crystalline form; or

Predominantly in the form of beta crystals and having a weight average primary particle size of from 3 to 30 microns.

In another aspect, the laundry detergent comprises a bleach stable fluorescent whitening agent, such as may be tradenameBis (sulfobenzofuranyl) biphenyl, commercially available from Ciba Specialty Chemicals by PLC.

In another aspect, the laundry detergent may comprise a fabric hueing agent (sometimes referred to as a colorant, bluing agent, or brightener). Toners generally provide a blue or violet shade to fabrics. Toners can be used individually or in combination to create specific hueing shades and/or to tint different fabric types. This may be provided, for example, by mixing red and blue-green dyes to produce a blue or violet hue. The hueing agent may be selected from any known chemical class of dyes, including, but not limited to acridine, anthraquinones (including polycyclic quinones), azines, azones(e.g., monoazo, disazo, trisazo, tetraazo, polyazo) including premetallized azo, benzodifuran and benzodifuranone, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethane, formazan, hemicyanines, indigoids, methane, naphthalimides, naphthoquinones, nitro and nitroso groups,Oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof.

Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include dyes selected from the classes of direct, basic, reactive, or hydrolyzed reactive, solvent, or disperse dyes classified under the color Index (c.i.) and individually or in combination providing the desired hue, for example, as blue, violet, red, green, or black. In another aspect, suitable small molecule dyes include the following numbered small molecule dyes selected from the dye index (Society of Dyers and Colourists, Bradford, UK): direct violet dyes such as 9, 35, 48, 51, 66 and 99, direct blue dyes such as 1, 71, 80 and 279, acid red dyes such as 17, 73, 52, 88 and 150, acid violet dyes such as 15, 17, 24, 43, 49 and 50, acid blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, acid black dyes such as 1, basic violet dyes such as 1,3, 4, 10 and 35, basic blue dyes such as 3, 16, 22, 47, 66, 75 and 159, disperse or solvent dyes such as those described in EP1794275 or EP1794276, or dyes as disclosed in US 7208459B2, and mixtures thereof. In another aspect, suitable small molecule dyes include those selected from the following color index numbers: acid violet 17, direct blue 71, direct violet 51, direct blue 1, acid red 88, acid red 150, acid blue 29, acid blue 113, or mixtures thereof.

Suitable polymeric dyes include polymeric dyes selected from polymers (dye-polymer conjugates) comprising covalently bonded (sometimes referred to as conjugated) chromogens, e.g. polymers having chromogens copolymerized into the polymer backbone, and mixtures thereof. Polymeric dyes include those described in PCT publication: those of WO2011/98355, WO2011/47987, US2012/090102, WO2010/145887, WO2006/055787 and WO 2010/142503.

In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of: by name(Milliken, Spartanburg, South Carolina, USA), a fabric-entity colorant, a dye-polymer conjugate formed from at least one reactive dye, and a polymer selected from polymers comprising: hydroxyl moieties, primary amine moieties, secondary amine moieties, thiol moieties, and mixtures thereof. In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of:violet CT, hydroxymethyl CELLULOSE (CMC) covalently bonded to reactive blue, reactive Violet or reactive red dyes such as CMC conjugated to c.i. reactive blue 19, sold under the product name AZO-CM-cell by Megazyme, Wicklow, Ireland under the product code S-ACMC, alkoxylated triphenylmethane polymeric colorants, alkoxylated thiophene polymeric colorants and mixtures thereof.

Preferred hueing dyes include brighteners, which can be found in PCT publication: WO 2008/87497A1, WO2011/011799 and WO 2012/054835. Toners preferred for use in the present invention may be the preferred dyes disclosed in these references, including those selected from examples 1-42 in table 5 of PCT publication WO 2011/011799. Other preferred dyes are disclosed in U.S. patent 8,138,222. Other preferred dyes are disclosed in PCT publication WO 2009/069077.

Suitable dye clay conjugates include dye clays selected from the group comprising: comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof. In another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of: a cationic/basic dye selected from the group consisting of c.i. basic yellow 1 to 108, c.i. basic orange 1 to 69, c.i. basic red 1 to 118, c.i. basic violet 1 to 51, c.i. basic blue 1 to 164, c.i. basic green 1 to 14, c.i. basic brown 1 to 23, CI basic black 1 to 11, and a clay selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof. In another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of: montmorillonite basic blue B7 c.i.42595 conjugate, montmorillonite basic blue B9 c.i.52015 conjugate, montmorillonite basic violet V3 c.i.42555 conjugate, montmorillonite basic green G1 c.i.42040 conjugate, montmorillonite basic red R1 c.i.45160 conjugate, montmorillonite c.i. basic black 2 conjugate, hectorite basic blue B7 c.i.42555 conjugate, hectorite basic blue B9 c.i.52015 conjugate, hectorite basic violet V3 c.i.42555 conjugate, hectorite basic green G7 c.i.42040 conjugate, hectorite basic red R1 c.i.45160 conjugate, hectorite c.i. basic black 2 conjugate, saponite basic blue B7 c.i.42595 conjugate, saponite basic blue B9 c.i.15 conjugate, saponite basic blue B4203 v.i.420595 conjugate, saponite basic black 2 conjugate, saponite basic blue B9 c.i.15 conjugate, saponite basic blue b.i.42595 conjugate, saponite basic blue b.15 conjugate, saponite basic blue b.i.42595 conjugate, saponite basic red r.60 c.g.15 conjugate, saponite basic red r.15 conjugate, saponite basic red r.42595 conjugate, saponite basic red.

Suitable pigments include pigments selected from the group consisting of: flavanthrone, indanthrone, chlorinated indanthrone containing 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromo-dichloropyranthrone, dibromo-dichloropyranthrone, tetrabromo-pyranthrone, perylene-3, 4,9, 10-tetracarboxylic acid diimide, wherein the imide groups may be unsubstituted or substituted with C1-C3 alkyl or phenyl or heterocyclic groups, and wherein the phenyl and heterocyclic groups may additionally bear substituents that do not impart solubility in water, anthrapyrimidine carboxylic acid amides, anthrone violet, isoanthrone violet, diazine pigments, copper phthalocyanines that may contain up to 2 chlorine atoms per molecule, polychlorinated copper phthalocyanines or polychlorinated copper phthalocyanines that contain up to 14 bromine atoms per molecule, and mixtures thereof.

In another aspect, suitable pigments include pigments selected from the group consisting of: ultramarine blue (c.i. pigment blue 29), ultramarine violet (c.i. pigment violet 15), and mixtures thereof.

The foregoing fabric hueing agents may be used in combination (any mixture of fabric hueing agents may be used).

In another aspect, the cleaning active comprises an enzyme. Suitable enzymes include proteases, amylases, cellulases, lipases, xyloglucanases, pectate lyases, mannanases, bleaches, cutinases, and mixtures thereof. For enzymes, the accession numbers and IDs shown in parentheses refer to the entry numbers in the databases Genbank, EMBL and/or Swiss-Prot. For any mutation, the standard 1-letter amino acid coding is used together with the one representing the deletion. The accession number prefixed with DSM is the microorganism deposited at Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH (Mascheroder Weg 1b, 38124Brunswick (DSMZ)).

Protease: the composition may comprise a protease. Suitable proteases include metalloproteases and/or serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisin (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable proteases may be derived from a microorganism. Suitable proteases include chemically or genetically modified mutants of the above-described suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases or/and trypsin-type proteases. Examples of suitable neutral or alkaline proteases include:

(a) subtilisins (EC3.4.21.62), including those derived from Bacillus, such as Bacillus lentus (Bacillus lentus), Bacillus alkalophilus (Bacillus alkalophilus) (P27963, ELYA _ BACAO), Bacillus subtilis (Bacillus subtilis), Bacillus amyloliquefaciens (Bacillus amyloliquefaciens) (P00782, SUBT _ BACAM), Bacillus pumilus (Bacillus pumilus) (P07518) and Bacillus gibsonii (Bacillus gibsonii) (DSM 14391).

(b) Trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g. porcine-or bovine-derived trypsin), including fusarium protease and chymotrypsin derived from cellulomonas (A2RQE 2).

Suitable proteases include those derived from Bacillus gibsonii (Bacillus gibsonii) or Bacillus lentus such as subtilisin 309(P29600) and/or DSM5483 (P29599).

Suitable commercially available proteases include: by Novozymes A/S (Denmark) Andthose that are sold; tradename from Genencor International Andthose that are sold; sold under the trade name SolvayEnzymesAndthose that are sold; those available from Henkel/Kemira, i.e., BLAP (P29599 having the following mutations S99D + S101R + S103A + V104I + G159S), and variants thereof, including BLAPR (BLAP plus S3T + V4I + V199M + V205I + L217D),BLAPX (BLAP plus S3T + V4I + V205I) and BLAP F49(BLAP plus S3T + V4I + a194P + V199M + V205I + L217D); and KAP from Kao (alkalophilic bacillus subtilisin with mutations a230V + S256G + S259N).

In another aspect, a suitable proteolytic enzyme (protease) may be a catalytically active protein material that degrades or alters the type of stain protein present as a fabric stain in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin. Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges from 4 to 12 are available. Proteases with both high and low isoelectric points are suitable.

Amylase: suitable amylases are alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. Suitable alkaline alpha-amylases are derived from a strain of Bacillus, such as Bacillus licheniformis (Bacillus licheniformis), Bacillus amyloliquefaciens (Bacillus amyloliquefaciens), Bacillus stearothermophilus (Bacillus stearothermophilus), Bacillus subtilis, or other Bacillus, such as Bacillus NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM 9375, DSM 12368, DSM No.12649, KSM AP1378, KSM K36, or KSM K38. Suitable amylases include:

(a) an alpha-amylase derived from bacillus licheniformis (P06278, AMY _ BACLI) and variants thereof, particularly variants having substituents at one or more of the following positions: 15. 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444;

(b) AA560 amylases (CBU30457, HD066534) and variants thereof, especially variants with substitution at one or more of the following positions: 26. 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, optionally further comprising variants with deletions of D183 and G184;

(c) DSM 12649, having: (a) a mutation at one or more of positions 9, 26, 149, 182, 186, 202, 257, 295, 299, 323, 339, and 345; and (b) optionally having one or more, preferably all, substitutions and/or deletions in the following positions: 118. 183, 184, 195, 320 and 458, if present, preferably comprise R118K, DI83, GI84, N195F, R320K and/or R458K; and is

(d) Variants exhibiting at least 90% identity with the wild-type enzyme from Bacillus SP722(CBU30453, HD066526), in particular those lacking at positions 183 and 184.

Suitable commercially available alpha-amylases are TermamylStainzymeAnd(Novozymes A/S)，and variants thereof (Biocon India Ltd.),AT 9000(Biozym Ges.m.b.H，Austria)，Optisize HTand Purastar(Genencor International Inc.), and(KAO, Japan). Suitable amylases areAnd Stainzyme

Cellulase: the laundry detergent may comprise cellulase. Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases derived from bacillus, pseudomonas, humicola, fusarium, rhizopus, acremonium, e.g., fungal cellulases from humicola insolens, myceliophthora thermophila, and fusarium oxysporum.

Commercially available cellulases includeAnd(Novozymes A/S)，and Puradax(Genencor International Inc.), and(Kao Corporation)。

the cellulase may comprise an endoglucanase of microbial origin having endo-beta-1, 4-glucanase activity (e.c.3.2.1.4) comprising a budEndogenous bacterial polypeptides of bacillus member AA349 and mixtures thereof. Suitable endoglucanases are known under the trade name endoglucanaseAnd(Novozymes A/S (Bagsvaerd, Denmark)).

Suitable cellulases may also exhibit xyloglucanase activity, e.g.

Lipase: the composition may comprise a lipase. Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of lipases that can be used include those from the genus Humicola (the synonym thermophilic), for example from Humicola lanuginosa (Thermomyces lanuginosus), or from Humicola insolens lipase; pseudomonas lipases, for example from Pseudomonas alcaligenes or Pseudomonas pseudoalcaligenes, Pseudomonas cepacia, Pseudomonas stutzeri, Pseudomonas fluorescens, the species of Pseudomonas strain named SD705, Pseudomonas wisconsin; bacillus lipases, for example Bacillus subtilis, Bacillus stearothermophilus or Bacillus pumilus.

The lipase may be a "first cycle lipase", optionally a variant of a wild-type lipase derived from thermomyces lanuginosus comprising a T231R and N233R mutation. The wild-type sequence is 269 amino acids (amino acids 23-291) with the Swissprot accession number Swiss-ProtO59952 (from Thermomyces lanuginosus (Humicola lanuginosa)). Suitable lipases will include those known under the trade nameAndthose sold by Novozymes (Bagsvaerd, Denmark).

The laundry detergent or cleaning composition may comprise a variant of thermomyces lanuginosus (O59952) lipase having > 90% identity with the wild type amino acid and comprising one or more substituents at T231 and/or N233, optionally at T231R and/or N233R.

Xyloglucanase: suitable xyloglucanases have enzymatic activity on both xyloglucan and amorphous cellulose substrates. The enzyme may be a Glycosyl Hydrolase (GH) selected from GH families 5, 12, 44, 45 or 74. Glycosyl hydrolases selected from GH family 44 are particularly suitable. Suitable glycosyl hydrolases from GH family 44 are those derived from bacillus polymyxa (ATCC832) XYG1006 glycosyl hydrolases and variants thereof.

Also particularly suitable are glycosyl hydrolases selected from GH family 45 having a molecular weight of 17kDa to 30kDa, for example under the trade name GHEndoglucanases sold by NCD, DCC and DCL (AB Enzymes (Darmstadt, Germany)).

Pectate lyase: suitable pectate lyases are wild-type or are variants derived from Bacillus pectin lyases (CAF05441, AAU25568), under the trade name "pectate lyase And(purchased from Novozymes A/S, Bagsvaerd, Denmark).

Mannanase: suitable mannanases are known under the trade name(from Novozymes A/S, Bagsvaerd, Denmark) and(Genencor International Inc., Palo Alto, California).

Bleaching enzyme: suitable bleaching enzymes include oxidoreductases, for example oxidases such as glucose, choline or carbohydrate oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose-or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products are under the trade nameAndseries are sold by Novozymes. It may be advantageous to incorporate additional organic compounds, especially aromatic compounds, into the bleaching enzyme for use therewith; these compounds interact with bleaching enzymes to enhance the activity of oxidoreductases (enhancers) or to facilitate electron flow between the oxidase and the stain (regulators), usually with strongly different redox potentials on the oxidase and stain.

Other suitable bleaching enzymes include perhydrolases, which catalyze the formation of peracids from an ester substrate and a peroxygen source. Suitable perhydrolases include variants of Mycobacterium smegmatis perhydrolase, variants of perhydrolase commonly known as CE-7, and variants of wild-type surfactin having perhydrolase activity.

Cutinase: suitable cutinases are defined by e.c. class 3.1.1.73, optionally exhibiting at least 90%, or 95%, or most optionally at least 98% identity to a wild type derived from lanthanin against one of fusarium, pseudomonas mendocina, or humicola insolens.

Identity: the relationship between two amino acid sequences is described by the parameter "identity". For the purposes of the present invention, the alignment of two amino acid sequences is determined by the Needle program from EMBOSS software package (http:// EMBOSS. org), version 2.8.0. The Needle program performs the full sequence alignment algorithm described in (1970) J.Mol.biol.48, 443-. The substitution matrix used is BLOSUM62, the gap opening penalty is 10, and the gap extension penalty is 0.5.

In another aspect, the laundry detergent comprises a fabric softener. Suitable fabric softeners include clays, silicones and/or quaternary ammonium compounds. Suitable clays include montmorillonite clay, hectorite clay and/or laponite clay. A suitable clay is montmorillonite clay. Suitable silicones include aminosilicones and/or Polydimethylsiloxanes (PDMS). Suitable fabric softeners are particles comprising clay and silicone, such as particles comprising montmorillonite clay and PDMS.

In another aspect, the laundry detergent comprises a flocculant. Suitable flocculants include polyethylene oxide; for example having an average molecular weight of 300,000Da to 900,000 Da.

In another aspect, the laundry detergent comprises a suds suppressor. Suitable suds suppressors include silicones and/or fatty acids such as stearic acid.

In another aspect, the laundry detergent comprises a perfume. Suitable perfumes include perfume microcapsules, polymer assisted perfume delivery systems including schiff base perfume/polymer complexes, starch encapsulated perfume accords, perfume loaded zeolites, blooming perfumes, and any combination thereof. Suitable perfume microcapsules are based on melamine formaldehyde, typically comprising a perfume encapsulated by a shell comprising melamine formaldehyde. Such perfume microcapsules are highly suitable for containing cationic and/or cationic precursor materials, such as polyvinyl formamide (PVF) and/or cationically modified hydroxyethylcellulose (catHEC), in the shell.

In another aspect, the laundry detergent comprises other aesthetic agents. Other suitable aesthetic particles can include soap rings, layered aesthetic particles, gelatin beads, carbonate and/or sulfate speckles, colored clay particles, and any combination thereof.

Builder: suitable builders include zeolites, phosphates, citrates, and any combination thereof.

Zeolite builder: the laundry detergent may be substantially free of zeolite builder. Substantially free of zeolite builder typically means comprising from 0 wt% to 10 wt% zeolite builder, or to 8 wt%, or to 6 wt%, or to 4 wt%, or to 3 wt%, or to 2 wt%, or even to 1 wt% zeolite builder. Substantially free of zeolite builder preferably means "unintentionally added" zeolite builder. Typical zeolite builders include zeolite a, zeolite P, zeolite MAP, zeolite X and zeolite Y.

Phosphate builders: the laundry detergent may be substantially free of phosphate builder. Substantially free of phosphate builder typically means comprising from 0 wt% to 10 wt% phosphate builder, or to 8 wt%, or to 6 wt%, or to 4 wt%, or to 3 wt%, or to 2 wt%, or even to 1 wt% phosphate builder. Substantially free of phosphate builder preferably means "unintentionally added" phosphate builder. A typical phosphate builder is Sodium Tripolyphosphate (STPP), which can be used in combination with sodium orthophosphate and/or sodium pyrophosphate.

Additionally or alternatively, other inorganic builders that may be present include sodium carbonate and/or sodium bicarbonate.

Organic builders that may be present include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartic acid; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol monosuccinates, glycerol disuccinates and glycerol trisuccinates, carboxymethoxysuccinates, carboxymethoxymalonates, bipyridinates, hydroxyethyliminodiacetates, alkyl-and alkenylmalonates and succinates; and sulfonated fatty acid salts.

Buffers and alkalinity sources: suitable buffering agents and alkalinity sources include carbonates and/or silicates and/or double salts such as burkeite.

Carbonate salt: suitable carbonates are sodium carbonate and/or sodium bicarbonate. The laundry detergent may comprise bicarbonate. The composition may suitably comprise a small amount of carbonate, for example, the composition may suitably comprise from 0 wt% to 10 wt% carbonate, or to 8 wt%, or to 6 wt%, or to 4 wt%, or to 3 wt%, or to 2 wt%, or even to 1 wt% carbonate. The laundry detergent may even be substantially free of carbonate; substantially free means "not intentionally added".

The carbonate salt may have a weight average particle size of 100 microns to 500 microns. Alternatively, the carbonate salt may have a weight average particle size of 10 to 25 microns.

Silicate salt: the laundry detergent may comprise from 0 wt% to 20 wt%, or to 15 wt%, or to 10 wt%, or to5 wt%, or to 4 wt%, or even to 2 wt% silicate, and may comprise more than 0 wt%, or 0.5 wt%, or even 1 wt% silicate. The silicate may be crystalline or amorphous. Suitable crystalline silicates include crystalline layered silicates such as SKS-6. Other suitable silicates include 1.6R silicate and/or 2.0R silicate. A suitable silicate is sodium silicate. Another suitable silicate is sodium metasilicate.

Filling: the laundry detergent may comprise from 0 wt% to 70 wt% of a filler. Suitable fillers include sulphate and/or bio-filler materials.

Sulfate: a suitable sulphate is sodium sulphate. The sulfate salt may have a weight average particle size of 100 to 500 micrometers, alternatively, the sulfate salt may have a weight average particle size of 10 to 45 micrometers.

Biological filling material: suitable bio-fill materials are alkali and/or bleach treated agricultural wastes.

Calcium carbonate crystal growth inhibitor: the laundry detergent may comprise a calcium carbonate crystal growth inhibitor, such as one selected from the group consisting of: 1-hydroxyethyl diphosphonic acid (HEDP) and salts thereof; n, N-dicarboxymethyl-2-aminopentane-1, 5-dioic acid or its salt; 2-phosphonobutane-1, 2, 4-tricarboxylic acid and salts thereof; and any combination thereof.

Antiredeposition agents such as cellulose esters and ethers, for example sodium carboxymethylcellulose, may also be present.

Other ingredients that may be present include solvents, hydrotropes such as sodium or calcium cumene sulphonate, potassium naphthalene sulphonate and the like, fluorescers, foam boosters or foam control agents (defoamers) (optionally sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, sodium acetate, TEA-25 (polyethylene glycol ether or cetyl alcohol), calcium chloride, other inorganic salts), flow aids such as silica and amorphous aluminosilicates, fabric conditioning compounds, other clay and soil removal/anti-redeposition agents, other perfumes or pro-perfumes, and combinations of one or more of these cleaning aids.

Method of using laundry detergent or cleaning compositions

The compositions are generally used for cleaning and/or treating a situs, especially a surface or fabric. As used herein, "surface" may include surfaces such as dishes, glass, and other cooking surfaces, hard surfaces, hair, or skin. Such methods include the steps of: embodiments of laundry detergents or cleaning compositions (in pure form or diluted in the wash liquor) are contacted with at least a portion of a surface or fabric, and such surface or fabric is optionally rinsed. The surface or fabric may be subjected to a washing step prior to the rinsing step described above. For purposes of the present invention, "washing" includes, but is not limited to, scrubbing, wiping, and mechanical agitation.

The pH of the composition solution is selected to be most suitable for the target surface to be cleaned, across a wide range of pH, from about 5 to about 11. The pH of the above compositions is preferably from about 5 to about 8 for personal care such as skin and hair cleansing, and from about 8 to about 10 for laundry cleansing compositions. The composition is preferably used at a concentration of about 200ppm to about 10,000ppm in solution. The water temperature is preferably in the range of about 5 ℃ to about 100 ℃.

As will be appreciated by those skilled in the art, the laundry detergents of the present invention are ideally suited for use in laundry applications. Accordingly, the present invention includes a method for laundering fabrics. The method may comprise the step of contacting the fabric to be laundered with a laundry detergent comprising a carboxyl group-containing polymer. The fabric may comprise most any fabric capable of being laundered under normal consumer use conditions. The solution preferably has a pH of about 8 to about 10.5. The laundry detergent may be used at a concentration of about 500ppm to about 15,000ppm in solution, and more dilute wash conditions may optionally be employed. The water temperature is typically in the range of about 5 ℃ to about 90 ℃. The water to fabric ratio is typically from about 1:1 to about 30: 1.

The method of laundering fabrics may be carried out in a top-loading or front-loading automatic washing machine, or may be used in hand-wash laundry applications. In these applications, the concentration of the formed wash liquor and laundry detergent composition in the wash liquor is those in the main wash cycle. During any optional rinse step or steps, when determining the volume of the wash liquor, no added water is included.

The wash liquor may comprise 40 litres or less of water, or 30 litres or less, or 20 litres or less, or 10 litres or less, or 8 litres or less, or even 6 litres or less of water. The wash liquor may comprise from above 0 litres to 15 litres, or 2 litres, and to 12 litres, or even to 8 litres of water. In the case of dilute wash conditions, the wash liquor may comprise 150 liters or less of water, 100 liters or less of water, 60 liters or less of water, or 50 liters or less of water, especially for hand wash conditions, and may depend on the number of rinses.

Usually 0.01kg to 2kg of fabrics per litre of wash liquor are added to the wash liquor. Usually 0.01Kg, or 0.05Kg, or 0.07Kg, or 0.10Kg, or 0.15Kg, or 0.20Kg, or 0.25Kg of fabric per litre of washing liquor is added to the washing liquor.

Optionally contacting 50g or less, or 45g or less, or 40g or less, or 35g or less, or 30g or less, or 25g or less, or 20g or less, or even 15g or less, or even 10g or less of the composition with water to form a wash liquor.

As will be appreciated by those skilled in the art, the above cleaning compositions are ideally suited for use in household care (hard surface cleaning compositions) and/or dish cleaning compositions.

Test method

Various techniques are known in the art to determine the performance of the laundry detergent or cleaning compositions of the present invention comprising carboxyl group containing polymers, however the following determination must be used in order for the invention described and claimed herein to be fully understood.

Test 1: determination of weight average molecular weight (Mw)

The weight average molecular weight of the polymer was determined via Gel Permeation Chromatography (GPC) technique under the following conditions.

A measuring device: l-7000 series (Hitachi Ltd. product)

A detector: HITACHI RI Detector, L-7490

Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B (product of Showa Denko K.K.)

Column temperature: 40 deg.C

Flow rate: 0.5mL/min

Calibration curve: polyacrylic acid standard (product of Sowa Kagaku Co., Ltd.)

Eluting the solution; 0.1N sodium acetate/acetonitrile 3/1 (mass ratio)

And (3) testing 2: limitation of monomers and adducts

Ether bond-containing monomers, sulfonic acid group-containing monomers, acrylic acid group monomers, and bisulfite adducts were quantified via High Pressure Liquid Chromatography (HPLC) using the following conditions.

A measuring device: l-7000 series (Hitachi Ltd. product)

A detector: UV Detector, L-7400 (product of Hitachi Ltd.)

Column: SHODEX RSpak DE-413 (product of Showa Denko K.K.)

Temperature: 40.0 deg.C

Eluting the solution; 0.1% phosphoric acid aqueous solution

Flow rate: 1.0mL/min

And (3) testing: measurement of solid content

A mixture of 1.0g of the carboxyl group-containing polymer composition of the present invention and 1.0g of water was left in an oven heated to 130 ℃ for one hour under a nitrogen atmosphere to dry it. From the mass change before and after the drying step, the solid content (%) and the volatile component content (%) were calculated.

And (4) testing: anti-soil redeposition test (hard water condition)

This test measures the ability of the polymer to prevent soil deposition onto the fabric. The anti-soil redeposition ability test was performed with carbon black according to the following method.

(1) Test fabrics selected from white cotton cloth (available from Testfabric Inc.) were cut into samples of 5cm x 5 cm. The whiteness of the white cloth samples was determined by measuring the reflectance with a colorimetric colorimeter (product of SE2000, Nippon Denshoku Industries co., ltd.).

(2) Pure (ion-exchanged) water was added to calcium chloride dihydrate (8.82g) so that hard water conditions (20Kg) were made.

(3) A mixture (90.0g) was prepared by adding pure (ion-exchanged) water to sodium dodecylbenzenesulfonate (4g), sodium bicarbonate (4.75g) and sodium sulfate (4g), and adjusting to pH 10 with aqueous sodium hydroxide solution. Pure water was further added thereto so that an aqueous surfactant solution (total 100.0g) was prepared.

(4) The scale remover was set to 25 ℃. Hard water (1L), aqueous surfactant solution (2.5g), 0.4% (based on solids content) aqueous polymer solution (2.5g), zeolite (0.075g) and carbon black (0.5g) were stirred in a reaction kettle at 100rpm for one minute. Subsequently, seven samples of white cloth were placed into the mixture and the mixture was stirred at 100rpm for ten minutes.

(5) The white cloth sample was wrung by hand and hard water (1L) at 25 ℃ was poured into the reaction kettle and stirred at 100rpm for two minutes.

(6) The white cloth swatches were each covered with a piece of cloth and dried by ironing while ironing wrinkles. The whiteness of the cloth sample was measured again by reflectance with a colorimeter.

(7) Based on the measurement results, the anti-soil redeposition rate was determined by the following formula:

and (5) testing: and a surfaceCompatibility testing of active Agents

Laundry detergents each comprising a carboxyl group-containing polymer were prepared using the following materials:

SFT-70H (polyoxyethylene alkyl ether, product of NIPPON shokubali co., ltd.): 40g of

NEOPELEX F-65 (sodium dodecylbenzenesulfonate, product of Kao Corp.): 7.7g

(active ingredient: 5g)

Kohtamin 86W (stearyltrimethylammonium chloride, product of Kao corp.): 17.9g

(active ingredient: 5g)

Diethanolamine: 5g

Ethanol: 5g

Propylene glycol: 5g

Testing a sample: 1.5g (based on solid content)

Ion exchange water: the balance to provide 100g of the detergent composition.

(1) The mixture was stirred well so that all the components were uniformly dispersed. The turbidity of the mixture (kaolin turbidity, mg/L) was assessed from the measured turbidity using a turbidimeter ("NDH 2000", product of Nippon Denshoku co., ltd.) at 25 ℃.

(2) The results were rated based on the following criteria:

good taste: kaolin turbidity is not less than 0 and less than 50 mg/L; no phase separation, precipitation and turbidity were visually observed.

Medium and high grade: the kaolin turbidity is not less than 50mg/L and less than 200 mg/L; slight cloudiness was visually observed.

Difference (D): the turbidity of the kaolin is not less than 200mg L; cloudiness was visually observed.

And 6, testing: whiteness retention measurement

The test is intended to measure the ability of a laundry detergent to prevent the loss of whiteness of a fabric (i.e. whiteness maintenance). Fabric whiteness retention was assessed by image analysis after single or multiple cycles of washing. Generally, "whiteness" can be reported in its whiteness index, which can be conveniently converted from CIELAB (an international certified color scale system developed by CIE ("Commission international de I' Eclairage"). The CIE scale of whiteness is the most commonly used index of whiteness and relates to measurements made under D65 illumination, which is a standard representation of outdoor daylight. Whiteness, in the generic term, is a single numerical index relating to the relative degree of whiteness (of a near-white material under particular lighting conditions), and the higher the number, the whiter the material. For example, for a fully reflective non-fluorescent white material, the CIE whiteness index (L x) would be 100.

The procedure for assessing whiteness retention of the laundry detergent of the invention was as follows:

(1) 1.1g of laundry detergent raw material was dissolved in 600g of triple filtered (using 0.1 micron Millipore membrane filter with vacuum Brinell filtration apparatus) deionized water according to the concentrations provided in Table 1 herein.

Table 1:detergent solution

(2) 14mL of the wash solution was transferred to a 20mL glass vial. The wash solution is then mixed with the polymer of the invention or the comparative polymer to produce a "modified" laundry detergent wash solution. For each polymer or comparative polymer tested, two glass vials were prepared and 14 μ l and 56 μ l of 1% solution were added. Teflon coated magnets were added for additional stirring.

(3) Mu.l of a 1% stock hardness solution were added to the wash solution. A 1% water hardness solution was prepared according to the following procedure.

(4) A 1% water hardness solution was prepared according to the following procedure. Into a 1L beaker, 168.09g of CaC1 were added₂-2H₂O and 116.22g MgC1₂-6H₂And O. 800mL of deionized water was added. Using a stir bar and a stir station, the solution was stirred until mixedThe material dissolved and the solution became clear. The solution was poured into a 1L volumetric flask and filled to the 1L score line. The stir bar was added to the flask and stirred for an additional 5 minutes. The stir bar was removed and refilled with deionized water to 1L of score line. The solution was stored in a plastic bottle until ready for use.

(5) 6.1 μ L of the artificial body scale was added to the wash solution in a 20mL glass vial. Artificial body scale compositions were prepared according to table 2.

Table 2:artificial body dirt composition

(6) The test fabric was selected from 1.5cm diameter polyester fabric (PW19) and/or 1.5cm diameter cotton fabric (CW120) available from Emerical Manufacturing Company (Blue Ash, Cincinnati). Nine pieces of polyester fabric and nine pieces of cotton fabric were added to a 20mL glass vial of wash solution. A 20mL wash vial was securely mounted to a model 75 Wrist Action shaker (Burrell Scientific, Pittsburgh, Pennsylvania). A timer was used and the wash was run for 30 minutes. At the end of the wash, the glass vial on the buchner funnel was emptied of the contents of the wash solution. The test fabric discs were transferred to another 20mL vial and 14mL of rinse solution was added.

(7) To prepare the rinse solution, 28 μ L of a 1% strength solution was added to 14mL of deionized filtered water. The vial was mounted to a Wrist Action shaker and rinsed for 3 minutes. At the end of the rinse, the fabric was removed from the Wrist Action shaker and the test fabric was placed on a black plastic template. It was allowed to air dry for at least two hours. For a multi-cycle wash, only the above steps are repeated.

(8) Two whiteness index measurements before (i.e., initial) and after (i.e., treated) wash cycles were performed for each test fabric using CIELab color parameters with a Datacolor spectrometer. The relative whiteness index (i.e., loss of whiteness) between the initially unwashed fabric and the finally washed fabric is reported.

(9) For each fabric tested, aw (i.e., aw) representing the difference in whiteness index measurements between the initial and treated fabrics was calculated and is represented by the following calculation:

Δ W — initial whiteness index-treated whiteness index.

Generally, Δ W is negative because whiteness tends to decrease after washing.

(10) In addition, the percent whiteness maintenance effect (i.e. -%) was determined using the following calculation

WME)：

Wherein:

ΔW_PiΔ W ═ of polymers of interest

ΔW_PrΔ W of a base polymer (e.g. comparative polymer 1 or 2)

% WME stands for laundry detergent (especially polymer) to prevent fabric whiteness after laundering

The ability to be lost. At higher% WME, whiteness retention is improved.

Examples of the invention

Hereinafter, the present invention is described in more detail based on examples. All parts are by weight unless otherwise indicated and all percentages are by mass unless otherwise indicated.

Example 1: synthesis of carboxyl group-containing polymers

The carboxyl group-containing polymers in table 3 below were prepared by the methods disclosed herein, but may be synthesized by other methods known to those skilled in the art. Thus, the following synthetic examples are intended to illustrate methods for synthesizing polymers and are not intended to limit the scope of the invention.

Table 3:properties of the synthesized carboxyl group-containing Polymer

Example 1A: synthesis of Polymer 1

(1)Synthesis of monomers

In a 500mL four-necked glass flask equipped with a reflux condenser and a stirrer (blade), n-butanol (370.0g) and sodium hydroxide pellets (4.27g) were stirred while heating to 60 ℃. Allyl glycidyl ether (hereinafter referred to as "AGE") (57.0g) was then added thereto over 30 minutes, followed by allowing the mixture to react for five hours. The resulting solution was transferred to a 1000mL recovery flask and the solvent was removed therefrom via a rotary evaporator. To the residue was added a 20 mass% aqueous solution of sodium chloride (200.0g), and the resulting aqueous solution was transferred to a 500mL separatory funnel. The solution was shaken well and then allowed to stand until the solution separated into phases. The lower phase was removed and the upper phase was transferred to a 300mL recovery flask to remove the solvent therein via a rotary evaporator. The precipitated salt was removed by filtration, thereby obtaining a polymer (1).

(2)Polymerisation

In a 1000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (128.4g) and ferrous ammonium sulfate (0.0187g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% acrylic acid aqueous solution (hereinafter also referred to as 80% AA) (270.0g), 40% 3-allyloxy-2-hydroxypropanesulfonic acid sodium aqueous solution (hereinafter also referred to as 40% HAPS) (192.0g), monomer (1) (15.0g), 15% sodium persulfate aqueous solution (hereinafter also referred to as 15% NaPS) (68.7g), and 35% sodium bisulfite aqueous solution (hereinafter also referred to as 35% SBS) (19.6g) were separately added dropwise through different nozzles to the polymerization reaction system kept at 85 ℃. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

After completion of the addition of 80% AA, the reaction solution was kept (aged) at 85 ℃ for 30 minutes. Thus, the polymerization was completed. After completion of the polymerization, the polymerization reaction solution was allowed to cool under stirring, and then gradually added dropwise with a 48% aqueous solution of sodium hydroxide (hereinafter also referred to as 48% NaOH) (193.3g) to neutralize.

Through these steps, an aqueous polymer solution (1) comprising the polymer (1) of the present invention is produced. The solid content of the aqueous polymer solution (1) was 45%, and the weight-average molecular weight of the polymer (1) was 35,000. The polymer (1) contained 5 mass% of the structure (a), 23 mass% of the unit (b), and 72 mass% of the unit (c).

Example 1B: synthesis of Polymer 2

(1)Synthesis of monomers

In a 2L four-necked glass flask equipped with a reflux condenser and a stirrer (blade), pure water (491.0g) and di-n-butylamine (258.0g) were stirred under a nitrogen purge while controlling the liquid temperature at 50 ℃. AGE (232.8g) was then added dropwise gradually over two hours with stirring. The liquid temperature was maintained at 50 ℃ to 60 ℃. After completion of the dropwise addition, the resultant mixture was aged for two hours while keeping the liquid temperature at 60 ℃.

After cooling to room temperature, the liquid was transferred to a separatory funnel and left to stand. Thus, the liquid separates into two phases. The lower aqueous phase was removed. The upper phase was washed with pure water. The resulting liquid was transferred to a recovery flask and the water was completely removed therefrom via a rotary evaporator. Thus, monomer (2) was obtained.

(2)Polymerisation

In a 1000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (128.6g) and ferrous ammonium sulfate (0.0186g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (270.0g), 40% HAPS (192.0g), monomer (2) (15.0g), 15% NaPS (68.3g), and 35% SBS (14.6g) were added dropwise separately through different nozzles to the polymerization system maintained at 85 ℃ under stirring. The dropping times of 80% AA, 40% HAPS, monomer (2), 15% NaPS, and 35% SBS were 180 minutes, 150 minutes, 120 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (2) comprising the polymer (2) of the present invention is produced. The solid content of the aqueous polymer solution (2) was 45%, and the weight-average molecular weight of the polymer (2) was 37,000. The polymer (2) contained 15 mass% of the structure (a), 13 mass% of the unit (b), and 72 mass% of the unit (c).

Example 1C: synthesis of Polymer 3

In a 1000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (146.8g) and ferrous ammonium sulfate (0.0186g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (270.0g), 40% HAPS (150.2g), monomer (1) (30.0g), 15% NaPS (68.7g), and 35% SBS (19.6g) were added dropwise separately through different nozzles to the polymerization reaction system maintained at 85 ℃ with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 130 minutes, 140 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

After completion of the addition of 80% AA, the reaction solution was kept (aged) at 85 ℃ for 30 minutes. Thus, the polymerization was completed. After completion of the polymerization, the polymerization reaction solution was allowed to cool under stirring, and then neutralized gradually dropwise with 48% NaOH (197.5 g).

Through these steps, an aqueous polymer solution (3) comprising the polymer (3) of the present invention is produced. The solid content of the aqueous polymer solution (3) was 45%, and the weight-average molecular weight of the polymer (3) was 46,000. The polymer (3) contained 10 mass% of the structure (a), 18 mass% of the unit (b), and 72 mass% of the unit (c).

Example 1D: poly(s) are polymerizedSynthesis of Compound 4

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (184.1g) and ferrous ammonium sulfate (0.0252g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (400.0g), 40% HAPS (166.9g), monomer (1) (20.0g), 15% NaPS (102.4g), and 35% SBS (22.2g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 200 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (4) comprising the polymer (4) of the present invention is produced. The solid content of the aqueous polymer solution (4) was 45%, and the weight-average molecular weight of the polymer (4) was 35,000. The polymer (4) contains 5 mass% of the structure (a), 15 mass% of the unit (b), and 80 mass% of the unit (c).

Example 1E: synthesis of Polymer 5

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (222.5g) and ferrous ammonium sulfate (0.0249g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (450.0g), 40% HAPS (55.6g), monomer (1) (20.0g), 15% NaPS (111.1g), and 35% SBS (22.3g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 150 minutes, 200 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (5) comprising the polymer (5) of the present invention is produced. The solid content of the aqueous polymer solution (5) was 45%, and the weight-average molecular weight of the polymer (5) was 37,000. The polymer (5) contains 5 mass% of the structure (a), 5 mass% of the unit (b), and 90 mass% of the unit (c).

Example 1F: synthesis of Polymer 6

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (184.1g) and ferrous ammonium sulfate (0.0251g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (400.0g), 40% HAPS (166.9g), monomer (1) (20.0g), 15% NaPS (102.4g), and 35% SBS (18.0g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 200 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (6) comprising the polymer (6) of the present invention is produced. The solid content of the aqueous polymer solution (6) was 45%, and the weight-average molecular weight of the polymer (6) was 47,000. The polymer (6) contained 5 mass% of the structure (a), 15 mass% of the unit (b), and 80 mass% of the unit (c).

Example 1G: synthesis of Polymer 7

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (187.8g) and ferrous ammonium sulfate (0.0251g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (400.0g), 40% HAPS (166.9g), monomer (1) (20.0g), 15% NaPS (97.2g), and 35% SBS (20.8g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (7) comprising the polymer (7) of the present invention is produced. The solid content of the aqueous polymer solution (7) was 45%, and the weight-average molecular weight of the polymer (7) was 39,000. The polymer (7) contained 5 mass% of the structure (a), 15 mass% of the unit (b), and 80 mass% of the unit (c).

Example 1H: synthesis of Polymer 8

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (187.8g) and ferrous ammonium sulfate (0.0252g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (400.0g), 40% HAPS (166.9g), monomer (1) (20.0g), 15% NaPS (97.2g), and 35% SBS (23.6g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (8) comprising the polymer (8) of the present invention is produced. The solid content of the aqueous polymer solution (8) was 45%, and the weight-average molecular weight of the polymer (8) was 32,000. The polymer (8) contained 5 mass% of the structure (a), 15 mass% of the unit (b), and 80 mass% of the unit (c).

Example 1I: synthesis of Polymer 9

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (182.6g) and ferrous ammonium sulfate (0.0253g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (400.0g), 40% HAPS (166.9g), monomer (1) (20.0g), 15% NaPS (102.4g), and 35% SBS (30.5g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 200 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (9) comprising the polymer (9) of the present invention is produced. The solid content of the aqueous polymer solution (9) was 45%, and the weight-average molecular weight of the polymer (9) was 25,000. The polymer (9) contained 5 mass% of the structure (a), 15 mass% of the unit (b), and 80 mass% of the unit (c).

Example 1J: synthesis of Polymer 10

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (295.5g) and ferrous ammonium sulfate (0.0354g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (590.6g), 40% HAPS (125.2g), monomer (1) (45.0g), 15% NaPS (140.7g), and 35% SBS (30.1g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 150 minutes, 200 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (10) comprising the polymer (10) of the present invention is produced. The solid content of the aqueous polymer solution (10) was 45%, and the weight-average molecular weight of the polymer (10) was 46,000. The polymer (10) contains 8 mass% of the structure (a), 8 mass% of the unit (b), and 84 mass% of the unit (c).

Example 1K: synthesis of Polymer 11

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (250.4g) and ferrous ammonium sulfate (0.0360g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (522.0g), 40% HAPS (371.1g), monomer (1) (29.0g), 15% NaPS (132.8g), and 35% SBS (26.6g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (11) comprising the polymer (11) of the present invention is produced. The solid content of the aqueous polymer solution (11) was 45%, and the weight-average molecular weight of the polymer (11) was 43,000. The polymer (11) contained 5 mass% of the structure (a), 23 mass% of the unit (b), and 72 mass% of the unit (c).

Example 1L: synthesis of Polymer 12

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (280.4g) and ferrous ammonium sulfate (0.0352g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (548.6g), 40% HAPS (185.5g), monomer (1) (50.0g), 15% NaPS (134.1g), and 35% SBS (55.5g) were added dropwise separately through different nozzles to the polymerization system maintained at 85 ℃ under stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 150 minutes, 200 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (12) comprising the polymer (12) of the present invention is produced. The solid content of the aqueous polymer solution (12) was 45%, and the weight-average molecular weight of the polymer (12) was 22,000. The polymer (12) contained 9 mass% of the structure (a), 12 mass% of the unit (b), and 79 mass% of the unit (c).

Example 1M: synthesis of Polymer 13

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (252.1g) and ferrous ammonium sulfate (0.0356g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (566.7g), 40% HAPS (268.0g), monomer (1) (17.0g), 15% NaPS (137.6g), and 35% SBS (29.5g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 200 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (13) comprising the polymer (13) of the present invention is produced. The solid content of the aqueous polymer solution (13) was 45%, and the weight-average molecular weight of the polymer (13) was 34,000. The polymer (13) contains 3 mass% of the structure (a), 17 mass% of the unit (b), and 80 mass% of the unit (c).

Example 1N: synthesis of Polymer 14

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (101.9g) and ferrous ammonium sulfate (0.0222g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (332.5g), 40% HAPS (237.5g), monomer (1) (19.0g), 15% NaPS (85.6g), and 35% SBS (30.6g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 150 minutes, 120 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (14) comprising the polymer (14) of the present invention is produced. The solid content of the aqueous polymer solution (14) was 45%, and the weight-average molecular weight of the polymer (14) was 28,000. The polymer (14) contains 5 mass% of the structure (a), 1523 mass% of the unit (b), and 8072 mass% of the unit (c).

Example 1O: synthesis of Polymer 15

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (130.2g) and ferrous ammonium sulfate (0.0185g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (270.0g), 40% HAPS (192.0g), monomer (1) (15.0g), 15% NaPS (68.7g), and 35% SBS (9.8g) were added dropwise separately to the polymerization system maintained at 85 ℃ through different nozzles, with stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, an aqueous polymer solution (15) comprising the polymer (15) of the present invention is produced. The solid content of the aqueous polymer solution (15) was 45%, and the weight-average molecular weight of the polymer (15) was 58,000. The polymer (15) contained 5 mass% of the structure (a), 23 mass% of the unit (b), and 72 mass% of the unit (c).

Example 2: synthesis of comparative polymers

The comparative polymers in table 4 below were prepared by the methods disclosed herein, but may be synthesized by other methods known to those skilled in the art. Thus, the following synthetic examples are intended to illustrate the methods used to synthesize the polymers and are not intended to limit the scope of the invention.

Table 4:properties of the comparative Polymer synthesized

Example 2A: synthesis of comparative Polymer 1

In a 2000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (125.7g) and ammonium ferrous sulfate (0.0190g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (270.0g), 40% HAPS (192.0g), monomer (1) (15.0g), 15% NaPS (68.7g), and 35% SBS (34.3g) were added dropwise separately through different nozzles to the polymerization system kept at 85 ℃ under stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, a comparative polymer aqueous solution (2) containing the comparative polymer (2) was prepared. The solid content of the comparative aqueous polymer solution (2) was 45%, and the weight average molecular weight of the comparative polymer (2) was 17,000. The comparative polymer (2) contained 5 mass% of the structure (a), 23 mass% of the unit (b), and 72 mass% of the unit (c).

Example 2B: synthesis of comparative Polymer 2

Comparative polymer 4 ("CP 4") can be made by the methods disclosed in PCT publication WO2010/04468, the methods disclosed herein, or methods known to those skilled in the art. Alternatively, CP4 may be made as follows.

In a 1000mL glass separatory flask equipped with a reflux condenser and a stirrer (blade), pure water (121.1g) and ammonium ferrous sulfate (0.0194g) were stirred while heating to 85 ℃. Thus, a polymerization reaction system was established. Next, 80% AA (270.0g), 40% HAPS (192.0g), monomer (1) (15.0g), 15% NaPS (68.7g), and 35% SBS (58.9g) were added dropwise separately through different nozzles to the polymerization system maintained at 85 ℃ under stirring. The dropping times of 80% AA, 40% HAPS, monomer (1), 15% NaPS, and 35% SBS were 180 minutes, 120 minutes, 150 minutes, 190 minutes, and 175 minutes, respectively. The dropwise addition of each solution was continuously performed at a constant rate.

Through these steps, a comparative polymer aqueous solution (2) containing the comparative polymer (2) was prepared. The solid content of the comparative aqueous polymer solution (2) was 45%; the weight average molecular weight of the comparative aqueous polymer solution (2) was 8,200; and the soil redeposition resistance of the comparative aqueous polymer solution (2) was 32.6% according to the above test method. The comparative polymer (2) contained 5 mass% of the structure (a), 23 mass% of the unit (b), and 72 mass% of the unit (c).

Example 3: results from anti-soil redeposition analysis

Selected examples of carboxyl group-containing polymers of the present invention versus comparative polymers were analyzed for their anti-soil redeposition rate (i.e., ability) in the methods described in the test methods section. The results are provided in table 5 herein. For each polymer and comparative polymer, the mass ratios (mass%) between the structural units (a), (b), and (c) are provided in table 5; 3-sulfopropionic acid (3SPA) content (ppm); and weight average molecular weight (g/mol). In addition, "OBu" and "OBu" as used in Table 5₂"refers to an n-butanol group in which a hydrogen atom of n-butanol is removed, and a di-n-butylamine group in which a hydrogen atom of di-n-butylamine is removed, respectively.

Results: the results show that carboxyl group-containing polymers comprising specific contents of structural units (a) derived from an ether bond-containing monomer (a), structural units (B) derived from a sulfonic acid group-containing monomer (B), and structural units (C) derived from an acrylic acid group-containing monomer (C) and having a specific weight average molecular weight, and compositions comprising these carboxyl group-containing polymers and preferably having a specific amount of an adduct of bisulfite with an acrylic acid group-containing monomer (C), have high anti-soil redeposition ability, especially under high hard water washing conditions. In addition, the difference in anti-soil redeposition ability between the carboxyl group containing polymers of the present invention was much higher than comparative polymer 1(m.w.17,000) and indicates that when formulated into the laundry detergents of the present invention, the carboxyl group containing polymers would have the requisite level of performance enhancement required to prevent soil components from reattaching to the fabric under higher hard water conditions. Additionally, without intending to be limited by theory, it is believed that the anti-soil redeposition ratio is a good and reproducible predictive value for the overall whiteness maintenance characteristics of the polymer when the polymer is added to a laundry detergent composition according to the present invention.

Table 5:resistance of selected examplesRate of soil redeposition

Example 4: whiteness maintenance of selected examples

The whiteness maintenance performance of the carboxyl group-containing polymers of the invention was assessed in a sample laundry detergent formulation as compared to a comparative polymer in a method described in the whiteness maintenance assay as described herein. The purpose of this test is to demonstrate the improved whiteness maintenance performance of the carboxyl group-containing polymers of the present invention. Specifically, the inventors identified representative polymers from PCT publication WO2010/04468, which are disclosed herein as comparative polymers 1 and 2 (also referred to as "CP 1" and "CP 2," respectively).

CP1 is a carboxyl group-containing polymer having a weight average molecular weight of 17,000, and a molar ratio of 5 mass% of an ether bond-containing monomer, 23 mass% of a sulfonic acid group monomer, and 72 mass% of an acrylic acid group monomer. And CP2 is a carboxyl group-containing polymer having a weight average molecular weight of 8,200, and a molar ratio of 5 mass% of an ether bond-containing monomer, 23 mass% of a sulfonic acid group monomer, and 72 mass% of an acrylic acid group monomer.

Thus, comparative polymers 1 and 2 are not within the claimed weight average molecular weight range of about 20,000 to about 60,000 due to their lower weight average molecular weight. A complete list of the polymers selected for evaluation and the comparative polymers is shown in table 6.

TABLE 6Selection of polymers for whiteness evaluation and comparative polymers

Results: the results for high concentrations (i.e.40 ppm under conventional washing conditions) of carboxyl group containing polymers or comparative polymers are provided in tables 7 and 8. The results for low concentrations (i.e., 10ppm under conventional washing conditions) of carboxyl group-containing polymers or comparative polymers are provided in tables 9 and 10。

The results in tables 7 and 8 show that at high concentrations, carboxyl group containing polymers 1 and 4 show superior W whiteness index (i.e., whiteness index) than any of the comparative polymers the improved whiteness retention is even more pronounced when laundry detergents are formulated using low concentrations of carboxyl group containing polymers compared to the comparative polymers, as shown in tables 9 and 10. The results tend to show that the carboxyl group-containing polymer is significantly more reactive than the comparative polymer on a molar basis, and thus the carboxyl group-containing polymer can be sufficiently reactive, especially under dilute wash conditions, to achieve the desired cleaning performance, i.e., whiteness maintenance. These results facilitate the use of the carboxyl group containing polymers of the present invention in laundry detergent or cleaning compositions rather than the prior art polymers (specifically the carboxyl group containing polymers of WO' 468) in terms of the benefits and/or uses described herein, since higher whiteness maintenance activity can be achieved at lower concentration levels without adversely affecting performance.

In addition, the influence of the molecular weight of comparative polymer 1 on the whiteness retention is shown in fig. 1. According to fig. 1, higher molecular weight carboxyl group containing polymers show significantly enhanced whiteness maintenance performance.

Table 7:high concentration (40 ppm): polyester (PW 19); single cycle washing

Table 8:high concentration (40 ppm): polyester (PW 19); single cycle washing

Table 9:low concentration (10 ppm): polyester (PW 19); single cycle washing

Table 10:low concentration (10 ppm): polyester (PW 19); single wash

Example 5: synthesis of laundry detergent formulations

Sample laundry detergent formulations were prepared using a carboxyl group-containing polymer according to one aspect of the present invention. The formulations are prepared by mixing the ingredients using standard industry practice. The formulations are shown in table 11. Example laundry detergent formulations were tested to determine their ability to improve soil redeposition and whiteness maintenance from treated fabric surfaces during the washing process.

Table 11:sample laundry detergent formulations

All enzyme levels are expressed as carpet active enzyme protein per 100g detergent composition.

Suitable ingredients are available from BASF (Ludwigshafen, Germany)Shell Chemicals(London，UK)；Stepan(Northfield，Ill.，USA)；Huntsman(Huntsman，Salt Lake City，Utah，USA)；Clariant(Sulzbach，Germany)

Sodium tripolyphosphate is available from Rhodia (Paris, France).

Zeolites are available from Industrial Zeolite (UK) ltd. (Grays, Essex, UK).

Citric acid and sodium citrate are available from Jungbunzlauer (Basel, Switzerland).

NOBS is sodium nonanoyloxybenzenesulfonate supplied by Eastman (Batesville, ark., USA).

TAED is tetraacetylethylenediamine, trade nameSupplied by Clariant GmbH (Sulzbach, Germany).

Sodium carbonate and sodium bicarbonate are available from Solvay (Brussels, Belgium).

Polyacrylate, polyacrylate/maleate copolymers are available from BASF (Ludwigshafen, Germany).

Available from Rhodia (Paris, France).

Available from Clariant (Sulzbach, Germany).

Sodium percarbonate and sodium carbonate are available from Solvay (Houston, tex, USA).

The sodium salt of ethylenediamine-N, N' -disuccinic acid, the (S, S) isomer (EDDS) was supplied by Octel (Ellesmie Port, UK).

Hydroxyethane diphosphonate (HEDP) was supplied by Dow Chemical (Midland, michh., USA).

EnzymeUltra、Plus、 Plus、ultra andavailable from Novozymes (Bagsvaerd, Denmark).

EnzymeFN3, FN4, and Optisize are available from Genencor International Inc. (Palo Alto, California, US).

Direct violet 9 and 99 are available from BASF DE (Ludwigshafen, Germany).

Solvent violet 13 is available from Ningbo Lixing Chemical co., Ltd. (Ningbo, Zhejiang, China).

Whitening agents are available from Ciba Specialty Chemicals (Basel, Switzerland).

All percentages and ratios are by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition, unless otherwise indicated.

It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, the disclosed dimension "40 mm" is intended to mean "about 40 mm".

Each document cited herein, including any cross-referenced or related patent or patent application, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

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Laundry detergent and cleaning compositions comprising polymers containing carboxyl groups

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