WO2021259722A1

WO2021259722A1 - A concentrated liquid detergent composition

Info

Publication number: WO2021259722A1
Application number: PCT/EP2021/066201
Authority: WO
Inventors: Yan KANG; Roland Ettl; Xiao Li ZHANG; Shan Ling GE
Original assignee: Basf Se
Priority date: 2020-06-24
Filing date: 2021-06-16
Publication date: 2021-12-30

Abstract

A concentrated liquid detergent composition, comprising more than 30 wt.% of at least one sur-factant relative to the weight of the concentrated liquid detergent composition and at least one rheology modifier, wherein the rheology modifier is obtainable by polymerizing (i) at least one ethylenically unsaturated carboxylic acid; (ii) optionally at least one nonionic ethylenically un-saturated surfactant monomer, (iii) at least one C₁-C₂-alkyl methacrylate, and/or (iv) at least one C₂-C₄-alkyl acrylate, where the alkyl chain length averaged over the number of alkyl groups of the alkyl acrylate is 2.1 to 4.0; in the presence of hydrocarbon comprising at least one XH-group, wherein X is selected from the group consisting of O, P, N and S.

Description

A concentrated liquid detergent composition

Technology Field

The present invention relates to a concentrated liquid detergent composition, comprising more than 30 wt.% of at least one surfactant relative to the weight of the concentrated liquid detergent composition and at least one rheology modifier, wherein the rheology modifier is obtainable by polymerizing

(i) at least one ethylenically unsaturated carboxylic acid;

(ii) optionally at least one nonionic ethylenically unsaturated surfactant monomer,

(iii) at least one CrC2-alkyl methacrylate, and/or

(iv) at least one C2-C4-alkyl acrylate, where the alkyl chain length averaged over the number of alkyl groups of the alkyl acrylate is 2.1 to 4.0; in the presence of hydrocarbon comprising at least one XH-group, wherein X is selected from the group consisting of O, P, N and S.

Background

Concentrated liquid detergent having high content of surfactant becomes more and more popu lar in the market. The broad use of concentrated liquid detergent could contribute to sustainabil ity by using less water, less package and saving energy in production and transportation.

However, in the concentrated liquid detergents, due to the addition of high percentage of surfac tants, solvents are generally added at an elevated amount. The addition of solvent leads to the decrease of the viscosity of the liquid detergent, which requires the addition of thickener to the detergent to adjust the viscosity. Furthermore, particles, such as capsules are additives often used in liquid detergents to provide additional benefits, e.g. long-lasting fragrance. While, parti cles tend to sedimentate or cream in formulation and therefore a rheology modifier is further required. However, rheology modifier usually causes the washed fabric to turn grey. Therefore, it will be a challenge for the selection of a suitable rheology modifier in the concentrated liquid detergent composition to deliver capsule stabilization effects with a reasonable viscosity and less greying to the fabric.

Use of the rheology modifier in the regular detergent of low surfactant content is known in the prior art. For example, W0201679003A1 discloses a rheology modifier obtainable by polymeriz ing

(i) at least one ethylenically unsaturated carboxylic acid; (ii) optionally at least one nonionic ethylenically unsaturated surfactant monomer,

(iii) at least one CrC2-alkyl methacrylate, and/or

However, W02016/079003 only discloses the use of rheology modifier in a regular detergent of low surfactant content, wherein the content of the surfactant is no more than 30 wt.%. In addi tion, WO2016/079003 does not realize the greying problem of the washed fabric.

Summary of the Invention

It is an object of the invention to provide a concentrated liquid detergent composition comprising a rheology modifier, wherein the rheology modifier can deliver good capsule stabilization effects, has good thickening effect, and also causes the washed fabric less greying.

Another object of the present invention is to provide use of the rheology modifier in the concen trated liquid detergent composition.

A further objection of the present invention is to provide a concentrated liquid formulation com prising the rheology modifier and at least one component selected from the group consisting of gas bubbles, nanoparticles, microcapsules made of or with active, enzymes, perfumes, phar maceuticals, organic particles, pigments, fibers, biocides, herbicides and fungicides.

It has been surprisingly found that the above objects can be achieved by following embodiments:

1. A concentrated liquid detergent composition, comprising more than 30 wt.% of at least one surfactant relative to the weight of the concentrated liquid detergent composition and at least one rheology modifier, wherein the rheology modifier is obtainable by polymerizing

(i) at least one ethylenically unsaturated carboxylic acid;

(iii) at least one CrC2-alkyl methacrylate, and/or

(iv) at least one C2-C4-alkyl acrylate, where the alkyl chain length averaged over the number of alkyl groups of the alkyl acrylate is 2.1 to 4.0; in the presence of hydrocarbon comprising at least one XH-group, wherein X is selected from the group consisting of O, P, N and S. 2. The concentrated liquid detergent composition according to item 1, wherein the concen trated liquid detergent composition comprises 31 to 70 wt.%, preferably 35 to 60 wt.%, more preferably 40 to 50 wt.% of the at least one surfactant based on the weight of the concentrated liquid detergent composition.

3. The concentrated liquid detergent composition according to item 1 or 2, wherein it com prises at least one anionic surfactant and at least one nonionic surfactant.

4. The concentrated liquid detergent composition according to item 3, wherein anionic sur factant is comprised in an amount from 18 to 55 wt.%, preferably 20 to 35 wt.%, in each case relative to the weight of the concentrated liquid detergent composition.

5. The concentrated liquid detergent composition according to item 3 or 4, wherein nonionic surfactant is comprised in an amount from 13 to 40 wt.%, preferably 15 to 25 wt.%, in each case relative to the weight of the concentrated liquid detergent composition.

6. The concentrated liquid detergent composition according to any one of items 3 to 5, wherein the anionic surfactant is selected from alkylbenzenesulfonic acid salts, olefinsulfonic acid salts, C12-C18 alkanesulfonic acid salts, salts of sulfuric acid monoesters with a fatty alco hol, a fatty acid soap, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants.

7. The concentrated liquid detergent composition according to any one of items 3 to 6, wherein the anionic surfactant is selected from alkylbenzenesulfonic acid salts, fatty acid soaps, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol and mixtures thereof, prefera bly the mixture of alkylbenzenesulfonic acid salts, fatty acid soaps and salts of sulfuric acid mo noesters with an ethoxylated fatty alcohol.

8. The concentrated liquid detergent composition according to any one of items 3 to 7, wherein the nonionic surfactant is selected from alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxyfatty acid amides, al- kylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.

9. The concentrated liquid detergent composition according to any one of items 3 to 8, wherein the nonionic surfactant comprises an alkoxylated fatty alcohol and the amount of the alkoxylated fatty alcohol is at least 20 wt.%, preferably at least 40 wt.%, more preferably at least 60wt.%, most preferably at least 80 wt.%, in each case relative to the total weight of the nonionic surfactant.

10. The concentrated liquid detergent composition according to item 8 or 9, wherein the alkoxylated fatty alcohol is an alkoxylated straight-chain fatty alcohol and the alcohol residue in the alkoxylated fatty alcoholhas 6 to 20, preferably 10 to 18, more preferably 12 to 16 carbon atoms.

11. The concentrated liquid detergent composition according to any one of items 8 to 10, wherein the alkoxylated fatty alcohol is ethoxylated and has on average 4 to 12 mol ethylene oxide (EO), preferably on average 5 to 10 EO per mol alcohol.

12. The concentrated liquid detergent composition according to any one of items 1 to 11, wherein said hydrocarbon is oligo- and/or polysaccharide, optionally substituted.

13. The concentrated liquid detergent composition according to any one of items 1 to 12, wherein said hydrocarbon is carboxymethylcellulose and/or starch.

14. The concentrated liquid detergent composition according to any one of items 1 to 13, wherein the nonionic ethylenically unsaturated surfactant monomer has the general formula (I)

R-0-(CH₂-CHR'-0)n-C0-CR"=CH₂ (I) in which R is C6-C3o-alkyl,

R' is hydrogen or methyl,

R" is hydrogen or methyl, and n is from 2 to 100.

15. The concentrated liquid detergent composition according to any one of items 1 to 14, wherein the ethylenically unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid.

16. The concentrated liquid detergent composition according to any one of items 1 to 15, wherein the hydrocarbons are present in an amount of 1 to 50 wt.%, preferably 5 to 20 wt.%, based on the weight of the copolymer in the rheology modifier.

17. The concentrated liquid detergent composition according to any one of items 1 to 16, wherein it comprises particles of a particulate solid, preferably microcapsules and/or pigments. 18. The concentrated liquid detergent composition according to any one of items 1 to 17, wherein said particles of a particulate solid, preferably microcapsules and/or pigments, have an average particle size D (4,3) of 0.5 to 200 pm, preferably from 1 to 100 pm, particularly pre ferred from 2 to 50 pm.

19. The concentrated liquid detergent composition according to any one of items 1 to 18, wherein the amount of the said particles of a particulate solid, preferably microcapsules and/or pigments is in the range of from 0.05 to 3 wt.%, preferably 0.08 to 2 wt.%, more preferably 0.1 to 1 wt.%, based on the weight of the concentrated liquid detergent composition.

20. Use of the rheology modifier as defined in any one of items 1 and 12 to 16 in the concen trated liquid detergent, wherein the concentrated liquid detergent composition comprises more than 30 wt.%, preferably 31 to 70 wt.%, more preferably 35 to 60 wt.%, even more preferably 40 to 50 wt.% of at least one surfactant relative to the weight of the concentrated liquid detergent.

21. A concentrated liquid formulation comprising the rheology modifier as defined in any one of items 1 and 12 to 16 and at least one component selected from the group consisting of gas bubbles, nanoparticles, microcapsules made of or with active, enzymes, perfumes, pharmaceu ticals, organic particles, pigments, fibers, biocides, herbicides and fungicides, wherein the con centrated liquid formulation comprises more than 30 wt.%, preferably 31 to 70 wt.%, more pref erably 35 to 60 wt.%, even more preferably 40 to 50 wt.% of at least one surfactant relative to the weight of the concentrated liquid formulation.

The rheology modifier in the concentrated liquid detergent composition according to the present invention shows improved effect of stabilizing particles, has good thickening effect even if the solvent is added, and also causes the washed fabric less greying, especially after several wash ing rounds, compared with the regular liquid detergent composition of low surfactant content.

Embodiment of the Invention

The undefined article “a”, “an”, “the” means one or more of the species designated by the term following said article.

The term “regular detergent” or “regular detergent composition”, as used herein, means that the total content of surfactant in the regular detergent or regular detergent composition is no more than 30 wt.%, based on the weight of the regular detergent or detergent composition. The term “concentrated liquid detergent composition”, as used herein, means that the total con tent of surfactant in the concentrated liquid detergent composition is in the range from above 30 wt.%, preferably 31 to 70 wt.%, more preferably 35 to 60 wt.%, even more preferably 40 to 50 wt.%, based on the weight of the regular detergent or detergent composition. The concentrated liquid detergent composition according to the present invention can also be in the form of a sin gle unit dose.

One aspect of the present invention is directed to a concentrated liquid detergent composition, comprising more than 30 wt.% of at least one surfactant relative to the weight of the concentrat ed liquid detergent composition and at least one rheology modifier, wherein the rheology modi fier is obtainable by polymerizing

(i) at least one ethylenically unsaturated carboxylic acid;

(iii) at least one CrC2-alkyl methacrylate, and/or

In a preferred embodiment, the concentrated liquid detergent composition comprises 31 to 70 wt.%, preferably 35 to 60 wt.%, more preferably 40 to 50 wt.% of at least one surfactant based on the weight of the concentrated liquid detergent composition.

A preferred concentrated liquid detergent composition of this embodiment comprises at least one anionic surfactant.

Suitable anionic surfactants comprise alkylbenzenesulfonic acid salts, olefinsulfonic acid salts, C12-C18 alkanesulfonic acid salts, salts of sulfuric acid monoesters with a fatty alcohol, fatty acid soaps, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants. Among these anionic surfactants, alkylbenzenesulfonic acid salts, fatty acid soaps, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol and mixtures thereof are more preferred, and the mixture of alkylbenzenesulfonic acid salts, fatty acid soaps and salts of sulfuric acid monoesters with an ethoxylated fatty alcohol is the most preferred. The amount of anionic surfactant is in the range from 18 to 55 wt.%, preferably from 18 to 40 wt.%, more preferred 20 to 35 wt.%, particularly preferred 22 to 28 wt.%, in each case relative to the weight of the concentrated liquid detergent composition.

Surfactants of the sulfonate type which may here preferably be considered are C9-C13 alkylben- zenesulfonates, olefinsulfonates, i.e. mixtures of alkenesulfonates and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C12-C18 monoolefins with a terminal or in ternal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. C12-C11 alkanesulfonates and the esters of a-sulfofatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Preferred alk(en)ylsulfates are the salts of sulfuric acid semi-esters of C12-C18 fatty alcohols for example prepared from coco fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C10-C20 oxo alcohols and those semi-esters of secondary alcohols of these chain lengths. C12-C16 alkylsulfates and C12-C15 alkylsulfates and C14-C15 alkylsulfates are preferred because of their washing characteristics. 2,3-Alkylsulfates are also suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C7-C21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable, such as 2-methyl-branched C9-C11 alcohols with on average 3.5 mol ethylene oxide (EO) or C12-C18 fatty alcohols with 1 to 4 EO.

Fatty acid soaps are further suitable anionic surfactants. Preferably, the fatty acid soap is de rived from a fatty acid having 8 to 22 carbon atoms. Saturated and unsaturated fatty acid soaps are in particular suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and in particular soap derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids or mixture thereof.

The anionic surfactants including the fatty acid soaps may be present in the form of the sodium, potassium, magnesium or ammonium salts thereof. The anionic surfactants are preferably pre sent in the form of the sodium or ammonium salts thereof. Amines usable for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methyle- thylamine or a mixture thereof, wherein monoethanolamine, diethanolamine, triethanolamine is preferred.

A particularly preferred liquid detergent composition of this embodiment comprises at least one anionic surfactant and at least one nonionic surfactant. The amount of nonionic surfactant is in the range of from 13 to 40 wt.%, preferably 13 to 30 wt.%, more preferably 15 to 25 wt.%, even more preferably 18 to 22 wt.%, in each case relative to the weight of the concentrated liquid detergent composition.

Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxyfatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.

In a preferred embodiment, the nonionic surfactant comprises an alkoxylated fatty alcohol and the amount of the alkoxylated fatty alcohol is at least 20 wt.%, preferably at least 40 wt.%, more preferably at least 60wt.%, most preferably at least 80 wt.%, in each case relative to the total weight of the nonionic surfactant.

Preferably, the alkoxylated fatty alcohol is straight-chained and the alcohol residue in the alkoxylated fatty alcohol has 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, even more preferably 12 to 16 carbon atoms.

Compared with alkoxylated branched fatty alcohol, alkoxylated straight-chain fatty alcohol is more advantageous to stabilize particles of a particulate solid, such as microcapsules and/or pigments in the concentrated liquid detergent composition. In one embodiment, the nonionic surfactant comprises an alkoxylated straight-chain fatty alcohol and the amount of the alkoxylated straight-chain fatty alcohol is at least 20 wt.%, preferably at least 40 wt.%, more preferably at least 60wt.%, most preferably at least 80 wt.%, in each case relative to the total weight of the nonionic surfactant. In one embodiment, the concentrated liquid detergent composition comprises the alkoxylated straight-chain fatty alcohol as the only nonionic surfactant.

Preferably used alkoxylated fatty alcohols are ethoxylated, in particular primary alcohols with 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms and on average 4 to 12 mol, preferably 5 to 10 mol ethylene oxide (EO) per mol alcohol, in which the alcohol residue is straight-chained. In particular, alcohol ethoxylates with 12 to 18 carbon atoms, for example prepared from coconut, palm, tallow fat or oleyl alcohol, and on average 5 to 8 EO per mol of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 4 EO or 7 EO, C9-C11 alcohol with 7 EO, C12-C18 alcohols with 5 EO or 7 EO and mixtures of these. The stated degrees of ethoxylation are statistical averages which, for a specific product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homologue distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in one molecule may also be used according to the invention. A mixture of a branched ethoxylated fatty alcohol and an ethoxylated straight-chain fatty alcohol, such as for example a mixture of a straight-chain Cie- Ci₈ fatty alcohol with 7 EO and 2-propylheptanol with 7 EO, is also suitable. Most preferably, the at least one nonionic surfactant is selected from ethoxylated straight-chain fatty alcohol, such as ethoxylated straight-chain C16-C18 fatty alcohol with 7 EO.

According to the present invention, the concentrated liquid detergent composition comprises at least one rheology modifier, wherein the rheology modifier is obtainable by polymerizing

(i) at least one ethylenically unsaturated carboxylic acid;

(iii) at least one CrC2-alkyl methacrylate, and/or

In a preferred embodiment, the rheology modifier is obtainable by polymerizing

(i) at least one ethylenically unsaturated carboxylic acid;

(ii) at least one nonionic ethylenically unsaturated surfactant monomer,

(iii) at least one CrC2-alkyl methacrylate, and/or

In a preferred embodiment, the rheology modifier is obtainable by polymerizing

(i) at least one ethylenically unsaturated carboxylic acid;

(ii) at least one nonionic ethylenically unsaturated surfactant monomer,

(iii) at least one CrC2-alkyl methacrylate, and

The hydrocarbon according to the present invention comprise preferably at least one OH-group. Hydrocarbons that can be used in accordance with the present invention can be naturally occur ring hydrocarbons having at least one XH-group, wherein X is selected from the group consist ing of O, P, N and S, e.g., casein, agarose, maltodextrin, alginic acid or its salts, fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, polysaccharide such as starch, dex- tran, sucrose or cellulose.

Hydrocarbons that can be used in accordance with the present invention can be semi-synthetic hydrocarbons having at least one XH-group, wherein X is selected from the group consisting of

O, P, N and S, e.g., chemically modified or substituted cellulose, such as celluloseester and - ether, celluloseacetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose (CMC), derivatives of starch, starchether and -ester; water soluble modified cellulose, hydroxyethylcellulose, carboxymethylhydroxyethylcellulose or methylhydrox- yethylcellulose,.

Hydrocarbons that can be used in accordance with the present invention can be synthetic hy drocarbons having at least one XH-group, wherein X is selected from the group consisting of O,

P, N and S, e.g., polymers with polyacrylate, polyvinylphosphate, polyvinylphosphonate, poly amide, polyvinylalcohol, polyvinylpyrrolidon (PVP) or water soluble polymers made from N- vinylamide and polyvinylpyrrolidon.

In a preferred embodiment, the hydrocarbons in accordance with the present invention are oli- go- and/or polysaccharides which can be optionally substituted. Oligo- and polysaccharides are known in the art. An oligosaccharide is a saccharide polymer containing a small number (typi cally three to nine) of simple sugars (monosaccharides). Polysaccharides are polymeric carbo hydrate molecules composed of long chains of monosaccharide units bound together by glyco- sidic linkages and on hydrolysis give the constituent monosaccharides or oligosaccharides. The oligo- and/or polysaccharides are present in an amount of less than 150 pphm (parts per hun dred monomer), preferably in an amount of from 1 pphm to 150 pphm, more preferably in an amount of from 2 pphm to 75 pphm, most preferably in an amount of from 5 pphm to 50 pphm.

In a preferred embodiment, the polysaccharide in accordance with the present invention is a polymer of pyranose monomers, at least 30% of which monomers are in the a-anomeric con formation. A pyranose monomer is a monomer of a pyranose polysaccharide that is based upon a (tetrahydro)pyran ring like the tetrahydropyran

In polysaccharides, pyranose monomers are linked together by the formation of ether bonds involving an -OH group attached to a C-atom that is also attached to the O-atom of the (tetrahy- dro)pyran ring. This -OH group can be present in the cyclic monomer group in one of two con formations, namely the a- and the b-anomeric conformations (illustrated below by use of a par ticular "chair" conformation of the pyranose ring).

a-anomer b-anomer

(OH axial) (OH equatorial)

The C-atom in the above-depicted structures to which the two O-atoms are attached is called the anomeric carbon, and also represents a chiral centre when the molecule is locked in the ring conformation. In this respect, it is to be noted that the formation of the ring is reversible in aque ous solution for pyranose monomers, due to interconversion of the molecules between linear (hydroxyaldehyde) and cyclic (hemiacetal) forms.

The a-anomeric conformation in a polysaccharide is illustrated below by reference to the struc ture of amylose (which is used as an illustrative example only).

a-anomeric conformation in amylose

In amylose, the ether bonds are formed between the 1- and 4-positions of pyranose monomer (i.e. between the anomeric carbon and the C-atom in the 4-position in the ring relative to that carbon). Such linkages are described as a(1- ). However, the polysaccharides employed in the first aspect of the invention may contain any ether linkages found in polysaccharides derived from natural sources, such as a(1- 6), b(1- 4) and/or b(1- 6), provided that less than 50% of the pyranose monomers are present in the a-anomeric conformation. In a preferred embodi ment, the hydrocarbon is a starch, like corn starch, potato starch, wheat starch, tapioca starch and soluble starch.

In a more preferred embodiment, the hydrocarbons of the present invention are one or more of amylose, amylopectin, agarose and agaropectin; a mixture of amylose and amylopectin; or a mixture of agarose and agaropectin. In another preferred embodiment, the hydrocarbons are b-I, O-VIίΐoorgGqhoe^be which may be optionally substituted. The, b-I, O-VIuoorgGqhoe^be are present in an amount of less than 150 pphm (parts per hundred monomer), preferably in an amount of from 1 pphm to 150 pphm, more preferably in an amount of from 2 pphm to 75 pphm, most preferably in an amount of from 5 pphm to 50 pphm.

In an even more preferred embodiment, the hydrocarbons are carboxymethylcellulose (CMC) and/or starch. Carboxymethylcellulose (CMC) is present in an amount of less than 150 pphm (parts per hundred monomer), preferably in an amount of from 1 pphm to 150 pphm, more pref erably in an amount of from 2 pphm to 75 pphm, most preferably in an amount of from 5 pphm to 50 pphm. In a further preferred embodiment, starch is present in an amount of less than 150 pphm (parts per hundred monomer), preferably in an amount of from 1 pphm to 150 pphm, more preferably in an amount of from 2 pphm to 75 pphm, most preferably in an amount of from 5 pphm to 50 pphm.

If CMC and starch are present, CMC is present in an amount less than 90 pphm (parts per hun dred monomer), preferably in an amount of from 1 pphm to 50 pphm, most preferably in an amount of from 3 pphm to 35 pphm and starch is present in an amount of less than 60 pphm (parts per hundred monomer), preferably in an amount of from 1 pphm to 25 pphm, most pref erably in an amount of from 2 pphm to 15 pphm.

The ethylenically unsaturated carboxylic acid (i) is generally a monoethylenically unsaturated mono- or dicarboxylic acid having 3 to 8 carbon atoms. Suitable ethylenically unsaturated car boxylic acids are selected, for example, from acrylic acid, methacrylic acid, itaconic acid and maleic acid. Of these, methacrylic acid is particularly preferred.

The amount of the ethylenically unsaturated carboxylic acid can be in the range from about 10 to 50 wt.%, preferably from about 15 to 40 wt.%, based on the total weight of all monomers.

Nonionic ethylenically unsaturated surfactant monomers which are suitable as monomer ii) are known per se. These are, for example,

(a) urethane-group-containing reaction products of a monoethylenically unsaturated isocya nate and nonionic surfactants,

(b) esters of ethylenically unsaturated carboxylic acids and nonionic surfactants, (c) vinyl or allyl ethers of nonionic surfactants.

Suitable nonionic surfactants are preferably alkoxylated C6-C30-alcohols, such as fatty alcohol alkoxides or oxo alcohol alkoxides. At least 2, e.g. 2 to 100, preferably 3 to 20, mol of at least one C2-C4-alkylene oxide is used per mole of alcohol. Different alkylene oxide units can be ar ranged blockwise or be present in random distribution. Preferably, the alkylene oxide used is ethylene oxide and/or propylene oxide.

A further class of suitable nonionic surfactants is alkylphenol ethoxides with C6-Ci4-alkyl chains and 5 to 30 mol of ethylene oxide units.

In preferred embodiments, the nonionic ethylenically unsaturated surfactant monomer has the general formula (I)

R-0-(CH₂-CHR'-0)n-C0-CR"=CH₂ (I) in which R is C6-C3o-alkyl, preferably C₈-C₂₂-alkyl, more preferably Ci₆-C₂₂-alkyl R' is hydrogen or methyl, preferably hydrogen,

R" is hydrogen or methyl, preferably methyl, and n is from 2 to 100, preferably 3 to 50, more preferably 10 to 35, most preferably 25.

The repeat units in the brackets are derived from ethylene oxide or propylene oxide. The mean ing of R¹ is independent in each repeat unit from other repeat units. Different alkylene oxide units can be arranged blockwise or be present in random distribution.

The amount of nonionic ethylenically unsaturated surfactant monomer can be in the range from 0.1 to 8 wt.%, preferably from 0.2 to 5 wt.%, more preferably from 0.3 to 2 wt.%, based on the total weight of all monomers.

Suitable CrC₂-alkyl methacrylates (iii) are methyl methacrylate and ethyl methacrylate, of which methyl methacrylate is particularly preferred.

The amount of CrC₂-alkyl methacrylate can be in the range from 5 to 60 wt.%, preferably from 10 to 50 wt.%, more preferably from 15 to 45 wt.%, based on the total weight of all monomers. Suitable C2-C4-alkyl acrylates (iv) are ethyl acrylate, n-propyl acrylate and n-butyl acrylate. The type and amount of the C2-C4-alkyl acrylates are chosen such that a certain alkyl chain length averaged over the number of alkyl groups of the C2-C4-alkyl acrylate units is established, as stated above. The average alkyl chain length is calculated by multiplying the number of carbons in the longest alkyl chain of the alkyl radical (i.e. for example 2 for ethyl and 4 for n-butyl) by the molar fraction of the alkyl acrylate of the total amount of the C2-C4-alkyl acrylates, and adding the individual contributions.

The amount of C2-C4-alkyl acrylate can be in the range from 5 to 85 wt.%, preferably from 10 to 60 wt.%, more preferably from 15 to 45 wt.%, based on the total weight of all monomers.

Preferably, the C2-C4-alkyl acrylate comprises at least n-butyl acrylate, in particular a mixture of n-butyl acrylate with ethyl acrylate. Preferably, the copolymer in the rheology modifier comprises 5 to 85% by weight, based on the total weight of the copolymer, of copolymerized units of n-butyl acrylate, where a range from 10% by weight to 60% by weight is preferred and a range from 15% by weight to 45% by weight is particularly preferred. The term “copolymer” in the rhe ology modifier, as used herein, means a polymer formed by polymerizing the monomers in addi tion to the hydrocarbon.

Ethylenically polyunsaturated monomers that can be used are, for example, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, divinylbenzene and the like.

The rheology modifier may further comprise an anionic and/or a nonionic emulsifier.

Typical emulsifiers are anionic emulsifiers, such as, for example, sodium lauryl sulfate, sodium tridecyl ether sulfates, dioctyl sulfosuccinate sodium salt and sodium salts of alkylaryl polyether sulfonates; and nonionic emulsifiers, such as, for example, alkylaryl polyether alcohols and eth ylene oxide-propylene oxide copolymers.

Preferred emulsifiers have the general formula (II)

R-0-(CH₂-CHR'-0)_n-Y (II) in which R is C6-C3o-alkyl,

R' is hydrogen or methyl,

Y is hydrogen or SO₃M,

M is hydrogen or an alkali metal, and n is from 2 to 100.

In a preferred embodiment, the hydrocarbons comprising at least one XH-group in accordance with the present invention are present in an amount of 1 to 100% by weight, preferably 1 to 50% by weight, more preferably 5 to 50% by weight, even more preferably 5 to 20% by weight, based on the total weight of the copolymer. That is, given that the hydrocarbons comprising at least one XH-group are not grafted into the copolymer, if the hydrocarbons comprising at least one XH-group are present, e.g., in an amount of 100% based on the total weight of the copoly mer, both components (i.e. the hydrocarbons comprising at least one XH-group on the one hand and the copolymer on the other hand) are present in a ratio of 1:1 by weight.

The rheology modifier of the present invention can be prepared in various ways, preferably by emulsion polymerization.

For the polymerization, a suitable polymerization initiator is used. Thermally activatable free- radical polymerization initiators are preferred.

Suitable thermally activatable free-radical initiators are primarily those of the peroxy and azo type. These include, inter alia, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t- butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-bis(hydroperoxy)hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, dieicosyl peroxydicarbonate, di-t- butyl perbenzoate, azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, ammonium per sulfate, potassium persulfate, sodium persulfate and sodium perphosphate.

The persulfates (peroxodisulfates), in particular sodium persulfate, are most preferred. While carrying out the emulsion polymerization, the initiator is used in an adequate amount to initiate the polymerization reaction. The initiator is usually used in an amount of from about 0.005 to 3% by weight, based on the total weight of the monomers used. The amount of initiator is preferably about 0.02 to 2% by weight and in particular 0.05 to 0.5% by weight, based on the total weight of the monomers used.

The emulsion polymerization usually takes place at 35 to 100°C. It can either be carried out as a batch process or else in the form of a feed method. Preference is given to the feed procedure in which at least some of the polymerization initiator and, if appropriate, some of the monomers are initially introduced and heated to the polymerization temperature, and then the remainder of the polymerization mixture is introduced via a plurality of separate feeds, of which one or more comprise the monomers in pure or emulsified form, continuously or stepwise while maintaining the polymerization. Preferably, the monomer feed takes place in the form of a monomer emul sion. In parallel to the monomer feed, a further polymerization initiator can be metered in.

In preferred embodiments, the entire amount of initiator is initially introduced, i.e. no further me tered addition of initiator takes place in parallel to the monomer feed. It has surprisingly been found that this procedure leads to particularly high transparency of the rheology modifier.

In a preferred embodiment, therefore, the thermally activatable free-radical polymerization initia tor is initially introduced in its entirety, and the monomer mixture, preferably in the form of a monomer emulsion, is run in. Before the monomer mixture feed is started, the initial charge is brought to the activation temperature of the thermally activatable free-radical polymerization initiator or to a higher temperature. The activation temperature is regarded as being the temper ature at which at least half the initiator has disintegrated after one hour.

According to another preferred type of preparation, the rheology modifier of the present inven tion is obtained through polymerization of a monomer mixture in the presence of a redox initiator system. A redox initiator system comprises at least one oxidizing agent component and at least one reducing agent component, where, in the reaction medium, preferably heavy metal ions are additionally present as catalyst, for example cerium salts, manganese salts or iron(ll) salts.

Suitable oxidizing agent components are, for example, peroxides and/or hydroperoxides, such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide, dicyclohexyl percarbonate, dibenzoyl peroxide, dilauroyl per oxide and diacetyl peroxide. Hydrogen peroxide and tert-butyl hydroperoxide are preferred. Suitable reducing agent components are alkali metal sulfites, alkali metal dithionites, alkali met al hyposulfites, sodium hydrogensulfite, sodium hydroxymethansulfinate, mono- and dihydroxy- acetone, sugars (e.g. glucose or dextrose), ascorbic acid and its salts, acetone bisulfite adduct and/or an alkali metal salt of hydroxymethanesulfinic acid. Ascorbic acid is preferred.

Also suitable as reducing agent component or catalyst are iron(ll) salts, such as, for example, iron(ll) sulfate, tin(ll) salts, such as, for example, tin(ll) chloride, titanium(lll) salts, such as titani- um(lll) sulfate.

The use amounts of oxidizing agent are 0.001 to 5.0% by weight, preferably from 0.005 to 1.0% by weight and particularly preferably from 0.01 to 0.5% by weight, based on the total weight of the monomers used. Reducing agents are used in amounts of from 0.001 to 2.0% by weight, preferably from 0.005 to 1.0% by weight and particularly preferably from 0.01 to 0.5% by weight, based on the total weight of the monomers used.

A particularly preferred redox initiator system is the system sodium peroxodisulfate/ascorbic acid, e.g. 0.001 to 5.0% by weight of sodium peroxodisulfate and 0.001 to 2.0% by weight of ascorbic acid, in particular 0.005 to 1.0% by weight of sodium peroxodisulfate and 0.005 to 1.0% by weight of ascorbic acid, particularly preferably 0.01 to 0.5% by weight of sodium perox odisulfate and 0.01 to 0.5% by weight of ascorbic acid.

A further particular redox initiator system is the system t-butyl hydroperoxide/hydrogen perox ide/ascorbic acid, e.g. 0.001 to 5.0% by weight of t-butyl hydroperoxide, 0.001 to 5.0% by weight of hydrogen peroxide and 0.001 to 2.0% by weight of ascorbic acid, in particular 0.005 to 1.0% by weight of t-butyl hydroperoxide, 0.005 to 1.0% by weight of hydrogen peroxide and 0.005 to 1.0% by weight of ascorbic acid, particularly preferably 0.01 to 0.5% by weight of t-butyl hydroperoxide, 0.01 to 0.5% by weight of hydrogen peroxide and 0.01 to 0.5% by weight of ascorbic acid.

In a preferred embodiment, a monomer mixture, preferably in the form of a monomer emulsion, is run into an aqueous initial charge which is heated to the polymerization temperature. In paral lel to the monomer feed, at least times, an oxidizing agent component and a reducing agent component of the redox initiator system are run in. Preferably, some of the oxidizing agent component of the redox initiator system is initially introduced. If appropriate, some of the mon omers can be initially introduced. The rheology modifier of the present invention can be subjected to a chemical deodorization. During the chemical deodorization, a further initiator, e.g. a redox initiator, is added after the end of the actual emulsion polymerization. Redox initiators suitable for the chemical deodorization comprise, as oxidizing component, for example at least one organic peroxide and/or hydroper oxide, such as hydrogen peroxide, tert-butyl peroxide, cumene hydroperoxide, pinane hydrop eroxide, diisopropylphenyl hydroperoxide, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide and, as reducing component, for example iron(ll) salts, alkali metal sulfites, ascorbic acid, acetonebisulfite adduct and/or an alkali metal salt of hydroxymethanesulfinic acid.

If the rheology modifier is in the form of a dispersion, generally the dispersion has a solid con tent of from 12 to 40% by weight, in particular from 15 to 35% by weight.

In unneutralized form, the rheology modifier has a relatively low viscosity. It is therefore easy to handle and can be metered or circulated by pumping without problems. As a result of neutrali zation, e.g. to a pH of more than 5.5, preferably more than 6, in particular 8 to 10, the rheology modifier becomes soluble and the viscosity of the aqueous medium increases considerably. Suitable neutralizing agents are, for example, sodium hydroxide, potassium hydroxide, ammo nium hydroxide, amines, such as triethylamine, triethanolamine, monoethanolamine, and other alkaline materials.

The viscosity of the concentrated liquid detergents can be measured by means of customary standard methods and is preferably in the range from 200 to 8000 mPa.s. Preferred concentrat ed liquid detergents have viscosities of from 500 to 7000 mPa.s, with values between 800 and 6000 mPa.s being particularly preferred.

The rheology modifier can be used in an amount of from 0.05 to 5 wt.%, from 0.8 to 3 wt.%, from 0.1 to 2 wt.%, from 0.12 to 1 wt.%, or from 0.15 to 0.8 wt.%, in each case relative to the weight of the concentrated liquid detergent composition. If the rheology modifier is used in the form of a dispersion, the amount is calculated based on the solid content of the dispersion.

According to one preferred embodiment, the concentrated liquid detergent composition accord ing to the present invention comprises particles of a particulate solid, preferably microcapsules and/or pigments.

Particles of a particulate solid, preferably microcapsules and/or pigments, have an average par ticle size D (4,3) of 0.5 to 200 pm, preferably from 1 to 100 pm, particularly preferred from 2 to 50 pm. Said particle size can be determined by laser diffraction, for example by Matersizer 2000.

Said particles of a particulate solid are particularly chosen from agglomerates, granules, cap sules, pigments, fibers or mixtures thereof. Agglomerates, granules, capsules, pigments or mix tures thereof are particularly preferred, whereas capsules and/or pigments (especially particu larly preferred microcapsules and/or effect pigments) are most preferred dispersed components in said concentrated liquid detergent composition.

Capsules are core-shell-particles, comprising a solid shell which envelopes a core. The core is preferably a liquid. Capsules and microcapsules are known in the art. The average particle size D (4,3) of the capsules or microcapsules are in the range from 0.5 to 200 pm, preferably from 1 to 100 pm, particularly preferred from 2 to 50 pm.

Particularly suited capsules have a bulk density of 0.80 to 1.20 g/cm³, especially preferred of 0.90 to 1.10 g/cm³ (according to ISO 697:1981).

Preferred capsules, especially microcapsules, used in the concentrated liquid detergent compo sition are water insoluble microcapsules. Said water insoluble capsules, especially microcap sules, comprise a shell material, which does not dissolve or disintegrate in water at least at a temperature between 20 and 40°C. Water insoluble capsules, especially microcapsules, are advantageous, because they will not disrupt during the wash and allow disruption of the shell and the release of the core after the wash under mechanical stress.

Preferred capsules, especially microcapsules, comprise at least one material selected from pol yurethane, polyolefine, polyamide, polyester, polysaccharide, epoxide resin, silicon resin, reac tion product of carbonyl compounds (preferably formaldehyde) with compounds with NH- groups (preferably melamin or urea or mixture) in its shell.

The preparation of capsules, especially microcapsules, is known. Suitable methods are dis closed in US 3,516,941, US 3,415,758 or in EP 0 026 914 A1. One method is the acid induced condensation reaction of melamin-formaldehyde-prepolymers (and/or their Ci-C4-alkylethers) in a medium comprising water and a dispersed phase of the core material. Further microcapsules suitable for this invention are described in WO 2001/049817 A2.

The shell may comprise at least one compound bearing at least one cationic charge. Preferred cationic compounds in the shell are cationic polymers. Preferred cationic polymers are selected from Polyquaternium 7, Polyquaternium-10, Polyquaternium-11, Polyquaternium-16, Polyqua- ternium-55, Polyquaternium-69 ore mixtures thereof.

The shell surrounding the core of the capsules, especially microcapsules, has a preferred mean thickness from 0.01 und 50 pm, particularly preferred from 0.1 pm to 30 pm, most preferred from 0.5 pm to 8 pm.

The core of the capsules, especially microcapsules, comprises preferably an active ingredient, suitable for use for textiles. Such active ingredient is preferably selected from

(a) scent,

(b) actives for fibre care, especially silicon oils, solubilized cationic polymers,

(c) skin care actives (especially vitamin E, aloe vera extract, green tea extract, D-panthenol, plankton extract, urea and/or glycine).

Most preferred, the dispersed compound comprises perfume microcapsules, with at least one scent in the core. The preferred embodiments of the microcapsules are of course also mutatis mutandis preferred embodiments of said perfume microcapsule.

In another preferred embodiment, the component dispersed is particles of a particulate solid, which are preferably pigments. The pigments in accordance with the present invention are ef fect pigments or nacreous pigments. Nacreous pigments produce pearl-like, metallic and irides cent effects. Natural pearl essence, a mixture of guanine and hypoxanthine obtained from the scales of fish has long been used in cosmetic formulations. Synthetic nacreous pigments devel oped for cosmetic and liquid detergents use include mica-based pigments and bismuth oxychlo ride, or bismuth oxychloride mica. Muscovite mica platelets coated with a metallic oxide, such as titanium dioxide have been widely used. A relatively thin titanium dioxide coating produces a pearl-like or silvery luster. Mica platelets with thicker coatings produce color, even though the components are colorless, through the phenomenon of light interference; they are known as interference pigments. Platy pigments are also composed of a plurality of laminar platelets coated with one or more reflecting/transmitting layers. Typically, effect pigments are a laminar platy substrate such as natural mica or glass flake that has been coated with a metal oxide lay er.

A description of effect pigment’s properties can be found in the Pigment Handbook, Volume I, Second Edition, pp. 829-858, John Wiley & Sons, NY 1988. If colorless metal oxides are used to coat the laminar platy substrate, effect pigments exhibit pearl-like luster as a result of reflec tion and refraction of light, and depending on the thickness of the metal oxide layer, they can also exhibit interference color effects. If colored metal oxides are used, the observed effects depend on reflection, refraction and absorption.

The color, called the reflection color, is seen most effectively by specular or mirror-like reflection, where the angle of reflection equals the angle of incidence. The reflection color is a function of optical thickness, i.e. the geometrical thickness times the refractive index, of the coating. Optical thickness of about 100 nm to about 160 nm produce reflection which may be called white, silvery or pearly; optical thickness of about 190 nm or more produce colored reflections. Nacreous or pearlescent pigments containing mica or mica coated with titanium dioxide are known in the art. Reference is made, e.g., to U.S. Pat. Numbers 3,087,828; 3,926, 659; 4,146,403; 4,192,691; 4,744,832; 5,273,576; 5,433,779; 5,456,749; 6,899,757; WO

2013/138312.

BASF CHIONE™MSVA is a performance mineral composed of Synthetic Fluorophlogopite, commonly known as synthetic mica, coated with lauroyl lysine. The resulting powder is very white and have a velvety texture, which can enhance the optical brightness and the feel of both anhydrous, hydroalcoholic or pure aqueous formulations. This highly brilliant additive is suitable for all cosmetic or home and personal cleaning applications, including eye and lip area or liquid detergents use. It has without coloured additives a very white appearance in both anhydrous or aqueous formulations.

Especially preferred pigments stabilized by the rheology modifier of the present invention are the white Chione™ HD Infinite White S130V or the larger coloured pigment Flamenco Sparkle Gold 220J or Multi Reflections™ Soft Sparkle Orchid 580P or Reflecks ™ Pearlescent and Iridescent Pigment based on Borsilicate and T1O2 like Glimmers of Green G830L or Shiny rouge G450D based on Borsilicate and Fe₂0₃ or Purely Purple G536L based on Borsilicate and T1O2 and Ferric Ferrocyanide or Varying Violet G580D based on Borsilicate and T1O2 and S1O2 from BASF.

Particularly suited pigments have a bulk density of 80 to 900 kg/m³, especially preferred of 100 to 600 g/cm³ (according to ISO 697:1981).

In one embodiment, the amount of the said particles of a particulate solid, preferably microcapsules and/or pigments in the concentrated liquid detergent composition is in the range of from 0.05 to 3 wt.%, preferably 0.08 to 2 wt.%, more preferably 0.1 to 1 wt.%, based on the weight of the concentrated liquid detergent composition. The concentrated liquid detergent composition can further comprises one or more nonaqueous solvents. Nonaqueous solvents which can be used in the concentrated liquid detergent compo sition, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the stated concentration range. Preferably, the solvents are selected from ethanol, n- or isopropanol, butanols, glycol, propanediol (propylene glycol) or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n- butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or -ethyl ether, diisopropylene glycol monomethyl or -ethyl ether, methoxy-, ethoxy- or butoxytriglycol, isobutoxyethoxy-2-propanol, 3- methyl-3-methoxybutanol, propylene glycol t-butyl ether, and mixtures of these solvents. Nonaqueous solvents can be used in the concentrated liquid detergent composition in amounts between between 0.5 and 30 wt.%, preferably below 20 wt.% by weight, most preferably below 15 wt%.

In order to allow the concentrated liquid detergent composition has a pH within a desired range, using pH replenishers may be appropriate. All of the known acid or base here can be used, pro vided it was not due to reasons relating to application by the consumer protection reasons or ecological reasons or to the exclusion of their use. These supplements are usually not exceed ing the total weight of the formulation in an amount of 7 wt.%.

One aspect of the present invention relates to use of the rheology modifier as defined herein in the concentrated liquid detergent, wherein the concentrated liquid detergent composition com prises more than 30 wt.%, preferably 31 to 70 wt.%, more preferably 35 to 60 wt.%, even more preferably 40 to 50 wt.% of at least one surfactant, in each case relative to the weight of the concentrated liquid detergent.

A further aspect of the present invention relates to a concentrated liquid detergent composition comprising the rheology modifier as defined herein and at least one component selected from the group consisting of gas bubbles, nanoparticles, microcapsules made of or with active, en zymes, perfumes, pharmaceuticals, organic particles, pigments, fibers, biocides, herbicides and fungicides, wherein the concentrated liquid formulation comprises more than 30 wt.%, prefera bly 31 to 70 wt.%, more preferably 35 to 60 wt.%, even more preferably 40 to 50 wt.% of at least one surfactant, in each case relative to the weight of the concentrated liquid formulation. Examples

Materials and Abbreviations

AES: Texapon N 70; Alcohol Ethoxysulfate;

LAS: Disponil LDBS 55 (solid content 55%) for formulations 1 and 2; Disponil LDBS 23

(solid content 23%) for Formulation 3; Linear alkylbenzene sulfonate;

LABS: Maranil DBS/E; alkyl benzene sulfonates;

Soap: Coconut Fatty Acid; Distilled Coconut Fatty Acid (DC-1218), Wilmar Oleo (Lianyun- gang) Co., Ltd;

AEO: Lutensol A7N; straight C12/C14 fatty alcohol+7EO;

M7: Lutensol M7; branched C10-C18 alcohol+7 EO;

EA: Ethylacrylate;

BA: n-Butylacrylate;

EHA: Ethylhexylacrylate

MAS: Methacrylic acid;

AS: Acrylic acid

AM: Acrylamide

ASSOC: 60% Lutensol AT 25 Methacrylate: associative monomer [= (C16- C18)-(EO)25-

Methacrylate, 20% Methacrylic acid, 20% water];

PETIA: Pentaerythritol tri/tetraacrylate

BDA2: Butandioldiacrylate

Maltodextrin: Water soluble mixture obtained by hydrolysis of starch (Poly-a-glucose)

CMC80: Carboxymethylcellulose with 80 mPa.s at 20 rmp

CMC150: Carboxymethylcellulose with 150 mPa.s at 20 rpm

CMC230: Carboxymethylcellulose with 230 mPa.s at 20 rpm

PVP: Poly(1-vinyl-2-pyrrolidone) with viscosity of 20 mPa.s at 20 % aqueous solution

2-EHTG: 2-Ethylhexyl thioglycolate

SDS: Sodium lauryl sulfate

C12-Alkyldiphenyloxide disulfonate: benzene, 1,T-oxybis, tetrapropylene deriva-tives, sul- fonated, sodium salts

SLES: Sodium lauryl ether sulfate: Sodium lauryl ether sulphate with critical micel concentration of 0.38 g NaPS: Sodiumperoxodisulfate

H202: Hydrogen peroxide

PVP4: Poly(1-vinyl-2-pyrrolidone) with viscosity of 3.7 mPa.s at 20 % aqueous solution

Flamenco: Flamenco Sparkle Gold 220J Chione: Chione™ HD Infinite White S130V Trilon B: Tetrasodium ethylenediaminetetraacetate

Two perfume capsules based on melamine formaldehyde shell were used in formulation (Cap sule 1 (P1): D(4,3) = 13.4 pm; Capsule 2 (P2): D(4,3) = 8.3 pm).

Preparainq examples

Comparative Example V1.1 - Production of a rheology modifier in the absence of a hydrocarbon

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator reflux condenser, inside thermo sensor and metering station, 850.2 g deionized water, 0.66 g emulsifier SDS (15% in water) and 52.0 g PVP were mixed. At 85°C 1.86 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 213.56 g deionized water, monomers (78.0 g methacrylic acid, 175.5 g ethylacrylate, 8.13 g ASSOC, 7.8 g emulsifier SDS (15% in water), and 2.89 g emulsifier C12-Alkyldiphenyloxide disulfonate (45% in water)) were added and constantly stirred at 85°C. After complete addition of the emul sion 13.94 g deionized water was added. After 15 minutes following the addition of the emulsion 26 g H2O2 (1% in water) and 10.4 g ascorbic acid (1% in water) were added at a constant rate for 2 hours and 15 minutes to the mixture. Then 0.13 g ethylenediaminetetraacetic acid ferric potassium com (4% in water) was added. Subsequently the reaction mixture was cooled slowly to room temperature. During cooling 26 g H2O2 (1% in water) and 39 g ascorbic acid (1% in wa ter) were added at a constant rate for 1 hour. An aqueous polymer dispersion with 21% solid content was obtained.

Comparative Example V1.2 - Production of a rheoloqv modifier in the absence of a hydrocarbon

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 898.23 g deionized water, 2.72 g emulsifier sodium lauryl ether sulfate (28% in water) were mixed. At 75°C 8.71 g NaPS (7% in water) were added and the mixture was stirred at 75°C for 5 minutes. For 2 hours an emulsion consisting of 184.37 g deionized water, monomers (22.88 g acrylic acid, 45.75 g acrylamide, 228.75 g n- butylacrylate, 38.13 g ASSOC and 13.62 g emulsifier Sodium lauryl ether sulfate (28% in wa ter)) were added and constantly stirred at 75°C. After complete addition of the emulsion 14.64 g deionized water was added. For another 1 hour at 75°C further polymerization took place. Sub- sequently 0.15 g ethylenediaminetetraacetic acid ferric potassium complex (1% in water) and 6.1 g H2O2 (5% in water) were added to the mixture. Then 15.25 g sodium hy- droxymethansulfinate (1% in water) was added for 1 hour at 75°C. Subsequently the reaction mixture was cooled slowly to room temperature. An aqueous polymer dispersion with 21% solid content was obtained.

Comparative Example V1.3 - Production of a rheology modifier in the absence of a hy- drocarbon

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 844.12 g deionized water, 2.72 g emulsifier sodium lauryl ether sulfate (28% in water) were mixed. At 75°C 32.68 g NaPS (7% in water) were added and the mixture was stirred at 75°C for 5 minutes. For 2 hours an emulsion consisting of 184.37 g deionized water, monomers (22.88 g acrylic acid, 122 g acrylamide, 95.31 g n-butylacrylate, 95.31 g ethyl acrylate, 38.13 g ASSOC and 13.62 g emulsifier sodium lauryl ether sulfate (28% in water)) were added and constantly stirred at 75°C. After complete addition of the emulsion 14.64 g deionized water was added. For another 1 hour at 75°C further polymerization took place. Subsequently 0.15 g ethylenediaminetetraacetic acid ferric potassium complex (1% in water) and 6.1 g H2O2 (5% in water) were added to the mixture. Then 15.25 g sodium hy- droxymethansulfinate (1% in water) was added for 1 hour at 75°C. Subsequently the reaction mixture was cooled slowly to room temperature. An aqueous polymer dispersion with 21% solid content was obtained.

Comparative Example V2.2 - Production of a rheology modifier in the absence of a hydrocarbon

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator reflux condenser, inside thermo sensor and metering station, 701.48 g deionized water, 2.8 g emulsifier SDS (15% in water) were mixed. At 85°C 2 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 229.88 g deionized water, monomers (84 g methacrylic acid, 94.5 g n-butylacrylate, 94.5 g ethylacrylate, 8.75 g ASSOC, 8.4 g emulsifier SDS (15% in water), and 3.11 g emulsifier C12-Alkyldiphenyloxide disulfonate (45% in water)) were added and constantly stirred at 85°C. After 15 minutes following the addi tion of the emulsion 28 g H2O2 (1% in water) and 11.2 g ascorbic acid (1% in water) were added at a constant rate for 2 hours and 15 minutes to the mixture. After complete addition of the emulsion 15.12 g deionized water was added. Then 0.14 g ethylenediaminetetraacetic acid fer ric potassium complex (4% in water) was added. Subsequently the reaction mixture was cooled slowly to room temperature. During cooling 28 g H2O2 (1% in water) and 42 g ascorbic acid (1% in water) were added at a constant rate for 1 hour. An aqueous polymer dispersion with 21% solid content was obtained.

Comparative Example V2.3 - Production of a rheology modifier in the absence of a hy- drocarbon

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 651.92 g deionized water, 0.69 g emulsifier SDS (15% in water) were mixed. At 85°C 1.86 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 215.2 g deionized wa ter, monomers (78 g methacrylic acid, 182 g ethylacrylate, 7.8 g emulsifier SDS (15% in water), and 2.89 g emulsifier C12-Alkyldiphenyloxide disulfonate (45% in water)) were added and con stantly stirred at 85°C. After complete addition of the emulsion 13.94 g deionized water was added. After 15 minutes following the addition of the emulsion 26 g H2O2 (1% in water) and 10.4 g ascorbic acid (1% in water) were added at a constant rate for 2 hours and 15 minutes to the mixture. Then 0.13 g ethylenediaminetetraacetic acid ferric potassium complex (4% in water) was added. Subsequently the reaction mixture was cooled slowly to room temperature. During cooling 26 g H2O2 (1% in water) and 39 g ascorbic acid (1% in water) were added at a constant rate for 1 hour. An aqueous polymer dispersion with 21% solid content was obtained.

Example B1.4 - Production of a rheology modifier with CMC

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 847.55 g deionized water, 0.69 g emulsifier SDS (15% in water) and 52 g CMC150 were mixed. At 85°C 1.86 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 215.2 g deionized water, monomers (78 g methacrylic acid, 182 g ethylacrylate, 7.8 g emulsifier SDS (15% in water), and 2.89 g emulsifier C12-Alkyldiphenyloxide disulfonate (45% in water)) were added and constantly stirred at 85°C. After complete addition of the emulsion 13.94 g deionized water was added. After 15 minutes following the addition of the emulsion 26 g H2O2 (1% in wa ter) and 10.4 g ascorbic acid (1% in water) were added at a constant rate for 2 hours and 15 minutes to the mixture. Then 0.13 g ethylenediaminetetraacetic acid ferric potassium complex (4% in water) was added. Subsequently the reaction mixture was cooled slowly to room tem perature. During cooling 26 g H2O2 (1% in water) and 39 g ascorbic acid (1% in water) were added at a constant rate for 1 hour. An aqueous polymer dispersion with 21% solid content was obtained. Example B1.11 - Production of a rheoloqv modifier with CMC

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 806.82 g deionized water, 2.8 g emulsifier SDS (15% in water) and 28 g CMC150 were mixed. At 85°C 2 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 229.88 g deionized water, monomers (84 g methacrylic acid, 94.5 g n-butylacrylate, 94.5 g ethylacrylate, 8.75 g ASSOC, 8.4 g emulsifier SDS (15% in water), and 3.11 g emulsifier C12- Alkyldiphenyloxide disulfonate (45% in water)) were added and constantly stirred at 85°C. After 15 minutes following the addition of the emulsion 28 g H2O2 (1% in water) and 11.2 g ascorbic acid (1% in water) were added at a constant rate for 2 hours and 15 minutes to the mixture. Af ter complete addition of the emulsion 15.12 g deionized water was added. Then 0.14 g eth- ylenediaminetetraacetic acid ferric potassium complex (4% in water) was added. Subsequently the reaction mixture was cooled slowly to room temperature. During cooling 28 g H2O2 (1% in water) and 42 g ascorbic acid (1% in water) were added at a constant rate for 1 hour. An aque ous polymer dispersion with 21% solid content was obtained.

Examples B1.1 to B1.3, B1.5 to B1.10, B1.12 and B1.13 were produced via the same process except that the amount of the starting material was varied as can be derived from Table 1.

Example B2.1 - Production of a rheology modifier with CMC

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 882.14 g deionized water, 0.14 g ethylenedia- minetetraacetic acid ferric potassium complex (4% in water), 2.8 g emulsifier SDS (15% in wa ter) and 28 g CMC150 were mixed. At 85°C 2 g NaPS (7% in water) were added and the mix ture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 229.99 g deionized water, monomers (84 g methacrylic acid, 96.6 g n-butylacrylate, 96.6 g ethylacrylate, 3.5 g AS SOC, 8.4 g emulsifier SDS (15% in water), and 3.11 g emulsifier C12-Alkyldiphenyloxide disul fonate (45% in water)) were added and constantly stirred at 85°C. 11.2 g ascorbic acid (0.25% in water) was added in 2 hours and 30 minutes. After 15 minutes following the addition of the emulsion 0.56 g H2O2 (1% in water) was added. After complete addition of the emulsion 15.01 g deionized water was added. Subsequently the reaction mixture was cooled slowly to room tem perature. During cooling 1.12 g H2O2 (1% in water) and 21 g ascorbic acid (1% in water) were added at a constant rate for 1 hour. An aqueous polymer dispersion with 21% solid content was obtained. Example B2.2 was produced via the same process except that the amount of the starting mate rial was varied as can be derived from Table 1.

Example B3.1 - Production of a rheoloqv modifier with CMC and starch

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 740.52 g deionized water, 0.17 g ethylenedia- minetetraacetic acid ferric potassium complex (4% in water), 1.21 g emulsifier sodium lauryl ether sulfate (28% in water), 68 g maltodextrin (50% in water) and 17 g CMC150 were mixed. At 85°C 2.43 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 279.28 g deionized water, monomers (102 g methacrylic acid, 114.75 g n-butylacrylate, 114.75 g ethylacrylate, 10.63 g ASSOC, 13.96 g emulsifier sodi um lauryl ether sulfate (28% in water)) were added and constantly stirred at 85°C. 13.6 g ascor bic acid (0.25% in water) was added in 2 hours and 30 minutes. After 15 minutes following the addition of the emulsion 0.68 g H2O2 (1% in water) was added. After complete addition of the emulsion 10.91 g deionized water and 8.49 g NaPS (1% in water) were added during 10 minutes. Subsequently the reaction mixture was cooled slowly to room temperature. During cooling 1.36 g H2O2 (1% in water) and 25.5 g ascorbic acid (2% in water) were added at a con stant rate for 2 hour. An aqueous polymer dispersion with 26% solid content was obtained.

Examples B3.2 to B3.5 were produced via the same process except that the amount of the starting material was varied as can be derived from Table 1.

Example B4.1 - Production of a rheology modifier with starch

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 644.46 g deionized water, 2.46 g emulsifier sodium lauryl ether sulfate (28% in water) and 184 g maltodextrin (50% in water) were mixed. At 85°C 18.4 g NaPS (1% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 339.99 g deionized water, monomers (126.5 g methacrylic acid, 143.75 g n-butylacrylate, 143.75 g ethylacrylate, 57.5 g ASSOC, 22.18 g emulsifier sodium lau ryl ether sulfate (28% in water)73.6 g NaPS (1% in water)) were added and constantly stirred at 75°C. After complete addition of the emulsion 18.4 g deionized water was added. For another 1 hour at 85°C further polymerization took place. Subsequently 0.92 g ethylenediaminetetraacetic acid ferric potassium complex (1% in water) and 9.2 g H2O2 (5% in water) were added to the mixture. Then 23 g sodium hydroxymethansulfinate (1% in water) was added for 1 hour at 85°C. Subsequently the reaction mixture was cooled slowly to room temperature. An aqueous polymer dispersion with 31% solid content was obtained.

Example B4.2 - Production of a rheoloqv modifier with CMC

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 1473.3 g deionized water, 0.92 g ethylenedia- minetetraacetic acid ferric potassium complex (1% in water), 4.6 g emulsifier SDS (15% in wa ter) and 55.2 g CMC150 were mixed. At 85°C 3.29 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 229.88 g deion ized water, monomers (138 g methacrylic acid, 159.85 g n-butylacrylate, 159.85 g ethylacrylate, 2.88 g ASSOC, 13.8 g emulsifier SDS (15% in water) and 5.11 g C12-Alkyldiphenyloxide disul fonate (45% in water) were added and constantly stirred at 85°C. After complete addition of the emulsion 24.66 g deionized water was added. After 15 minutes following the addition of the emulsion 0.92 g H2O2 (25% in water) and 18.4 g ascorbic acid (0.25% in water) added in 2 hours and 15 minutes. Then 1.84 g H2O2 (25% in water) were added. Subsequently the reaction mixture was cooled slowly to room temperature. During cooling 46 g ascorbic acid (2% in water) were added at a constant rate for 2 hours. An aqueous polymer dispersion with 21% solid con tent was obtained.

Example B2.2 was produced via the same process except that the amount of the starting mate rial was varied as can be derived from Table 1.

Example B5.1 - Production of a rheology modifier with high CMC content

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 1240.6 g deionized water, 0.71 g emulsifier sodium lauryl ether sulfate (28% in water) and 100 g CMC80 were mixed. At 90°C 1.43 g NaPS (7% in water) were added and the mixture was stirred at 85°C for 5 minutes. For 3 hours an emulsion consisting of 226.66 g deionized water, monomers (80 g methacrylic acid, 60 g n-butylacrylate, 60 g ethylacrylate, 8 g PETIA (5% in 1,2-propandiole, 13.57 g emulsifier sodium lauryl ether sulfate (28% in water) were added and constantly stirred at 90°C. For 3 hours were simultane ously added 90 g NaPS (1% in Water). After complete addition of the emulsion and NaPS 10.72 g deionized water was added. For another 0.5 hour at 90°C further polymerization took place. Subsequently the reaction mixture was cooled slowly to room temperature. At 90°C 0.8 g H2O2 (25% in water) were added and during cooling 20 g ascorbic acid (2% in water) were added at a constant rate for 2 hours. An aqueous polymer dispersion with 16% solid content was obtained. Examples B5.2, B5.7, B5.8, B5.9, B5.10, B5.11, B5.13, B5.14, B5.15, B5.16, B5.18, B5.19, B5.21 were produced via the same process except that the amounts of the chemical ingredients were varied as can be derived from Table 1.

Example B5.3 - Production of a rheoloqv modifier with hiqh CMC content

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 1070.1 g deionized water, 0.54 g emulsifier sodium lauryl ether sulfate (28% in water) and 75 g CMC150 were mixed. At 75°C 6.43 g NaPS (7% in water) were added and the mixture was stirred at 75°C for 5 minutes. For 2 hours an emulsion consisting of 94.56 g deionized water, monomers (60 g methacrylic acid, 44.63 g n- butylacrylate, 44.63 g ethylacrylate, 0.94 g ASSOC, 10.18 g emulsifier sodium lauryl ether sul fate (28% in water) were added and constantly stirred at 75°C. After complete addition of the emulsion 8.04 g deionized water was added. For another 1 hour at 75°C further polymerization took place. Subsequently the reaction mixture was cooled slowly to room temperature. At 75°C 0.6 g H2O2 (25% in water) were added and during cooling 15 g ascorbic acid (2% in water) were added at a constant rate for 2 hours. An aqueous polymer dispersion with 16% solid content was obtained.

Examples B5.4, B5.12, B5.20 were produced via the same process except that the amounts of the chemical ingredients were varied as can be derived from Table 1.

Example B5.5 - Production of a rheology modifier with CMC

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 1927.6 g deionized water, 1.2 g ethylenediaminetet- raacetic acid ferric potassium complex (1% in water), 6 g emulsifier SDS (15% in water) and 72 g CMC150 were mixed. At 90°C 4.29 g NaPS (7% in water) were added and the mixture was stirred at 90°C for 5 minutes. For 2 hours an emulsion consisting of 492.84 g deionized water, monomers (180 g methacrylic acid, 208.5 g n-butylacrylate, 208.5 g ethylacrylate, 3.75 g AS SOC, 18 g emulsifier SDS (15% in water), and 6.67 g emulsifier C12-Alkyldiphenyloxide disul fonate (45% in water)) were added and constantly stirred at 90°C. After 15 minutes following the addition of the emulsion 1.2 g H2O2 (1% in water) were added and 18 g ascorbic acid (0.25% in water) were simultaneously added for 2 hours and 30 minutes. After complete addition of the emulsion 32.16 g deionized water was added. After complete addition of the ascorbic acid (0.25% in water) the reaction mixture was cooled slowly to room temperature. At 90°C 2.4 g H2O2 (25% in water) were added and during cooling 60 g ascorbic acid (2% in water) were add ed at a constant rate for 2 hours. An aqueous polymer dispersion with 21% solid content Examples B5.6, B5.17 were produced via the same process except that the amounts of the chemical ingredients were varied as can be derived from Table 1.

Example B5.22 - Production of a rheoloqv modifier with CMC

In a stirring apparatus consisting of a 4 liter HWS vessel with anchor agitator, reflux condenser, inside thermo sensor and metering station, 1474.3 g deionized water, 0.92 g ethylenedia- minetetraacetic acid ferric potassium complex (1% in water), 4.6 g emulsifier SDS (15% in wa ter), 1.15g Trilon B (tetrasodium ethylenediaminetetraacetate) and 55.2 g CMC150 were mixed. At 85°C 3.29 g NaPS (7% in water) was added and the mixture was stirred at 85°C for 5 minutes. For 2 hours an emulsion consisting of 377.84 g deionized water, monomers (138 g methacrylic acid, 159.85 g n-butylacrylate, 159.85 g ethylacrylate, 2.88 g ASSOC, 13.8 g emul- sifier SDS (15% in water) and 5.11 g C12-Alkyldiphenyloxide disulfonate (45% in water) were added and constantly stirred at 85°C. After complete addition of the emulsion 24.66 g deionized water was added. After 15 minutes following the addition of the emulsion 0.92 g H2O2 (25% in water) was added and 18.4 g ascorbic acid (0.25% in water) was added in 2 hours and 15 minutes. Then 1.84 g H2O2 (25% in water) was added. Subsequently the reaction mixture was cooled slowly to room temperature. During cooling 46 g ascorbic acid (2% in water) was added at a constant rate for 2 hours. An aqueous polymer dispersion with 21% solid content was ob tained.

Table 1: summary of examples

* C12-Alkyldiphenyloxide disulfonate

Comparative example 1 : Polymer B Polymer B was synthesized without the addition of hydrocarbon and the monomer composition is as follows: ethylacrylate 33.75 wt.%, n-butylacrylate 33.75 wt.%, methacrylic acid 30 wt.% and ASSOC 2.5 wt.%. 1. Determination of stability of microcapsules

Preparation of formulations 1 to 3 Water and LAS were added to the beaker and then heated to 50 °C, followed by the addition of soap. NaOH was then added until a transparent solution was obtained and then stirring was continued for 15 min. The water bath was then removed and AES, propylene glycol (or ethanol), NIS surfactants (e.g. AEO, M7), and sodium citrate were added sequentially. The pH of the above mixture was adjusted to ca. 10 and then perfume capsules and rheology modifier (poly- mer A from example B4.2 or polymer B from comparative example 1) were added. The formula tion was stirred further for 30 min after the addition of polymer modifer. The final pH was adjust ed to 7-8 if needed. The formulation was left overnight to stabilize. The final formulation was then applied to measure viscosity and check stability at different temperature (-20 °C, 5 °C, 20°C and 50 °C).

Table 2: The weight percentage of components in formulations 1 to 3

*Disponil LDBS 55 (solid content 55%) for formulations 1 and 2; *Disponil LDBS 23 (solid con tent 23%) for Formulation 3.

The percentage of Polymer A or Polymer B is calculated based on the solid content.

Table 3

+ +: Good compatibility

+: little perfume capsules to formulation surface - : significant perfume capsules to formulation surface - - : almost all perfume capsules to formulation surface

*Viscosity: spindle DV-2T, rotator:31#, 5rpm, 20-24°C; last one sample: spindle DV-2T, rota- tor:31#, 2rpm, RT

Stability check at 5 °C, 20 °C and 50 °C was performed by continuously storaging for a time as shown in above table 3; Stability check at - 20 °C was performed by 5 frozen cycles (1 cycle includes storage at - 20 °C for 24 hours and then recover at room temperature for 24 hours) 2. Determination of qrevinq to fabric

Preparation of Formulation 1A Water and LABS were added to the beaker and then heated to 50 °C, followed by the addition of coconut Fatty Acid. TEA was then added until pH 7 and then stirring was continued further for 15 min. The water bath was then removed and AES, propylene glycol, AEO, and sodium citrate were added sequentially. The pH of the above mixture was adjusted to ca. 8 and then rheology modifier was added. The formulation was stirred further for 30 min after the addition of rheology modifier and the final pH was adjusted to 7-8 if needed. The above formulation was left over night to stabilize. The final formulation was then applied to measure viscosity and washing tests.

Table 4: The weight percentage of components in Formulation 1A

Table 5: Washing conditions:

* WFK 10A, WFK 30A and WFK 80A are from the Cleaning Technology Institute in Germany (WFK). Whiteness test method:

The degree of whiteness of the test fabric was used to determine the degree of soiling. The dif ference of whiteness was determined by photometric measurement of the reflectance using an Elrepho 2000 photometer (Datacolor) at a wavelength of 457 nm. The higher value of whiteness decrease (i.e. the lower value of whiteness as shown in Table 6) was observed for the white test fabric in comparison to the initial whiteness before the test, the higher re-deposition of soil onto fabric was found.

The degree of whiteness of WFK 10A (abbreviated as 10A in table 6), WFK 30A (abbreviated as 30A) and WFK 80A (abbreviated as 80A) before washing are 85.9, 85.7 and 84.3, respec- tively. The whiteness of WFK 10A, WFK 30A and WFK 80A after washing according to the washing conditions in above table 5 are sumarrized in table 6.

Table 6: Washing results obtained by using formulation 1A and formulation 3

Claims

(i) at least one ethylenically unsaturated carboxylic acid;

(iii) at least one CrC2-alkyl methacrylate, and/or

2. The concentrated liquid detergent composition according to claim 1, wherein the concen trated liquid detergent composition comprises 31 to 70 wt.%, preferably 35 to 60 wt.%, more preferably 40 to 50 wt.% of the at least one surfactant based on the weight of the concentrated liquid detergent composition.

3. The concentrated liquid detergent composition according to claim 1 or 2, wherein it com prises at least one anionic surfactant and at least one nonionic surfactant.

4. The concentrated liquid detergent composition according to claim 3, wherein anionic sur factant is comprised in an amount from 18 to 55 wt.%, preferably 20 to 35 wt.%, in each case relative to the weight of the concentrated liquid detergent composition.

5. The concentrated liquid detergent composition according to claim 3 or 4, wherein nonionic surfactant is comprised in an amount from 13 to 40 wt.%, preferably 15 to 25 wt.%, in each case relative to the weight of the concentrated liquid detergent composition.

6. The concentrated liquid detergent composition according to any one of claims 3 to 5, wherein the anionic surfactant is selected from alkylbenzenesulfonic acid salts, olefinsulfonic acid salts, C12-C18 alkanesulfonic acid salts, salts of sulfuric acid monoesters with a fatty alco hol, a fatty acid soap, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants.

7. The concentrated liquid detergent composition according to any one of claims 3 to 6, wherein the anionic surfactant is selected from alkylbenzenesulfonic acid salts, fatty acid soaps, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol and mixtures thereof, prefera bly the mixture of alkylbenzenesulfonic acid salts, fatty acid soaps and salts of sulfuric acid mo noesters with an ethoxylated fatty alcohol.

8. The concentrated liquid detergent composition according to any one of claims 3 to 7, wherein the nonionic surfactant is selected from alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxyfatty acid amides, al- kylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.

9. The concentrated liquid detergent composition according to any one of claims 3 to 8, wherein the nonionic surfactant comprises an alkoxylated fatty alcohol and the amount of the alkoxylated fatty alcohol is at least 20 wt.%, preferably at least 40 wt.%, more preferably at least 60wt.%, most preferably at least 80 wt.%, in each case relative to the total weight of the nonionic surfactant.

10. The concentrated liquid detergent composition according to claim 8 or 9, wherein the alkoxylated fatty alcohol is an alkoxylated straight-chain fatty alcohol and the alcohol residue in the alkoxylated fatty alcohol has 6 to 20, preferably 10 to 18, more preferably 12 to 16 carbon atoms.

11. The concentrated liquid detergent composition according to any one of claims 8 to 10, wherein the alkoxylated fatty alcohol is ethoxylated and has on average 4 to 12 mol ethylene oxide (EO), preferably on average 5 to 10 EO per mol alcohol.

12. The concentrated liquid detergent composition according to any one of claims 1 to 11, wherein said hydrocarbon is oligo- and/or polysaccharide, optionally substituted.

13. The concentrated liquid detergent composition according to any one of claims 1 to 12, wherein said hydrocarbon is carboxymethylcellulose and/or starch.

14. The concentrated liquid detergent composition according to any one of claims 1 to 13, wherein the nonionic ethylenically unsaturated surfactant monomer has the general formula (I)

R-0-(CH₂-CHR'-0)n-C0-CR"=CH₂ (I) in which R is C6-C3o-alkyl,

R' is hydrogen or methyl,

R" is hydrogen or methyl, and n is from 2 to 100.

15. The concentrated liquid detergent composition according to any one of claims 1 to 14, wherein the ethylenically unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid.

16. The concentrated liquid detergent composition according to any one of claims 1 to 15, wherein the hydrocarbons are present in an amount of 1 to 50 wt.%, preferably 5 to 20 wt.%, based on the weight of the copolymer in the rheology modifier.

17. The concentrated liquid detergent composition according to any one of claims 1 to 16, wherein it comprises particles of a particulate solid, preferably microcapsules and/or pigments.

18. The concentrated liquid detergent composition according to any one of claims 1 to 17, wherein said particles of a particulate solid, preferably microcapsules and/or pigments, have an average particle size D (4,3) of 0.5 to 200 pm, preferably from 1 to 100 pm, particularly pre ferred from 2 to 50 pm.

19. The concentrated liquid detergent composition according to any one of claims 1 to 18, wherein the amount of the said particles of a particulate solid, preferably microcapsules and/or pigments is in the range of from 0.05 to 3 wt.%, preferably 0.08 to 2 wt.%, more preferably 0.1 to 1 wt.%, based on the weight of the concentrated liquid detergent composition.

20. Use of the rheology modifier as defined in any one of claims 1 and 12 to 16 in the concen trated liquid detergent, wherein the concentrated liquid detergent composition comprises more than 30 wt.%, preferably 31 to 70 wt.%, more preferably 35 to 60 wt.%, even more preferably 40 to 50 wt.% of at least one surfactant relative to the weight of the concentrated liquid detergent.

21. A concentrated liquid formulation comprising the rheology modifier as defined in any one of claims 1 and 12 to 16 and at least one component selected from the group consisting of gas bubbles, nanoparticles, microcapsules made of or with active, enzymes, perfumes, pharmaceu ticals, organic particles, pigments, fibers, biocides, herbicides and fungicides, wherein the con centrated liquid formulation comprises more than 30 wt.%, preferably 31 to 70 wt.%, more pref erably 35 to 60 wt.%, even more preferably 40 to 50 wt.% of at least one surfactant relative to the weight of the concentrated liquid formulation.