EP3545064A1

EP3545064A1 - Copolymers and their use in detergent compositions

Info

Publication number: EP3545064A1
Application number: EP17801458.5A
Authority: EP
Inventors: Kevin MUTCH; Mike SAHL; Natascha SCHELERO; Dorothee GABEL
Original assignee: Clariant International Ltd
Current assignee: Clariant International Ltd
Priority date: 2016-11-28
Filing date: 2017-11-21
Publication date: 2019-10-02
Also published as: AR110263A1; US20200063070A1; JP2020513442A; DE102016223585A1; WO2018095916A1; CN110023472A; MX2019006054A; CN110023472B; BR112019010199A2

Abstract

The invention relates to copolymers and their use in detergent compositions. Disclosed are copolymers which contain cationic structural units and macromonomer structural units. The copolymers can advantageously be used in detergent compositions and are advantageously suitable in particular for cleaning cotton-containing textiles or for reducing the tendency of resoiling of cotton-containing textiles, on which the copolymers or the detergent compositions have been applied.

Description

Copolymers and their use in detergent compositions

The present invention relates to copolymers which contain one or more cationic structural units and one or more macromonomer structural units, detergent compositions containing such copolymers, and the use of the copolymers or detergent compositions for cleaning textiles, preferably for cleaning cotton-containing textiles, or Reduction of the re-soiling of the textiles and preferably the re-soiling of cotton-containing textiles bearing the copolymers or the detergent compositions

were applied. The copolymers according to the invention can thus function as soil release polymers, in particular when used on cotton-containing textiles. When washing with household laundry detergent compositions, certain impurities are difficult to remove from the fiber because they either adhere strongly to the fiber or penetrate deeply into the fiber interstices. That is why the use of Soil Release polymers in

Detergent compositions usual. It is believed that soil release polymers are deposited on the fiber, and their

Change surface properties so that dirt can be easily detached from the fiber. For predominantly polyester-based textiles are derivatives of polymers of terephthalic acid and polyethylene glycol

(e.g., E. P. Gosselink, "Soil Release Agents in Powdered Detergents", Chapter 7 (pp. 205-239) in Surfactant Science Series 71, "Powdered Detergents").

While for cleaning polyester-based textiles a distinct

Soil release is achieved by the addition of soil release polymers, the removal of fatty soiling of cotton is less well understood and thus more difficult. WO 97/42293 describes a detergent formulation having water-soluble or water-dispersible polyamines which have a functionalized polymer backbone that imparts soil release properties to cotton. EP 0936224 describes water-soluble or water-dispersible polymers which carry polysaccharide units. Among other things, the application is described in detergent compositions.

WO 01/88075 discloses the use of anionically-modified polysaccharides which provide better release of oily or solid soils to cotton in detergent compositions.

EP 1972683 describes ampholytic water-soluble polymers, which in detergent composition, the fibers from oily or fatty

Protect dirt.

US 7,160,947 describes graft copolymers having soil release properties in detergent compositions. These polymers are preferred

2-Dimethylaminoethyl (meth) acrylate side chains, polyethylene oxide (meth) acrylate side chains, and are obtained by free radical polymerization.

WO 2015/078736 describes polymers which contain polyethylene oxide and 2-dimethylaminoethyl (meth) acrylate-based hydrophilic side chains and provide improved soil release properties in detergent formulations.

In WO 2013/060708 comb or block copolymers as

Grayness inhibitors and soil release polymers used, inter alia, on cotton. Although these detergent systems have already improved

Dirt removal lead, but still room for improvement. Often, the active ingredients of the prior art do not draw in sufficient quantity on textile fibers and in particular on cotton-containing textile fibers, so that the soil release effect of these active substances is often unsatisfactory.

The object of the present invention was to develop polymer additives which are water-soluble or water-dispersible and detergent compositions can be added with the result that they can be applied to cotton, and a beneficial soil release effect on cotton can be observed. Surprisingly, it has been found that this object can be achieved by containing copolymers

a) 0.1 to 15.4 mol%, preferably 5.0 to 15.2 mol%, and especially

preferably 7.0 to 15.0 mol%, of one or more cationic

Structural units (A) and

b) 0.1 to 99.9 mol%, preferably 20.0 to 80.0 mol% and especially

preferably 25.0 to 75.0 mol% of one or more macromonomer structural units (B),

characterized in that the one or more cationic

Structural units (A) are represented by the following general formulas (I) and / or (II):

CO

Y (II)

V

wherein

R ¹ and R ^{1 a} are the same or different and are independent

each of each represents hydrogen and / or a methyl radical,

R ^{1 b} , R ³ , R ⁴ and R ⁵ are the same or different and are each independently

each one another by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, carbon atoms, a cycloaliphatic hydrocarbon radical with

5 to 20, preferably 5 to 8, C atoms, an aryl radical with

6 to 14 carbon atoms and / or polyethylene glycol (PEG) are represented, preferably in each case the same or different and are each independently represented by hydrogen and / or methyl and particularly preferably in each case methyl,

Y is the same or different and is oxygen, NH and / or

NR ^{3 is} represented,

V is the same or different and is denoted by - (CH 2) x-,

is represented, is the same or different and is represented by an integer from 1 to 6,

are the same or different and independent

each other by a halogen atom, ci- to

C4 alkyl sulfate and / or Ci- to C4 alkyl sulfonate are represented, and the one or more macromonomer structural units (B) represented by the general formula (III):

ZO (C ₃ H ₆ O), (CH ₂ CH ₂ O) _F H

is the same or different and is represented by H and / or methyl, is the same or different and is represented by C = O and / or O (CH 2) 4,

in molar average, is a number from 0 to 6 and preferably from 0 to 5, and

in molar average, a number from 1 to 150, preferably from 1 1 to 100 and particularly preferably from 12 to 50.

The invention therefore relates to copolymers

a) 0.1 to 15.4 mol%, preferably 5.0 to 15.2 mol%, and especially

preferably 7.0 to 15.0 mol%, of one or more cationic

Structural units (A) and

b) 0.1 to 99.9 mol%, preferably 20.0 to 80.0 mol% and especially

preferably 25.0 to 75.0 mol% of one or more macromonomer structural units (B), characterized in that the one or more cationic structural units (A) are represented by the following general formulas (I) and / or (II):

CO

Y (II)

V wherein

R ¹ and R ^{1 a} are the same or different and are independent

each of each represents hydrogen and / or a methyl radical,

each other by hydrogen, an aliphatic one

Hydrocarbon radical having 1 to 20, preferably 1 to 4, carbon atoms, a cycloaliphatic hydrocarbon radical with

5 to 20, preferably 5 to 8, C atoms, an aryl radical with

6 to 14 carbon atoms and / or polyethylene glycol (PEG) are represented, preferably in each case the same or

are different and are each independently represented by hydrogen and / or methyl and particularly preferably each methyl, is the same or different and is represented by oxygen, NH and / or NR ³ ,

is the same or different and is denoted by - (CH 2) x-, is represented,

x is the same or different and is an integer from 1 to

6 is represented,

X and Xi are the same or different and are independent

each other by a halogen atom, ci- to

C4 alkyl sulfate and / or Ci to C4 alkyl sulfonate are represented, and the one or more macromonomer structural units (B) represented by the general formula (III):

ZO (C ₃ H ₆ O), (CH ₂ CH ₂ O) _p H wherein

R ^{x is the} same or different and is represented by H and / or methyl, Z is the same or different and is represented by C = O and / or O (CH 2) 4,

I is in the molar average, a number from 0 to 6 and preferably from 0 to 5, and p is in the molar average, a number from 1 to 150, preferably from 1 1 to 100 and particularly preferably from 12 to 50.

An advantage of the invention is that the copolymers according to the invention can be prepared synthetically easily and in environmentally friendly solvent water. Another advantage of the invention is that the copolymers of the invention can be formulated into common detergent compositions because they

are water-soluble. In addition, they have a high affinity for cotton, but without acting as a dirt magnet. Textiles which are pretreated with the detergent compositions containing copolymers according to the invention are easier to clean from greasy stains. The copolymers of the invention protect textiles and in particular

Cotton textiles in an advantageous manner against dirt and lead to a very advantageous cleaning performance.

WO 2012/076365 A1 discloses cationic copolymers comprising cationic structural units and macromonomer structural units and their

Use as additive for building material systems, in particular based on calcium sulfate.

WO 2008/049549 A2 describes hydrophobically modified cationic copolymers which have at least three different structural units and of which one structural unit is a terminal phenyl group or especially substituted

Has phenyl group. With the help of the copolymers, in particular in

Combination with anionic surfactants even in the case of high salt loads a significant improvement in water retention in aqueous

Building material systems based on hydraulic binders, such as cement, can be achieved. WO 2008/141844 A1 describes dispersions comprising inorganic particles, water and at least one water-soluble polymer. The

at least one water-soluble polymer has repeating units derived from monomers having at least one quaternary ammonium group, Repeating units derived from monomers having at least one carboxy group, and repeating units derived from

Polyalkoxyalkylengruppen-containing ester monomers are derived with a number average molecular weight in the range of 3000 g / mol to 10,000 g / mol, on. The dispersions can be used in particular for the production of concrete and can be processed over a very long period of time.

WO 2008/046652 A1 describes graft polymers obtainable by copolymerization of at least one specific macromonomer and at least one further monomer which has a polymerizable ethylenically unsaturated double bond and their use as dispersants, for example in US Pat

Pigment concentrates.

In US 201 1/0144264 A1, the use of substances such. B.

Polyethylene glycol or poly (ethylene-co-propylene) glycol (meth) acrylic acid esters which may contribute to stabilization during the process of latex preparation by emulsion polymerizing at least one polymerizable monomer. JP 2008-05671 1 A discloses copolymers having a number average

Molecular weight of 5000 to 1,000,000 containing structural units which are formed by polymerization of certain cationic monomers, polyoxyalkylene-modified monomers and crosslinkable monomers and which may additionally contain further structural units obtained by polymerization of other monomers which are with the aforementioned

Monomers can be copolymerized. The copolymers may, for. B. be used as antistatic agents for thermoplastic polymers. Preferably, one or more cationic

Structural units (A) of the copolymers according to the invention

Polymerization product of at least one monomer species selected from the group consisting of [2- (acryloyloxy) ethyl] trimethylammonium chloride, [2- (acryloylamino) -ethyl] -trimethylammonium chloride, [2- (acryloyloxy) -ethyl] -methylammonium methosulfate, [2- (methacryloyloxy) -ethyl] -trimethylammonium chloride or methosulfate, [3- (acryloylamino) -propyl] -trimethylammonium chloride, [3- (methacryloylamino) -propyl] -trimethylammonium chloride and

Diallyldimethylammonium chloride (DADMAC),

Particularly preferably, the one or more cationic structural units (A) of the copolymers according to the invention represents the

A polymerization product of at least one monomer species selected from the group consisting of [3- (acryloylamino) -propyl] -trimethylammonium chloride, [3- (methacryloylamino) -propyl] -trimethylammonium chloride and

Diallyldimethylammonium chloride and

A polymerization product of at least one monomer species selected from the group consisting of [3- (methacryloylamino) -propyl] -trimethylammonium chloride and [3- (acryloylamino) -propyl] -trimethylammonium chloride.

Preferably, one or more of the macromonomers

Structural units (B) of the formula (III) of the copolymers according to the invention, the polymerization of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxy-butyl ether, polyethylene glycol co-polypropyleneglycol vinyloxybutylether (wherein I, in a molar average, a number from 1 to 6 , preferably from 1 to 5 and more preferably from 2 to 5), polyethylene glycol (meth) acrylate and polyethylene glycol-co-polypropylene glycol (meth) acrylate (wherein I, in molar ratio, a number from 1 to 6, preferably from 1 to 5 and more preferably from 2 to 5, means).

In the context of the present invention, the term "(meth) acrylate" includes both the corresponding acrylate compound and the corresponding one

Methacrylate compound.

Particularly preferred is in one or in the several macromonomer structural units (B) of the formula (III) of the copolymers of the invention i) R ^x H, I = 0 and p, in the molar average, a number from 1 to 150, preferably from 1 1 to 100 and particularly preferably from 12 to 50, when ZO is (CH 2) 4 or

ii) R ^{x is} identical or different and is represented by H and / or methyl, I, in molar average, a number from 1 to 6, preferably from 1 to 5 and particularly preferably from 2 to 5, and p, in the molar average, a number from 1 to 150, preferably from 1 to 100 and particularly preferably from 12 to 50, when ZC = O means. In a preferred embodiment of the invention, the

Copolymers of the invention

(I) one or more macromonomer structural units (B) of the formula (III), wherein R ^{x is} H, I = 0, p, in the molar average, a number from 1 to 150, preferably from 1 1 to 100 and particularly preferred is from 12 to 50, and Z is O (CH 2) 4 (hereinafter referred to as "macromonomer").

Structural units B-1 ") and

(Ii) one or more macromonomer structural units (B) of formula (III), wherein R ^{x is the} same or different and is represented by H and / or methyl, I, in the molar average, a number from 1 to 6, preferably from 1 to 5, and more preferably from 2 to 5, p, in molar average, is a number from 1 to 150, preferably from 1 to 100 and more preferably from 12 to 50, and ZC = O (hereinafter referred to as "macromonomer Preferably, the copolymers according to the invention contain both one or more macromonomer structural units B-1 and one or more

Macromonomer structural units B-2 and the molar ratio (macromonomer structural units B-1): (macromonomer structural units B-2) in these copolymers of the present invention is preferably from 1:10 to 2: 1, more preferably from 1: 8 to 1 , 5: 2 and more preferably from 1: 6 to 1: 1.

In addition to the structural units (A) and (B), the copolymers according to the invention preferably contain one or more structural units (C) which differ from the structural units (A) and (B) and wherein the one or more copolymers

preferably 0.1 to 15.4 mol% of the one or more structural units (A), 0.1 to 99.8 mol% of the one or more structural units (B) and 0.1 to 99.8 mol% % of the one or more structural units (C), more preferably 5.0 to 15.2 mol% of the one or more

Structural units (A), 20.0 to 80.0 mol% of the one or more

Structural units (B) and 10.0 to 64.8 mol% of the one or more structural units (C), and

especially preferably 7.0 to 15.0 mol% of the one or more

Structural units (A), 25.0 to 75.0 mol% of the one or more

Structural units (B) and 15.0 to 60.0 mol% of the one or more structural units (C). Preferably, the one or more structural units (C) of the copolymers of the invention is the polymerization product of at least one monomer species selected from the group consisting of non-cationic acrylamides, non-cationic methacrylamides, and N-vinyl substituted lactams having from 5 to 7 ring atoms.

Particularly preferred is the one or more structural units (C) of the copolymers of the invention selected from the group consisting of the polymerization of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and the structural units of the following general formulas (IV) and (V ):

NR ³ R ⁴ wherein

R ^{1 is the} same or different and is hydrogen and / or methyl

means, and

R ³ and each are the same or different and independently of one another by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, C atoms, a

cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, C atoms, an aryl radical having 6 to 14 C atoms, an alkylaryl radical having 7 to 14 C atoms, a branched or unbranched C 1 -C 5 -monohydroxyalkyl group and / or polyethylene glycol ( PEG)

H C = O

X wherein

R ^{11 is the} same or different and is represented by H and / or methyl; X is the same or different and is represented by NH- (C _n H2n) with n = 1, 2, 3 or 4; and

R ^{13 is the} same or different and is represented by OH, N (CH 3) 2,

SOsH, PO3H2, O-PO3H2 and / or para-substituted CehU-SOsH.

Below the polymerization product selected from N-vinyl-substituted

Lactams with 5 to 7 ring atoms is the polymerization product of

N-vinylpyrrolidone is preferred. The groups SO 3 H, PO 3 H 2, O-PO 3 H 2 and para-substituted C 6 H ₄ -SO 3 H in the structural units of the formula (V) may also be present in salt form, preferably as NH ₄ ⁺ , alkali metal or alkaline earth metal salt and more preferably as NH ₄ ⁺ - or as Na ⁺ salt.

Among the structural units of the formula (V) in which R ^{13 is} N (CH 3) 2, those structural units which contain the polymerization product of at least one monomer species selected from the group consisting of [3- (methacryloylamino) -propyl] -dimethylamine (R ¹¹ = methyl, X = NH- (C _n H2n) with n = 3 and R ¹³ = N (CH 3) 2) and [3- (acryloylamino) -propyl] -dimethylamine (R ¹¹ = H; X = NH- (R ¹¹ = H; CnH _2n ) with n = 3 and R ¹³ = N (CH ₃ ) ₂ ).

Preferred among the structural units of the formula (V) are those which contain the polymerization product of at least one monomer species selected from the group consisting of [3- (acryloylamino) -propyl] -dimethylamine,

[3- (methacryloylamino) -propyl] -dimethylamine, 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid, and particularly preferably those which contain the polymerization product of at least one monomer species selected from the group consisting of Acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid represent.

Particularly preferably, the one or more structural units (C) of the copolymers according to the invention is selected from the structural units of the formula (IV).

Most preferably, one or more provide

Structural units (C) of the copolymers according to the invention

Polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide,

Ν, Ν-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tertiary butylacrylamide, and

most preferably, one or more provides

Structural units (C) of the copolymers according to the invention

Polymerization product of at least one monomer species selected from the group consisting of Ν, Ν-dimethylacrylamide and N-isopropylacrylamide.

In a further preferred embodiment of the invention, the copolymers according to the invention contain only structural units (A), (B) and (C) as recurring structural units, but beyond that no further

recurring structural units. In this preferred embodiment of the invention, the copolymers according to the invention preferably contain the one or more structural units (A) in an amount of from 5.0 to

15.2 mol% and more preferably in an amount of 7.0 to 15.0 mol%, the one or more structural units (B) preferably in an amount of 20.0 to 80.0 mol%, and especially preferably in an amount of 25.0 to 75.0 mol% and the one or more structural units (C) preferably in an amount of 10.0 to 64.8 mol%, and more preferably in an amount of 15.0 to 60.0 mol%. In this preferred embodiment of the invention, more preferably, the one or more structural units (A) is the polymerization product of at least one monomer species selected from the group consisting of [3- (methacryloylamino) -propyl] trimethylammonium chloride and [3- (acryloylamino) -propyl ] - trimethylammonium chloride, the plurality of structural units (B) contain both macromonomer structural units B-1 and macromonomer structural units B-2 having a molar ratio (macromonomer structural units B-1): (macromonomer structural units B-2) of preferably 1: 6 to 1: 1, and the one or more structural units (C) is the polymerization product of at least one monomer species selected from the group consisting of Ν, Ν-dimethylacrylamide and N-isopropylacrylamide.

In a further preferred embodiment of the invention, the copolymers according to the invention contain in addition to the structural units (A), (B) and (C) one or more structural units (D) which differ from the structural units (A), (B) and (C) and wherein the one or more copolymers preferably 0.1 to 15.4 mol% of the one or more the plurality of structural units (A), 0.1 to 99.7 mol% of the one or more structural units (B), 0.1 to 99.7 mol% of the one or more structural units (C) and 0.1 to

99.7 mol% of the one or more structural units (D), more preferably 5.0 to 15.2 mol% of the one or more

Structural units (A), 20.0 to 50.0 mol% of the one or more

Structural units (B), 10.0 to 60.0 mol% of the one or more

Structural units (C) and 0.1 to 35.0 mol% of the one or more

Contain structural units (D), and

especially preferably 7.0 to 15.0 mol% of the one or more

Structural units (A), 25.0 to 40.0 mol% of the one or more

Structural units (B), 15.0 to 50.0 mol% of the one or more

Structural units (C) and 5.0 to 30.0 mol% of the one or more

Structural units (D) included.

If the copolymers according to the invention contain one or more structural units

(D) contain, in a particularly preferred embodiment of the invention, one or more structural units (D) selected from the

Structural units of the following general formula (VIII):

NR ³ R ⁴

is the same or different and represented by -CO-O- (CH 2) x,

is an integer from 1 to 6, preferably 2 or 3, is the same or different and is hydrogen and / or methyl, and

R ³ and R ^{4 are} each the same or different and independently of one another by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, C atoms, a

Cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, carbon atoms, an aryl radical having 6 to 14 carbon atoms and / or polyethylene glycol (PEG) are represented. If the copolymers according to the invention contain one or more structural units (D), these are in a particularly preferred embodiment of the invention selected from the structural units of the formula (VIII).

Preferred among the structural units of the formula (VIII) are those which contain the polymerization product of at least one monomer species selected from the group consisting of [2- (methacryloyloxy) ethyl] -dimethylamine,

[2- (acryloyloxy) -ethyl] -dimethylamine, [2- (methacryloyloxy) -ethyl] -diethylamine and [2- (acryloyloxy) -ethyl] -diethylamine. If the copolymers according to the invention contain one or more structural units (D), they contain in a further particularly preferred

Embodiment of the invention one or more structural units (D) selected from the structural units of the following general formulas (IX) and / or (X):

(IX)

wherein

R ^{11 is the} same or different and is represented by H and / or methyl; Z is the same or different and is represented by O and / or NH;

R 15 in which

R11 is the same or different and is represented by H and / or methyl;

Q is the same or different and is represented by O and / or NH; and

_R 15 is the same or different and is represented by H, (C _n H 2n) -SO 3 H where n = 0, 1, 2, 3 or 4; (C _n H _2n ) -OH with n = 0, 1, 2, 3 or 4; (CnH _2n ) -PO 3 H 2 with n = 0, 1, 2, 3 or 4; (CnH _2n ) -OPO 3 H 2 with n = 0, 1, 2, 3 or 4;

(C ₆ H) -SO ₃ H; (C6H) -PO ₃ H _2; (C ₆ H) -OPO ₃ H 2 and / or

(CmH2m) eO- (A'O) _u -R ¹⁶ with m = 0, 1, 2, 3 or 4, e = 0, 1, 2, 3 or 4, A '= Cx'H2x' with x '= 2, 3, 4 or 5, u = an integer from 1 to 350 and R ^{16 are} identical or different and represented by an unbranched or branched C 1 -C ⁴ -alkyl group. If the copolymers according to the invention contain one or more structural units (D), these are in a further particularly preferred

Embodiment of the invention selected from the structural units of the formulas (IX) and / or (X). The structural units of formula (X) can also be present in salt form, preferably as NH ₄ ⁺ -, alkali or alkaline earth salt, and most preferably as NH ⁺ - or Na ⁺ salt. Preferred among the structural units of the formulas (IX) and (X) are those which are the polymerization product of at least one monomer species selected from the group consisting of maleic anhydride, maleic acid and the salts of maleic acid. If the copolymers according to the invention contain one or more structural units (D), they contain in a further particularly preferred

Embodiment of the invention one or more structural units (D) selected from the structural units of the following general formula (VII):

is the same or different and represented by -COOMk, is the same or different and is represented by H and / or an unbranched or branched Ci-C4-alkyl group and is preferably represented by H or methyl; and

a cation selected from the group consisting of hydrogen ion, alkali ion and alkaline earth ion, where k = valency.

If the copolymers according to the invention contain one or more structural units (D), these are in a further particularly preferred

Embodiment of the invention selected from the structural units of the formula (VII).

Preferred among the structural units of the formula (VII) are those which comprise the polymerization product of at least one monomer species selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate,

Methacrylic acid, Nathummethacrylat and potassium methacrylate represent.

If the copolymers according to the invention contain one or more structural units (D), they contain in a further particularly preferred

Embodiment of the Invention One or more structural units (D) selected from the structural units of the following general formulas (Va), (Vb) and / or (Vc):

W

In which

R ^{11 is the} same or different and is represented by H and / or methyl; W is the same or different and is represented by O;

R ^{12 is the} same or different and is represented by a branched or unbranched C 1 -C 8 monohydroxyalkyl group;

R 13 in which

R ^{11 is the} same or different and is represented by H and / or methyl; X is the same or different and is represented by O- (C _n H2n) where n = 1, 2, 3 or 4;

R ^{13 is the} same or different and is represented by OH, SO 3 H, PO 3 H 2, O-PO 3 H 2 and / or para-substituted C 6 H ₄ -SO 3 H;

wherein

R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and are each independently represented by H and / or an unbranched or branched C 1 -C ⁴ -alkyl group;

n is the same or different and is represented by 0, 1, 2,

3 and / or 4;

R ^{17 is the} same or different and is represented by (C6H5),

OH, OR ^y wherein R ^{y is} an alkyl group having from 1 to 8 and preferably 4 carbon atoms, and / or

-OOCCHs.

Embodiment of the invention selected from the structural units of the formulas (Va), (Vb) and / or (Vc).

The groups SO3H, PO3H2, O-PO3H2 and para-substituted C 6 H ₄ -SO 3 H in the structural units of the formula (Vb) can also be present in salt form,

preferably as NH ₄ ⁺ , alkali or alkaline earth salt and more preferably as NH ⁺ or as Na ⁺ salt.

Preferred among the structural units of the formula (Vc) are those which are the polymerization product of at least one monomer species selected from the group consisting of vinyl butyl ether and vinyl acetate.

In a further preferred embodiment of the invention, the copolymers according to the invention contain only structural units (A), (B), (C) and (D) as recurring structural units, but beyond that no further

15.2 mol% and more preferably in an amount of 7.0 to 15.0 mol%, the one or more structural units (B) preferably in an amount of 20.0 to 50.0 mol% and especially preferably in an amount of 25.0 to 40.0 mol%, the one or more structural units (C) preferably in an amount of 10.0 to 60.0 mol%, and more preferably in an amount of 15.0 to 50.0 mol% and the one or more structural units (D) preferably in an amount of 0.1 to 35.0 mol%, and more preferably in an amount of 5.0 to 30.0 mol%. In this preferred embodiment of the invention, more preferably, the one or more structural units (A) represents the

A polymerization product of at least one monomer species selected from the group consisting of [3- (methacryloylamino) -propyl] -trimethylammonium chloride and [3- (acryloylamino) -propyl] -trimethylammonium chloride, the plurality of structural units (B) contain both macromonomer structural units B-1 also macromonomer structural units B-2, preferably with a molar ratio (macromonomer structural units B-1): (macromonomer structural units B-2) from 30: 70 to 70: 30, and particularly preferably from 40: 60 to 60: 40 , the one or the plurality of structural units (C) represents the polymerization product of at least one monomer species selected from the group consisting of Ν, Ν-dimethylacrylamide and N-isopropylacrylamide, preferably of N-isopropylacrylamide, and represents the one or more structural units ( D) the polymerization product of at least one monomer species selected from the group consisting of acrylic acid,

Methacrylic acid, the salts of acrylic acid and the salts of methacrylic acid.

Preferably, the structural units (A), (B) and optionally (C) and (D) of the copolymers according to the invention are present in random, block-shaped, alternating or gradient-like distribution in the copolymer.

Preferably, the weight average molecular weight M _{w is} the

Copolymers of the invention from 10,000 to 400,000 g / mol, more preferably from 15,000 to 350,000 g / mol and particularly preferably from

50,000 to 330,000 g / mol.

The weight-average molecular weight M _{w of} the copolymers according to the invention can be determined by gel permeation chromatography (GPC).

preferably as follows: 10 μΙ_ of the sample are injected into a PSS Novema Max Guard column of the following dimensions: 300 × 8 mm with a permeability of 1 × 30 A and 2 × 1000 A and particle size of 10 μιτι. Detection is by the refractive index at 25 ° C. The eluent used is 79.7% by volume 0.1 M NaCl + 0.3% by volume TFA (trifluoroacetic acid) + 20.0% by volume ACN (acetonitrile). Separation takes place at a flow rate of 1 mL / minute. The size is determined by comparison with the elution time of standard samples of

Poly (2-vinylpyridines) defined molecular weights in the range of 1 1 10 to 1 060 000 daltons.

The copolymers according to the invention contain recurring structural units (in general -C ( ^Rs1 ) ( ^Rs2 ) -C ( ^Rs3 ) ( ^Rs4 ) -) which contain the polymerization product of corresponding monomers having polymerizable olefinic double bonds (in general C ( ^Rs1 ) (R ^s2 ) = C (R ^s3 ) (R ^s4 )). The radicals ^R.sub.s1 , ^R.sub.s2 , ^R.sub.s3 and ^R.sub.s4 are not defined in more detail here, but are indicated only for the sake of completeness as radicals bonded to the corresponding carbon atoms C. The structural units (A) and (B) contained in the copolymers according to the invention and optionally additionally in the copolymers of the invention

Structural units (C) and (D) contained for example are such

recurring structural units. Structural units derived, for example, from radical initiators or from chain transferers optionally used in the copolymerization are not repetitive

Structural units. Accordingly, be under recurring

Structural units understood, for example, no terminal groups. The quantities in mol% indicated for the structural units (A), (B), (C) and (D) are based on the total amount of the compounds according to the invention

Copolymers contained recurring structural units. The copolymers according to the invention can be prepared by methods which are familiar to the person skilled in the art. Particularly preferably, the

Copolymers according to the invention can be prepared by free-radical solvent polymerization. Common solvents may be, for example, polar solvents such as alcohols or water, as well as alcohol-water mixtures. The

Polymerization is effected by radical sources, e.g. inorganic persulfates, organic azo compounds, peroxides, hydroperoxides, inorganic

Redox systems, or UV light started. In addition, you can

Chain transfer regulators are used, which are less reactive radicals to control the molecular weight of the copolymers. Such

Chain transfer controllers are e.g. Phenols, thiols, for example

2-mercaptoethanesulfonate sodium, or sodium hypophosphite. In a

By way of example, the monomers for preparing the

Copolymers according to the invention and optionally one

Dissolved chain transfer regulator in the solvent, expelled oxygen, then the temperature increased, and the radical initiator dosed. The copolymerization is then carried out at the desired temperature for the desired period of time. The reaction mixture is then optionally cooled and the copolymer formed either further processed in solution or worked up, for. B., the copolymer-containing solution by partial evaporation of the

Solvent, optionally under reduced pressure, be concentrated or the solvent can be completely removed by evaporation or else the copolymer can be otherwise isolated, for example by freeze-drying or precipitation.

As already mentioned, the copolymers according to the invention can be used advantageously in detergent compositions. In the

Detergent compositions represent the copolymers of the invention, the component Z1). These detergent compositions are described in more detail below.

Preferably, the detergent compositions contain one or more copolymers of component Z1) in an amount of 0.0005 to 10.0 wt .-%, particularly preferably in an amount of 0.001 to 5.0 wt .-%, and particularly preferably in one Amount of 0.1 to 2.0 wt .-%, based on the

Total weight of the detergent composition.

Component Z2)

The detergent compositions contain as component Z2) one or more surfactants. Preferably, the one or more surfactants of component Z2) of the detergent compositions are selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants. More preferably, the one or more surfactants is the

Component Z2) of the detergent compositions selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides,

Alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates,

Glucamides, amine oxides, betaines and quaternary ammonium compounds.

Examples of anionic surfactants are alkylbenzenesulfonates, alkyl sulfates,

Alkyl ether sulfates, alkanesulfonates, alkyl ether carboxylic acids, sulfosuccinates, isethionates, taurates, glycinates and / or acylglutamates. The alkyl chains of said surfactants may be of synthetic or natural origin and preferably consist of 8 to 30, more preferably 8 to 18 and

in particular preferably 12 to 14 carbon atoms in linear or branched

Arrangement.

Anionic surfactants which are used according to the invention are preferably aliphatic sulfates, such as fatty alcohol sulfates, fatty alcohol ether sulfates,

Dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such

Alkanesulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates,

Estersulfonates and lignosulfonates. Also usable in the context of the present invention are alkylbenzenesulfonates, fatty acid cyanamides,

Sulfosuccinates (sulfosuccinic acid esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides),

Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and

[alpha] sulfo fatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

Preferred thereof are the fatty alcohol sulfates and / or fatty alcohol ether sulfates, in particular the fatty alcohol sulfates. Fatty alcohol sulfates are products of

Sulfation reactions on corresponding alcohols while Fettal kholethersulfate products of sulfation of alkoxylated

Alcohols are. The skilled worker generally understands by alkoxylated

Alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols. In general, from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of

Addition products of different degrees of ethoxylation. Another

Embodiment of the alkoxylation is the use of mixtures of

Alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.

Preferred fatty alcohol ethers are the lower ethoxylated sulfates

Fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1, 3 EO.

Particularly preferred are alkylbenzenesulfonate, alkanesulfonate, alkyl ether sulfate or alkyl sulfate.

The anionic surfactants are usually used as salts, but also as acid. The salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts and mono-, di- or

Trialkanolammoniumsalze, for example, mono-, di- or

Triethanolammoniumsalze, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or potassium salts, particularly preferably sodium salts. Other surfactants may be nonionic, amphoteric and / or cationic surfactants, for example betaines, amidobetaines, amine oxides, amidoamine oxides,

Fettal koholpolyglykolether, alkyl polyglycosides or quaternary

Ammonium compounds. Other nonionic surfactants may be, for example, alkoxylates

Polyglycol ethers, fatty alcohol polyglycol ethers (fatty alcohol alkoxylates),

Alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also usable Ethylene oxide-propylene oxide block polymers, and fatty acid alkanolamides and

Fatty acid polyglycol. Another important class of nonionic surfactants that can be used according to the invention are the polyol surfactants, and in particular the glycated surfactants, such as alkyl polyglycosides, in particular

Alkylpolyglucosides.

Suitable fatty alcohol polyglycol ethers are with ethylene oxide (EO) and / or

Propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 8 -C 22 -alcohols having a degree of alkoxylation of up to 30,

preferably ethoxylated Cio-Ci8 fatty alcohols having a degree of ethoxylation of less than 30, more preferably 1 to 20, particularly preferably 1 to 12 and exceptionally preferably 1 to 8, for example Ci2-Ci4-fatty alcohol ethoxylates with 8 EO. Alkyl polyglycosides are surfactants produced by the reaction of sugars and

Alcohols can be obtained by the relevant methods of preparative organic chemistry, and depending on the nature of the preparation to a mixture of monoalkylated, oligomeric or polymeric sugar comes. Preferred alkylpolyglycosides are the alkylpolyglucosides, wherein the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs to C18-alkyl chains and the

Degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6, more preferably 1, 1 to 3 and particularly preferably 1, 1 to 1, 7, for example C8-Cio-alkyl-1, 5-glucoside (DP from 1, 5).

The amphoteric surfactants (zwitterionic surfactants) which can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants. Suitable betaines are the alkylbetaines, the alkylamidobetaines, the

Imidazoliniumbetaine, the sulfobetaines (INCI Sultaines) and the amidosulfobetaines and the phosphobetaines. Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: almondamidopropyl betaines, Apricotamidopropyl betaines, avocadamidopropyl betaines,

Babassuamidopropylbetaine, behenamidopropylbetaine, behenylbetaine, betaine, canolamidopropylbetaine, caprylic / capramidopropylbetaine, carnitine,

Cetylbetaines, cocamidoethylbetaines, cocamidopropylbetaines,

Cocamidopropyl hydroxysultaine, cocobetaines, cocohydroxy sultaine,

Coco / oleamidopropylbetaines, coco-sultaines, decylbetaines, dihydroxyethyl oleylglycinates, dihydroxyethyl soy glycinates, dihydroxyethylstearylglycinates, dihydroxyethyl tallow glycinates, dimethicones, propyl PG-betaines,

Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine,

Isostearamidopropyl betaines, lauramidopropyl betaines, lauryl betaines,

Laurylhydroxysultaine, laurylsultaine, milkamidopropylbetaine,

Minkamidopropylbetaine, myristamidopropylbetaine, myristylbetaine,

Oleamidopropylbetaines, oleamidopropylhydroxysultaines, oleylbetaines,

Olivamidopropyl betaines, palmamidopropyl betaines, palmitamidopropyl betaines, palmitoyl carnitines, palm kernel amidopropyl betaines, polytetrafluoroethylene acetoxypropyl betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, soy amidopropyl betaines, stearamidopropyl betaines, stearyl betaines,

Tallowamidopropylbetaine, tallowamidopropylhydroxysultaine, tallowbetaine, tallowdihydroxyethylbetaine, undecylenamidopropylbetaine and wheat

Germamidopropyl Betaine.

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and

Alkoxyalkyl.

Examples of suitable amine oxides are the following named according to INCI

Compounds: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide,

Decyltetradecylamines oxides, diaminopyrimidines oxides, dihydroxyethyl

C8-C10 alkoxypropylamines oxides, dihydroxyethyl C9-C11 alkoxypropylamines oxides, dihydroxyethyl C12-C15 alkoxypropylamines oxides, dihydroxyethyl cocamines oxides, dihydroxyethyl lauramines oxides, dihydroxyethyl stearamines oxides, Dihydroxyethyl Tallowan Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowanine Oxide, Hydroxyethyl Hydroxypropyl

C12-C15 alkoxypropylamines oxides, isostearamidopropylamines oxides,

Iso-Stearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide,

Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide, Myristyl / Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide,

Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowannine Oxide, Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxide. Exemplary alkylamidoalkylamines are the following compounds designated as INCI: cocoamphodipropionic acid, cocobetainamido amphopropionate, DEA-cocoamphodipropionate, disodium caproamphodiacetate, disodium

Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium

Capryloamphodipropionate, disodium cocoamphocarboxyethyl-hydroxypropylsulfonate, disodium cocoamphodiacetate, disodium

Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium

Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-lsodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium

Capryloamphohydroxypropylsulfonates, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonates, Sodium

Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium

Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium

Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium

Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium

Tallowamphoacetate, sodium undecylenoamphoacetate, sodium

Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate. Exemplary alkyl-substituted amino acids are the following compounds designated as INCI: aminopropyl laurylglutamine, cocaminobutyric acid, cocaminopropionic acid, DEA-lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium

Lauriminodipropionate, Disodium Steariminodipropionate, Disodium

Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium

C12-C15 alkoxypropyl iminodipropionate, sodium cocaminopropionate, sodium lauraminopropionate, sodium lauriminodipropionate, sodium lauroyl

Methylaminopropionate, TEA-Lauraminopropionate and

TEA Myristaminopropionate.

Preferably, the detergent compositions contain the one or more surfactants of component Z2) in an amount of 0.1 to 60.0 wt .-%, particularly preferably in an amount of 0.5 to 50 wt .-%, particularly preferably in from 1 to 45% by weight, and more preferably from 2 to 40% by weight, based on the total weight of the detergent composition.

Preferably, the detergent compositions contain one or more others in addition to the one or more copolymers of component Z1) and the one or more surfactants of component Z2)

Substances selected from the components Z3), Z4), Z5), Z6) and / or Z7): Z3) one or more complexing agents as component Z3), Z4) one or more solvents other than water as component Z4),

Z5) one or more further additives, preferably selected from

Group consisting of viscosity regulators, enzymes, bleaching agents,

Bleach activators, bleach catalysts, grayness inhibitors,

Dye transfer inhibitors, dye fixatives, optical brighteners, preservatives, perfumes, dyes, and

Buffer substances (but optionally also further additives, for example as described below) as component Z5),

Z6) water as component Z6),

Z7) one or more builders as component Z7).

The complexing agents (INCI chelating agents) of component Z3), too

Called sequestering agents, they are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, for example clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. In addition, the complexing agents support the

Cleaning effect.

For example, the following are suitable according to INCI

Complexing agents: aminotrimethylene, phosphonic acid, beta-alanine diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamine

Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacydoheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl

Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphates, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonates, Sodium Citrate, Sodium

Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethyl Glycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium

Metaphosphates, Sodium Metasilicate, Sodium Phytate, Sodium

Polydimethylglycinophenolsulfonates, sodium trimetaphosphates, TEA-EDTA, TEA polyphosphates, tetrahydroxyethyl ethylenediamines, tetrahydroxypropyl ethylenediamines, tetrapotassium etidronates, tetrapotassium pyrophosphates, tetrasodium EDTA, tetrasodium etidronates, tetrasodium pyrophosphates, tripotassium EDTA, trisodium dicarboxymethyl alaninates, trisodium EDTA, trisodium HEDTA, trisodium NTA and trisodium Trisodium phosphates.

Preferred complexing agents are i.a. organic phosphonates,

Alkane hydroxy phosphonates and carboxylates available under the trademark DEQUEST from Thermphos. A particularly preferred

Chelating agent is HEDP (1-hydroxyethylidene-1, 1-diphosphonic acid), which is marketed as Dequest 2010, for example. Dequest ^® 2066

(Diethylenetriamine penta (methylenephosphonic acid) or heptasodium DTPMP) is also suitable but less preferred because it is inferior

Cleaning results.

The proportion of component Z3), if different from 0%, is preferably from 0.001 to 10% by weight, more preferably from 0.005 to 7% by weight and most preferably from 0.01 to 5% by weight, each based on the total weight of the detergent composition.

If the detergent composition is liquid, it may also contain one or more nonaqueous solvents or hydrotropes as component Z4). In the context of the present invention, a hydrotrope is a solvent which is neither water nor a conventional surfactant which aids in solubilizing the surfactants and other components, especially polymer and complexing agent, in the liquid to make isotropic. Preferred hydrotropes include: monopropylene glycol (MPG), glycerol, sodium cumene sulfonate, ethanol, other glycols, eg dipropylene glycol, diether and urea. preferred

Hydrotropics are MPG and glycerin.

The proportion of component Z4), when different from 0%, is preferably from 0.001 to 50% by weight, more preferably from 0.01 to 30% by weight and most preferably from 0.1 to 20% by weight. %, in each case based on the total weight of the detergent composition.

In addition to the ingredients already listed as Z1), Z2), Z3) and Z4), the detergent compositions may contain one or more optional ingredients Z5), e.g. conventional ingredients commonly used in detergent compositions, especially laundry detergent compositions. Examples of optional ingredients include i.a. Viscosity regulators, bleaching agents, bleaching-active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors,

Dye fixatives, grayness inhibitors, dispersants, fabric softeners, antistatics, optical brighteners, enzymes, enzyme stabilizers, foam regulators, defoamers, deodorizing agents, preservatives, disinfectants, fiber lubricants, anti-shrinkage agents, buffering agents, fragrances,

Processing aids, colorants, dyes, pigments, corrosion inhibitors, fillers, stabilizers, and other conventional detergent composition ingredients.

In addition to the copolymers described as component Z1), the

Detergent compositions further polymers to promote

Washing power included. Examples of these are polyalkoxylated polyethylenimines, e.g. polyethoxylated polyethyleneimines (EPEI) and conventional polyester-based soil release polymers. Polyethyleneimines are

Substances composed of ethyleneimine units -CH2CH2NH-, wherein in the case of branching, the hydrogen on the nitrogen is replaced by another chain of ethyleneimine units. These polyethyleneimines can for example, by polymerization of ethyleneimine in the presence of a

Catalysts such as carbon dioxide, sodium bisulfite, sulfuric acid,

Hydrogen peroxide, hydrochloric acid, acetic acid and the like. Specific methods for preparing these polyamine backbones are found in US 2,182,306, US 3,033,746, US 2,208,095, US 2,806,839 and US 2,553,696.

The proportion of polyalkoxylated polyethylenimines is 0%

is different, preferably from 0.05 to 10 wt .-% and particularly preferably from 0.1 to 6 wt .-%, each based on the total weight of the detergent composition.

Polyester-based soil release polymers generally include polymers of aromatic dicarboxylic acids and alkylene glycols (including

Polymers which additionally contain polyalkylene glycols). To the here

Useful polymeric soil release agents include, in particular, those soil release agents having (a) one or more nonionic hydrophilic agents

Components consisting essentially of (i) polyoxyethylene segments having a degree of polymerization of at least 2 or (ii) oxypropylene or

Polyoxypropylene segments having a degree of polymerization of from 2 to 10, wherein the hydrophilic segment does not comprise an oxypropylene moiety except when attached via ether linkages to adjacent moieties at each end; or (iii) a mixture of oxyalkylene moieties, the oxyethylene and from 1 to about 30 oxypropylene units, said mixture containing such an amount of oxyethylene units that the hydrophilic component is hydrophilic enough to inhibit the hydrophilicity of conventional polyester fiber surfaces upon deposition of the soil release agent on such surface wherein the hydrophilic segments are preferably at least about 25% oxyethylene units and more preferably, especially for those

Components containing from about 20 to 30 oxypropylene units, containing at least about 50% oxyethylene units; or (b) one or more

hydrophobic components comprising: (i) C3 oxyalkylene terephthalate segments, wherein when the hydrophobic components also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate to C3 oxyalkylene terephthalate units is about 2: 1 or less,

(ii) C 4 -C 6 -alkylene or oxy-C 4 -C 6 -alkylene segments or mixtures thereof,

(iii) poly (vinyl ester) segments, preferably polyvinyl acetate, with a

Degree of polymerization of at least 2 or (iv) C 1 -C 4 alkyl ether or (II)

C4 hydroxyalkyl ether substituents or mixtures thereof, wherein the

Substituents in the form of C1-C4-Alkylether- or

C4 hydroxyalkyl ether cellulose derivatives or mixtures thereof, and such cellulose derivatives are amphiphilic, having a sufficient content of C1-C4 alkyl ether and / or C4 hydroxyalkyl ether units to deposit on conventional polyester fiber surfaces and adhered to such a conventional synthetic fiber surface to retain a sufficient content of hydroxyl groups to increase the hydrophilicity of the fiber surface, or a combination of (a) and (b). Typically, the polyoxyethylene segments of (a) (i) have a

Degree of polymerization of from about 1 to about 200, although higher levels may be used, preferably from 3 to about 150, and more preferably from about 6 to about 100. A preferred polymeric soil release agent is a polyester having

Repeating units of alkylene terephthalate units containing 10-30% by weight of alkylene terephthalate units together with 90-70% by weight

Polyoxyethylene terephthalate units derived from a polyoxyethylene glycol having an average molecular weight of 300-8000 contains. Examples of this polymer are commercially available substances TexCare ^® SRN170 and TexCare ^® SRN260 Clariant. See also US 4,702,857.

The proportion of the polyester-based soil release polymers, if it is different from 0%, preferably from 0.05 to 5 wt .-% and particularly preferably from 0.1 to 3 wt .-%, each based on the Total weight of the detergent composition. In addition to the described polyester-based soil release polymers and polyalkoxylated polyethyleneimines, the detergent compositions may contain other polymeric materials, for example:

dye transfer inhibiting polymers or graying-inhibiting polymers

Polymers. In particular, in the absence of polyalkoxylated polyethylenimines, the liquid detergent compositions may be a polymer of

Polyethylene glycol and vinyl acetate, for example, the slightly grafted copolymers according to WO 2007/138054. Such amphiphilic graft polymers based on water-soluble polyalkylene oxides as a grafting base and side chains formed by polymerization of a vinyl ester component are capable of allowing a reduction in surfactant contents while maintaining high levels of oily stain removal.

In the case of liquid detergent compositions, a buffer substance is preferably also used. In addition to funds, where appropriate to

Production of anionic surfactants, e.g. from LAS or fatty acids,

are used, the presence of buffer substances to regulate the pH is preferred. The buffer substance is one or more

Ethanolamines, e.g. Monoethanolamine (MEA) or triethanolamine (TEA), in

Consideration. Other suitable amino alcohol buffering agents may be selected from the group consisting of compounds having a molecular weight greater than 61 g / mol, including MEA. Also suitable are, in addition to the substances already mentioned: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoaminohexanol, 2 - [(2-methoxyethyl) methylamino] ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanolamine,

Isobutanolamine, monopentanolamine, 1-amino-3- (2-methoxyethoxy) -2-propanol, 2-methyl-4- (methylamino) -2-butanol, and mixtures thereof. Possible

Alternatives to aminoethanol buffers are alkali hydroxides such as sodium hydroxide or potassium hydroxide.

The proportion of the buffer substances is, if it is different from 0%, preferably from 0.01 to 10 wt .-% and particularly preferably from 0.1 to 8 wt .-%, each based on the total weight of the detergent composition.

The detergent compositions may contain one or more enzymes. Preferably, the one or more enzymes is selected from the group consisting of protease, mannanase, pectate lyase, cutinase, esterase, lipase, amylase and cellulase. Less preferred additional enzymes can be selected from peroxidase and oxidase. The enzymes are preferably present with corresponding enzyme stabilizers.

The proportion of the enzymes is, if it is different from 0%, preferably from 0.01 to 8 wt .-% and particularly preferably from 0.1 to 5 wt .-%, each based on the total weight of the detergent composition. It may be advantageous to use optical brightener and / or bleach catalyst in the detergent compositions as further highly efficient performance additives. Desirably, perfume and colorants are also included. The detergent compositions may additionally comprise foam enhancing agents, polyelectrolytes, anti-kick agents,

Anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents,

Antistatic and ironing aids included. Liquid detergent compositions may also contain viscosity modifiers, pearlescers and / or opacifiers, or other substances that cause visual effects. In addition to the components Z1), Z2), Z3), Z4) and Z5), water can also be used as component Z6) in the detergent compositions. When the detergent composition is liquid, the amount of water in the liquid detergent composition may be from 1 to 95 weight percent, based on the total weight of the liquid detergent composition. Very low water content compositions are best suited for water-soluble sachets and capsules. In the case of powdered detergent compositions, the amount of water is preferably less than 10 wt .-%, based on the total weight of the powdered detergent composition.

If appropriate, the detergent compositions also contain builders as component Z7). Builders include inorganic and / or organic

Builders to reduce the hardness of the water. They may be included in the detergent compositions at levels of from about 5 to about 80% by weight. Inorganic complexing agents include, for example, alkali metal, ammonium and alkanolammonium salts of

Polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

Examples of silicate builders are the alkali metal silicates, in particular those having a SiO 2: Na 2 O ratio between 1.6: 1 and 3.2: 1, and also phyllosilicates, for example sodium layer silicates, as described in US Pat

US 4,664,839. Aluminosilicate builders are particularly preferred for the present invention. These are, in particular, zeolites of the formula Na _z [(AIO 2) _z (SiO 2) _y ] x H 2 O, in which z and y are integers of at least 6, the ratio of z to y is between 1, 0 and about 0.5 and x is an integer from about 15 to about 264.

Suitable aluminosilicate-based ion exchangers are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically produced. Methods for the preparation of aluminosilicate based ion exchangers are described in US 3,985,669 and US 4,605,509. Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the designation zeolite A, zeolite P (B) (including those disclosed in EP-A-0 384 070) and zeolite X. Preferred are

Aluminosilicates with a particle diameter between 0.1 and 10 μιτι. Suitable organic builders include polycarboxylic compounds such as ether polycarboxylates and oxydisuccinates as described, for example, in US 3,128,287 and US 3,635,830. Reference should also be made to "TMS / TDS" builders from US 4,663,071.

Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether,

1, 3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well

Polycarboxylic acids, such as militic acid, succinic acid, oxydisuccinic acid, polymaleic acid,

Benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.

Citrate-based builders, e.g. Citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid builders which can also be used in granulated formulations, in particular together with zeolites and / or sheet silicates.

Other suitable builders are the 3,3-dicarboxy-4-oxa-1, 6-hexanedioates and the related compounds disclosed in US 4,566,984. If

Phosphorus-based builders can be used, and particularly where hand soap bars are to be formulated by hand, various alkali metal phosphates such as sodium tripolyphosphate,

Sodium pyrophosphate and sodium orthophosphate are used. Likewise, phosphonate builders,

such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates as disclosed, for example, in US 3,159,581, US 3,213,030, US 3,422,021, US 3,400,148 and US 3,422,137.

The proportion of component Z7), if it is different from 0%, preferably from 0.1 to 95 wt .-%, particularly preferably from 0.5 to 90 wt .-% and particularly preferably from 0.5 to 80 wt .-%, each based on the total weight of the detergent composition.

In a preferred embodiment of the invention, the detergent compositions contain:

(a) 0.0005 to 10.0% by weight of component Z1),

(b) 0.1 to 60.0% by weight of component Z2),

(c) from 0.0 to 10.0% by weight of component Z3),

(d) 0.0 to 50.0% by weight of component Z4),

(e) from 0.0 to 10.0% by weight of component Z5),

(f) 0.0 to 95.0% by weight of component Z6), and

(g) 0.0 to 95.0% by weight of component Z7),

each based on the total weight of the detergent composition. The detergent compositions according to the invention can under

Standard conditions (25 ° C, 1 atmosphere (1 atm)) in liquid form or as a powder.

In a preferred embodiment of the invention, the detergent compositions are liquid having a pH of from 6 to 14, preferably from 6 to 12, and more preferably from 7 to 12.

Another object of the present invention are also the detergent compositions containing one or more copolymers of the invention.

The copolymers of the invention and the detergent compositions according to the invention are advantageously suitable for cleaning textiles and preferably for cleaning cotton-containing textiles.

Another object of the invention is therefore the use of

Copolymers of the invention or the detergent composition according to the invention Compositions for cleaning textiles and preferably for

Cleaning cotton-containing textiles.

The copolymers according to the invention and the detergent compositions according to the invention are moreover advantageously suitable for reducing the re-soiling of the textiles and, preferably, the re-soiling of cotton-containing textiles on which the copolymers according to the invention or the detergent compositions according to the invention have been applied.

Another object of the invention is therefore the use of

copolymers according to the invention or the detergent compositions according to the invention for reducing the re-soiling of the textiles and preferably the re-soiling of cotton-containing textiles to which the copolymers according to the invention or the detergent compositions according to the invention have been applied.

The invention is explained in more detail below by examples without limiting it thereto. Unless explicitly stated otherwise in the examples, the percentages in the examples are to be understood as percent by weight (% by weight).

Examples

The following abbreviations are used

AAPTAC [3- (acryloylamino) -propyl] -trimethylammonium chloride

(75% by weight active in aqueous solution)

DMAA N, N-Dimethylacrylamide

(100% active)

DADMAC diallyldimethylammonium chloride

(65 wt .-% active in aqueous solution) MAPTAC [3- (methacylloylamino) -propyl] -trimethylammonium chloride

(50% by weight active in aqueous solution)

NIPAM N-isopropylacrylamide

(100% active)

PEG MA 1000 polyethylene glycol-co-polypropylene glycol methacrylate, 1000 g / mol,

4-5 propylene glycol units (70 wt .-% active in aqueous

Solution)

VA-44 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride

(100% active)

V-PEG 1 100 polyethylene glycol-vinyloxy-butyl ether, 1 100 g / mol

(100% active)

Preparation of Copolymers of the Invention

General procedure for the preparation of copolymers according to the invention

In a multi-necked flask equipped with a KPG stirrer, reflux condenser and N 2 connection, the amounts of chemicals (excluding the initiator) are distilled under nitrogen (5 liters / hour) for the examples given in Table 1 for the preparation of copolymers according to the invention in the stated amount Water dissolved. It should be noted that some of the substances used for the preparation of the copolymers are used in aqueous form (see the information on the substances used for the preparation of the copolymers). The distilled water indicated in Table 1 is added in addition to the water introduced via these substances. In the case of acidic monomers with base such. As alkali carbonate, such as potassium carbonate, preneutralized. Subsequently, the aqueous solution is purged with nitrogen for 30 minutes and heated to 60 ° C. In the next step, the amount of initiator (VA-44) indicated in Table 1 is dissolved in 10 g of distilled water and metered in over a period of 90 minutes. After completion of the metering is stirred for an additional hour at an internal temperature of 60 ° C. By a subsequent analysis of the solid is the conversion of the reaction tested and possibly unreacted monomers, if appropriate by slight addition of a 10 wt .-% aqueous solution of the previously used initiator reacted until a

full turnover is achieved. Thereafter, the reaction mixture

Room temperature (20-23 ° C) cooled.

Table 1 lists synthetic examples of copolymers according to the invention.

Table 1: Substances used for the preparation of copolymers according to the invention

The amounts shown in Table 1 are based on the active ingredient

Table 1 a: Relative amounts according to Table 1

Copolymer Total amount of structureStructureStructureNo. used monomer units (A) units (B) units (C) units (D)

[mmol] [mol%] [mol%] [mol%] [mol%]

1 42.0 15.0 65.0 20.0 -

2 42.0 8, 1 65.0 26.9 -

3,131, 1 12,0 33,4 34,5 20, 1

4 65.6 14.0 39.9 46.0 -

5 65.6 15, 1 45.0 39.9 -

Table 2: Measured weight average molecular weights M _w :

Adsorption experiments on cellulose-coated quartz crystal crystals

The experiments were carried out with the quartz crystal microbalance QCM-D (English Quartz Crystal Microbalance with Dissipation Monitoring, Q-Sense, Vastra Frolinda, Sweden). The method is based on the natural frequency change of a piezoelectric quartz crystal as soon as it is loaded with a mass. The surface of the quartz may be modified by spin-coating or vapor deposition. The quartz crystal is located in a measuring cell. The measuring cell is a flow cell, into which the solution to be investigated is pumped from sample vessels. The pumping speed is kept constant during the measuring time. Typical pumping speeds are between 50-250 μΙ / minute. During a measurement, make sure that the hoses and measuring cell are free of air bubbles. Each measurement starts with the recording of the baseline, with respect to which all frequency and dissipation measurements are set as zero.

Cellulose-coated quartz crystal crystals (low charged nanofibrillar cellulose, thickness: 50-100 nm, adhesion promoter: any polycation) were used in this example.

Aqueous solutions of the copolymers according to the invention having an active content of 1000 ppm were investigated. As water was tap water with 14 ° dH used. The pH was adjusted to pH 8.5 with NaOH or citric acid. From the measured data, the bound mass of hydrated copolymer was calculated. The results are in the following Table 3

summarized:

Table 3 QCM-D Wind-up behavior

The results of Table 3 show that the copolymers according to the invention are suitable for use on cellulose-containing textiles, for example as soil release polymers, since they adsorb on the surface being examined.

Detergent compositions with exemplary copolymers of the invention

A number of exemplary detergent compositions were prepared both without and with inventive copolymer according to Table 4. All samples contain sodium hydroxide as buffer system.

Key for the ingredients used in the compositions of Table 4

LAS linear C12-14 alkylbenzenesulfonate, sodium salt SLES 2EO Sodium lauryl ether sulphate (2 mol EO Genapol ^® LRO,

Clahant)

Nl 7EO nonionic C12-15 alcohol ethoxylate 7EO (Genapol ^®

LA070, Clariant)

Fatty acid stripped C12-18 palm kernel fatty acid

Table 4 Detergent compositions

There are prepared 5 detergent compositions containing inventive copolymer No. 1, 2, 3, 4 or 5. All 5 detergent compositions are clear at room temperature.

Claims

claims

1 . Containing copolymer

a) 0.1 to 15.4 mol%, preferably 5.0 to 15.2 mol% and particularly preferably 7.0 to 15.0 mol%, of one or more cationic

Structural units (A) and

b) from 0.1 to 99.9 mol%, preferably from 20.0 to 80.0 mol% and particularly preferably from 25.0 to 75.0 mol%, of one or more macromonomer structural units (B),

characterized in that the one or more cationic

wherein

R ¹ and R ^{1 a} are the same or different and are independent

each of each represents hydrogen and / or a methyl radical,

each other by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to

4 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, C atoms, an aryl radical having 6 to 14 carbon atoms and / or polyethylene glycol (PEG) are represented, preferably in each case identical or different and independently are each represented by hydrogen and / or methyl and more preferably each methyl,

is the same or different and is replaced by oxygen, NH and / or

NR ^{3 is} represented,

is the same or different and is denoted by - (CH 2) x-, is represented,

x is the same or different and is an integer from 1 to

6 is represented,

X and Xi are the same or different and are independent

each other by a halogen atom, ci- to

ZO (C ₃ H ₆ O), (CH ₂ CH ₂ O) _p H

in molar average, is a number from 0 to 6 and preferably from 0 to 5, and

2. Copolymer according to claim 1, characterized in that the one or more cationic structural units (A) the polymerization product of at least one monomer species selected from the group consisting of [2- (acryloyloxy) ethyl] trimethylammonium chloride, [2- (acryloylamino) -ethyl] - trimethylammonium chloride, [2- (acryloyloxy) -ethyl] -trimethylammonium methosulfate, [2- (methacryloyloxy) -ethyl] -trimethylammonium chloride

or methosulfate, [3- (acryloylamino) -propyl] -trimethylammonium chloride,

[3- (methacryloylamino) -propyl] -trimethylammonium chloride and

Diallyldimethylammonium chloride (DADMAC), preferably selected from the group consisting of [3- (acryloylamino) -propyl] trimethylammonium chloride, [3- (methacryloylamino) -propyl] -trimethylammonium chloride and diallyldimethylammonium chloride, and more preferably selected from the group consisting of

[3- (methacryloylamino) -propyl] -trimethylammonium chloride and [3- (acryloylamino) -propyl] -trimethylammonium chloride.

3. A copolymer according to claim 1 or 2, characterized in that the one or more macromonomer structural units (B) of the formula (III) the polymerization of at least one monomer species selected from Group consisting of polyethylene glycol vinyloxy-butyl ether, polyethylene glycol co-polypropyleneglycol vinyloxybutyl ether (in which I, by molar, denotes a number from 1 to 6, preferably from 1 to 5 and particularly preferably from 2 to 5), polyethylene glycol (meth) acrylate and polyethylene glycol-co-polypropylene glycol (meth) acrylate (wherein I, in molar terms, is an integer from 1 to 6, preferably from 1 to 5 and more preferably from 2 to 5).

4. Copolymer according to one or more of claims 1 to 3, characterized in that in the one or more macromonomers

Structural units (B) of the formula (III)

i) R ^{x is} H, I = 0 and p, in the molar average, a number from 1 to 150,

preferably from 1 to 100, and more preferably from 12 to 50, when Z is O (CH 2) 4 or

ii) R ^{x is the} same or different and is represented by H and / or methyl, I, by molar, is a number from 1 to 6, preferably from 1 to 5 and more preferably from 2 to 5, and p, in molar Means is a number from 1 to 150, preferably from 1 to 100 and more preferably from 12 to 50, when ZC = O means.

Copolymer according to one or more of Claims 1 to 4, characterized in that, in addition to the structural units (A) and (B), they contain one or more structural units (C) which are different from the structural units (A) and (B) distinguish and where it is

preferably 0.1 to 15.4 mol% of the one or more structural units (A), 0.1 to 99.8 mol% of the one or more structural units (B) and 0.1 to 99.8 mol% % of the one or more structural units (C), more preferably 5.0 to 15.2 mole% of the one or more

Structural units (A), 20.0 to 80.0 mol% of the one or more

Structural units (B) and 10.0 to 64.8 mol% of the one or more

Contains structural units (C), and

especially preferably 7.0 to 15.0 mol% of the one or more

Structural units (A), 25.0 to 75.0 mol% of the one or more Structural units (B) and 15.0 to 60.0 mol% of the one or more structural units (C).

6. A copolymer according to claim 5, characterized in that the one or more structural units (C) the polymerization of at least one monomer species selected from the group consisting of non-cationic acrylamides, non-cationic methacrylamides and N-vinyl-substituted lactams 5 to Represent 7 ring atoms.

7. A copolymer according to claim 5 or 6, characterized in that the one or more structural units (C) are selected from the group consisting of the polymerization of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and the structural units of the following general Formulas (IV) and (V):

NR ³ R ⁴ in which

R ^{1 is the} same or different and is hydrogen and / or methyl

means, and

H C O

X wherein

R ^{13 is the} same or different and is represented by OH, N (CH 3) 2,

Sosh, PO3H2, O-PO3H2 and / or para-substituted C 6 H ₄ -SO 3.

8. A copolymer according to claim 7, characterized in that the one or more structural units (C) are selected from the structural units of the formula (IV).

9. Copolymer according to one or more of claims 5 to 7, characterized in that the one or more structural units (C) the

Ν, Ν-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide,

Represent N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tertiary butylacrylamide, and are preferably selected from the group consisting of Ν, Ν-dimethylacrylamide and N-isopropylacrylamide.

10. A copolymer according to one or more of claims 1 to 9, characterized in that in addition to the structural units (A), (B) and (C) a or a plurality of structural units (D) different from the structural units (A), (B) and (C), and wherein

preferably 0.1 to 15.4 mol% of the one or more structural units (A), 0.1 to 99.7 mol% of the one or more structural units (B), 0.1 to 99.7 mol% % of the one or more structural units (C) and 0.1 to

Contains 99.7 mol% of the one or more structural units (D),

more preferably 5.0 to 15.2 mole% of the one or more

Structural units (A), 20.0 to 50.0 mol% of the one or more

Structural units (B), 10.0 to 60.0 mol% of the one or more

Structural units (C) and 0.1 to 35.0 mol% of the one or more

Contains structural units (D), and

especially preferably 7.0 to 15.0 mol% of the one or more

Structural units (A), 25.0 to 40.0 mol% of the one or more

Structural units (B), 15.0 to 50.0 mol% of the one or more

Structural units (C) and 5.0 to 30.0 mol% of the one or more

Structural units (D) contains.

1 1. Copolymer according to claim 10, characterized in that it contains one or more structural units (D) selected from the structural units of the following general formula (VII):

12. The copolymer of claim 1 1, characterized in that it contains one or more structural units (D) containing the polymerization of at least one monomer species selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid, sodium methacrylate and

Represent potassium methacrylate.

13. Copolymer according to one or more of claims 1 to 12, characterized in that the structural units (A), (B) and optionally (C) and (D) in random, block-shaped, alternating or gradient-like distribution in the copolymer.

14. Copolymer according to one or more of claims 1 to 13, characterized in that its weight-average molecular weight M _w of 10,000 to 400,000 g / mol, preferably from 15,000 to 350,000 g / mol and particularly preferably from 50,000 to 330 000 g / mol.

15. A detergent composition comprising one or more copolymers according to one or more of claims 1 to 14.

16. Use of a copolymer according to one or more of claims 1 to 14 or a detergent composition according to claim 15 for cleaning textiles and preferably for cleaning cotton-containing textiles.

17. Use of a copolymer according to one or more of claims 1 to 14 or a detergent composition according to claim 15 for reducing the re-soiling of the textiles and preferably the

Repulpation of cotton-containing fabrics to which the copolymer or detergent composition has been applied.