EP2106413A1

EP2106413A1 - Thermally sensitive polymeric dye transfer inhibitor

Info

Publication number: EP2106413A1
Application number: EP07858012A
Authority: EP
Inventors: Jürgen Detering; Heike Becker; Richard Baur; Guido Vandermeulen
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-12-21
Filing date: 2007-12-20
Publication date: 2009-10-07
Also published as: WO2008077910A1; JP2010513640A; BRPI0721265A2; KR20090096715A; MX2009005826A; US20100004154A1; CN101563376A; CA2671589A1

Abstract

The invention relates to the use of thermally sensitive polymers as dye transfer inhibitors. The invention also relates to novel thermally sensitive polymers suitable as dye transfer inhibitors, and to washing compositions which comprise these polymers.

Description

Thermosensitive polymeric dye transfer inhibitor

description

The invention relates to the use of thermosensitive polymers as color transfer inhibitors. The invention also relates to novel thermosensitive polymers useful as color transfer inhibitors, and to laundry detergent compositions containing these polymers.

During the washing process dyed textiles often replace dye molecules, which in turn can be applied to other textiles. To counteract this undesirable color transfer, so-called color transfer inhibitors are often used. These are often polymers which contain monomers having nitrogen-heterocyclic radicals in copolymerized form.

So describes z. For example, DE 4235798 copolymers of 1-vinylpyrrolidone, 1-vinylimidazole, 1-vinylimidazolium compounds or mixtures thereof; further nitrogen-containing, basic ethylenically unsaturated monomers; and optionally other monoethylenically unsaturated monomers and their use to inhibit dye transfer during the wash.

Similar copolymers are described for this purpose in DE 19621509 and WO 98/30664.

The copolymers described in these documents are characterized in part by a good inhibition of color transfer in washing processes. However, they generally have low compatibility with the other commonly used detergent ingredients. Thus, there is the danger of incompatibilities, in particular in the case of liquid detergents, for example in the form of turbidity or phase separations.

There have been various reports of the use of thermosensitive polymers having a lower critical solubility temperature (LCST) in detergent formulations.

GB 2377451 discloses a detergent for a dishwashing machine wherein a surfactant is enclosed by a water-soluble polymer which retards its release until the cloud point of the surfactant is exceeded in the machine.

JP 09192469 describes a surfactant with an LCST polymer. The surface-active effect can be controlled by the temperature. WO 2001/40420 describes a washing and cleaning agent with conventional ingredients, which contains an active ingredient preparation, which is formulated with an LCST polymer.

DE 19958472 discloses a particulate composite material for the controlled release of an active substance with an active ingredient or a preparation which contains this active ingredient in admixture with an LCST substance.

WO 2002/08137 discloses a particulate composite material for controlled release of a drug or drug preparation wherein the drug or drug formulation is coated with an LCST polymer. The LCST polymer is mixed with an additive, with which the film formation can be improved or the LCST temperature can be adjusted.

WO 2002/44462 describes a particulate textile aftertreatment agent containing a fabric care active ingredient formulated such that the bulk of the active ingredient is delayed in the main wash or released after the main wash. For example, the active ingredient may be coated with an LCST polymer.

DE 10064635 describes laundry detergent or cleaning product tablets made of compacted particulate detergent or cleaner containing builder (s), surfactant (s) and optionally further detergent or cleaning agent components, which is formulated such that it has a delayed solubility on contact with water having.

DE 10148353 describes a method for forming a release-delay layer on detergent tablets with an LCST functional layer.

WO 2001/044433 relates to a detergent, dishwashing or cleaning agent portion with two or more washing, rinsing or cleaning-active components, of which at least two are to be released into the liquor at different times of a washing, rinsing or cleaning process comprising at least one release (physical) chemical switch, which is not or not exclusively subject to temperature control, and one or more substances to increase the extent of the pH shift.

In all cases, the LCST polymer in the compositions serves to control, via temperature, the release of the active ingredient (surfactant) contained in the composition. It was an object of the present invention to provide substances with a good color transfer inhibiting effect during the washing process. These substances should also have good compatibility with conventional detergent ingredients, especially in liquid detergent formulations.

These and other objects are surprisingly achieved by thermosensitive polymers having a lower critical solubility temperature (LCST).

The invention therefore relates to the use of thermosensitive polymers having a lower critical solubility temperature (LCST) as color transfer inhibitors in detergent compositions for textiles.

The invention also relates to a process for washing dyed textiles, in which

(a) contacting the textiles with at least one thermosensitive polymer comprising an LCST and at least one surfactant in a wash liquor,

(b) raising the temperature of the wash liquor to the LCST of the at least one thermosensitive polymer or a higher temperature, and

(C) separating the at least one thermosensitive polymer with the wash liquor from the textiles.

The inventive method is particularly suitable for use as a machine wash, z. B. in a commercial washing machine.

In the present case, a polymer which has an LCST is referred to as thermosensitive. By those skilled in the art means a polymer whose solubility in aqueous solution depends on the temperature such that it is soluble in water below the LCST and insoluble above the LCST. Accordingly, a polymer-water mixture below the LCST is single-phase. Above the LCST, this polymer-water mixture shows segregation. In such cases, it is also said that the polymer has a negative temperature-dependent solubility coefficient.

The LCST is the temperature above which a water-polymer mixture becomes cloudy (cloud point or cloud point). The cloud point or LCST can be determined by heating a solution of the polymer in water over a certain temperature range at a certain heating rate. Various methods are used in the literature to measure the cloud point. Examples are the visual determination or the spectrophotometric measurement, wherein one follows the transmission of the solution at a certain wavelength as a function of the temperature.

Cloud points in this application were determined by transmission measurement at 550 nm of 1 wt. % polymer solutions (temperature range 20 to 85 ⁰ C, heating rate 1 ⁰ C per minute).

Presumably, the favorable properties of the polymers used according to the invention are based on the following contexts: At temperatures below the LCST, the dye transfer inhibitor binds or complexes free dye in the wash liquor via dye-affinitive groups. At temperatures at or above the LCST, the dye transfer inhibitor becomes hydrophobic and therefore insoluble. The dye is thereby trapped or retained by the dye transfer inhibitor and can be used in the rinse cycle e.g. be removed when draining the hot wash liquor from the textile.

The LCST of the polymers used in the invention is usually at least 20 ⁰ C. It is, for example in the range of 20 to 95 ° C, preferably in the range of 25 to 80 ⁰ C and in particular in the range of 30 to 60 ⁰ C.

Polymers comprising an LCST are known to those skilled in the art, for example from the cited prior art. The LCST of the polymers used according to the invention depends inter alia on the chemical composition, the molecular weight and the concentration of the polymer. For example, it is known that the LCST can be increased by copolymerizing a major portion of a hydrophilic monomer.

In principle, all polymers which have an LCST in water, which preferably lies in the abovementioned temperature ranges, are suitable as polymeric color transfer inhibitors. Examples of these are i) alkylated and hydroxyalkylated polysaccharides, such as hydroxypropylmethylcellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose

(HPC), methylcellulose (MC) and mixtures thereof and mixtures of alkylated and / or hydroxyalkylated polysaccharides with carboxymethylcellulose; ii) polyvinylcaprolactam, poly (N-alkyl) acrylamides and poly (N, N-dialkylacrylamides), iii) poly (hydroxypropyl acrylate) and poly (hydroxypropyl methacrylate), iv) polyethylene oxides and ethylene oxide / propylene oxide copolymers and alkylated acrylamide-based graft copolymers with polyethylene oxide. v) polyvinyl alcohol and partially saponified polyvinyl acetates; vi) polyvinylmethyl ether, vii) certain proteins such as poly (VAPGW) (where V = VaNn, A = alanine, P = proline, G = glycine). Surprisingly, copolymers based on ethylenically unsaturated monomers M which comprise at least one monoethylenically unsaturated monomer (a) whose homo- or copolymers exhibit thermosensitive behavior (ie have LCST) and at least one monoethylenically unsaturated monomer (b) with a dye affinity group , an LCST on. They are particularly suitable as color transfer inhibitors.

Such copolymers may also be prepared by polymerization of the monomers M in the presence of a grafting base. Such polymers are novel and also the subject of the present invention.

Accordingly, the invention relates to a copolymer suitable as a color transfer inhibitor which comprises units (a) of at least one ethylenically unsaturated monomer whose homo- or copolymers exhibit thermoresponsive behavior, (b) at least one ethylenically unsaturated monomer having a dye affinity group and optionally a graft base.

Based on the total amount of the monomers M, the monomer (a) (or a combination of different monomers (a)) makes 20 to 80 wt .-%, in particular 30 to 70 wt .-%, and the monomer (b) (or a Combination of monomers (b)) 5 to 50 wt .-%, preferably 10 to 40 wt .-% of. The copolymer may contain units of other monomers (c) other than monomers (a) and (b). If units of further monomers are present, their amount is preferably less than 40% by weight, in particular less than 30% by weight, based on the total amount of the monomers M and preferably less than 70% by weight, in particular less than 50 wt .-%, based on the sum of the units of the monomers (a) and (b). If the copolymer is prepared in the presence of a grafting base, its proportion is preferably less than 100% by weight, in particular less than 60% by weight, e.g. 5 to 100 wt .-%, in particular 10 to 60 wt .-%, based on the sum of the units derived from the monomers M.

The person skilled in the art is familiar with ethylenically unsaturated monomers (a) whose homopolymers or copolymers exhibit thermosensitive behavior and which are suitable for the preparation of a dye transfer inhibitor according to the invention.

These monomers are z. B. selected under

N-vinyl lactams having a ring size of at least 6 atoms, especially N-vinylcaprolactams and N-vinylvalerolactams, e.g. N-vinyl-3-methyl-ε-caprolactam, N-vinyl-ε-caprolactam and N-vinyl-δ-valerolactam;

N-mono-C 1 -C 8 -alkyl (meth) acrylamides, such as N-isopropylacrylamide; N, N-di-C 1 -C 8 -alkyl (meth) acrylamides, such as N, N-dimethylacrylamide and N, N-dimethylmethacrylamide;

Hydroxy C 2 -C 4 -alkyl (meth) acrylates, such as hydroxypropyl acrylate;

Vinyl alcohol, prepared e.g. By hydrolysis of vinyl acetate; and

Vinyl-Ci-Cβ-alkyl ethers, such as vinyl methyl ether.

Of these, N-vinylcaprolactam, N-isopropylacrylamide, hydroxypropyl acrylate, vinyl alcohol and vinyl methyl ether are preferred. N-vinylcaprolactam is particularly preferred.

Dye affine groups are functional groups that show high affinity for dyes such as direct dyes, reactive dyes and acid dyes. The nature of the dye interaction may be due to hydrogen bonds, π-π interactions, electrostatic forces, such as ion / ion interactions, ion / dipole interactions, intercalation or combinations or other suitable interactions.

Preferably, the dye affinity group in monomer (b) is a 5- or 6-membered nitrogen-containing heterocycle which is optionally fused. The 5- or 6-membered nitrogen-containing heterocycle (N-heterocycle) may be aromatic (heteroaryl) or partially or fully saturated. In addition, the N-heterocycle may optionally have one or more, for example 1, 2, 3 or 4, substituents selected from C ₁ -C ₄ -alkyl, C ₃ -C 6 -cycloalkyl and phenyl. Furthermore, the N-heterocycle may have a carbonyl group and / or an N-oxide group as a ring member. Incidentally, the N-heterocycle in quaternized form, for. B. by alkylation of at least one N-ring atom, are present. In addition, the N-heterocycle may also be present as a beta-structure, in which at least one N atom of the heterocycle has a C ₁ -C 20 -alkanediyl group with a lower -SO ₃ ^" , -OSO ₃ -, -COO ^" , -OPO (OH) O ^" , -OPO (OR ^f ) O" or -PO (OH) O "bridged, where R ^f is C 1 -C 6 -alkyl The nitrogen-containing heterocycle can be reacted with one or more ring systems The fused ring systems can be saturated, partially unsaturated, or aromatic, and a preferred fused ring system is a benzene ring.

In addition to the dye affinity group, the monomer has an ethylenically unsaturated group through which the monomer is incorporated in the copolymerization in the polymeric framework of the dye transfer inhibitor in the copolymerization. Suitable ethylenically unsaturated groups are, for. B. C2-C6 alkenyl radicals, especially vinyl radicals, or (meth) acryloxy or (meth) acrylamino groups. The monomers having a dye-affinitive group include 5-membered lactams which carry on their nitrogen atom a C 2 -C 6 -alkenyl radical, in particular a vinyl radical. Such lactams can be described by the general formula (I):

wherein n is O, 1 or 2; R ^{a is} H or C 1 -C ₄ -alkyl; R ^b is C 1 -C 4 -alkyl, ie one or more of the lactam ring-forming Chb-

Groups optionally have 1 or 2 selected from Ci-C4-alkyl

Substituents on.

Examples of such N-vinyl lactams are N-vinyl pyrrolidones, e.g. N-vinyl-3-methylpyrrolidone and N-vinylpyrrolidone. A preferred N-vinyl lactam is N-vinyl pyrrolidone.

Also suitable are N-vinyl oxazolidones, e.g. N-vinyl-5-methyloxazolidone and N-vinyl oxazolidone.

The monomers having a dye-affinitive group furthermore include N-vinylheterocyclic monomers having one of imidazoles, imidazolines and imidazolidines, pyridines, pyrroles, pyrrolidines, quinolines, isoquinolines, purines, pyrazoles, triazoles, tetrazoles, indolizines, pyridazines, pyrimidines, pyrazines, indoles, isoindoles , Oxazoles, oxazolidines, morpholines, piperazines, piperidines, isoxazoles, thiazoles, isothiazoles, indoxylenes, isatsines, dioxindiols and hydanthoines and derivatives thereof, eg. Barbituric acid, uracil and their derivatives, selected N-heterocycle. The monomers mentioned can also be used as betaine derivatives or quaternized products.

The N-heterocycles are selected in particular from imidazoles, triazoles, pyridines, pyridine-N-oxides and betainic derivatives and quaternization thereof, especially among imidazoles.

In a preferred embodiment, the monomers are N-vinylimidazoles of the general formula IV a, betainic N-vinylimidazoles of the general formula IV b, 2- and 4-vinylpyridines of the general formulas IV c and IV d and betainic 2- and 4-vinylpyridines general formulas IV e and IV f selected:

IV d IV e IV f

wherein

R ^b , R ^c , R ^d , R ^{e are} each independently H, Ci-C ₄ -AlkVl or phenyl, preferably H or Ci-C ₄ -AlkVl, more preferably H;

W ^{1 is} C ¹ -C ₂₀ -alkylene, for example -CH ₂ -, -CH (CH ₃ ) -, - (CH ₂ J ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ - , - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) 6-, preferably C ₁ -C ₃ -alkylene, in particular - CH ₂ -, - (CH ₂ J ₂ - or - ( CH ₂ J ₃ - is;

Q represents -SO ₃ -, -OSO ₃ -, -COO-, -OPO (OH) O ^" , -OPO (OR ^f ) O- or -PO (OH) O ^" ; and

R ^{f is} C 1 -C ₂₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl.

Also suitable are the acrylic or methacrylic esters of hydroxyalkyl-substituted N-heterocycles, the N-heterocycle being imidazoles, imidazolines and imidazolidines, pyridines, pyrroles, pyrrolidines, quinolines, isoquinolines, purines, pyrazoles, triazoles, tetrazoles, indolizines, pyridazines, pyrimidines , Pyrazines, indoles, isoindoles, oxazoles, oxazolidines, morpholines, piperazines, piperidines,

Isoxazoles, thiazoles, isothiazoles, indoxylene, isatins, dioxindoles and hydanthoines and their derivatives is selected. Suitable monomers are, for. As hydroxyethyl pyrrolidone (meth) acrylate or hydroxyethyl imidazoles (meth) acrylate.

Preferred N-vinyl heterocyclic monomers are N-vinylimidazole and C1-C4 alkylvinylimidazoles, e.g. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, in particular N-vinylimidazole and methylvinylimidazoles, especially N-vinylimidazole and N-vinyl 2-methylimidazole; 3-vinylimidazole N-oxide; 2- and 4-vinylpyridines, e.g. 2-vinyl-4-methylpyridine, 2-vinyl-6-methylpyridine and 2- and 4-vinylpyridine; Vinylpyridine N-oxides such as 2- and 4-vinylpyridine N-oxides, e.g. 2-vinyl-4-methylpyridine-N-oxide, 4-vinyl-2-methylpyridine-N-oxide and 2- and 4-vinylpyridine-N-oxide; and betaine derivatives and quaternization products thereof.

Particularly preferred betainic monomers are monomers of the formulas IV b, IV e and IV f, in which the grouping W ¹ -Q- is -CH ₂ -COO-, - (CH ₂ ) ₂ -SO ₃ - or - (CH ₂ ) ₃ - SO ₃ - and R ^b , R ^c , R ^d , R ^{e are} each H.

The quaternized monomers used are preferably vinylimidazoles and vinylpyridines, these being quaternized before or after the polymerization. Particular preference is given to using 1-methyl-3-vinylimidazolium methosulfate and methachloride.

The quaternization can be carried out in particular with alkylating agents such as alkyl halides, which generally have 1 to 24 C atoms in the alkyl radical, or dialkyl sulfates, which generally contain alkyl radicals having 1 to 10 C atoms. Examples of suitable alkylating agents from these groups are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and also dimethyl sulfate and diethyl sulfate. Other suitable alkylating agents are e.g. Benzyl halides, especially benzyl chloride and benzyl bromide; Chloroacetic acid; Fluorschwefelsäuremethylester; diazomethane; Oxonium compounds such as trimethyloxonium tetrafluoroborate; Alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrins. Preferred quaternizing agents are methyl chloride, dimethyl sulfate and diethyl sulfate.

The quaternization can also be carried out polymer-analogously.

In a preferred embodiment, the monomers (b) having a dye-affinitive group are N-vinylimidazole, quaternized N-vinylimidazole, N-vinylpyrrolidone, N-vinyltriazole, N-vinylbenzimidazole, hydroxyethylpyrrolidone (meth) acrylate and hydroxyethyl imidazole (meth) acrylate, 2 Vinylpyridine, 4-vinylpyridine and derivatives eg 4-vinylpyridine N-oxide thereof. In a particularly preferred embodiment, the monomers having a dye-affinitive group are selected from N-vinylpyrrolidone, N-vinylimidazole and mixtures of N-vinylpyrrolidone with N-vinylimidazole.

In addition to the monomers (a) and (b), the copolymers according to the invention may contain in copolymerized form one or more further monomers (c) copolymerizable with the monomers (a) and (b). Examples of monomers (c) are monoethylenically unsaturated C3-Cio-mono- and C4-Cio-dicarboxylic acids, eg. (Meth) acrylic acid, crotonic acid, fumaric acid and maleic acid; ethylenically unsaturated sulfonic acids and their salts, such as vinylsulfonic acid, 2-acryloyloxyethanesulfonic acid, 2- and 3-acryloyloxypropanesulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid and styrenesulfonic acid and their sodium salts; Vinyl esters of saturated C 1 -C 10 -carboxylic acids, eg. Vinyl acetate and vinyl propionate; Allyl ethers of linear or branched C 1 -C 10 alcohols, e.g. Allyl methyl ether, allyl ethyl ether and allyl propyl ether;

N-vinylamides of aliphatic carboxylic acids, in particular N-vinylformamides, eg. N-vinyl-N-methylformamide and N-vinylformamide itself; the quaternary products of N-vinyl and N-allylamines, such as alkylated N-vinyl and N-allylamines, e.g. N-vinylmethylamine, N-vinylethylamine, N-allylmethylamine, N-allylethylamine and N-allylpropylamine; the esters of monoethylenically unsaturated Cs-Cβ monocarboxylic acids or C4-C6 dicarboxylic acids with linear or branched aliphatic Ci-Cio-alcohols, eg. Methyl acrylate, ethyl acrylate, methyl methacrylate, methacrylic acid ethyl ester, dimethyl maleate, diethyl maleate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate; the half-esters of monoethylenically unsaturated C 4 -C 6 -dicarboxylic acids with linear or branched C 1 -C 10 -alcohols, eg. B. maleic acid monomethyl ester and maleic acid monoethyl ester; the anhydrides of monoethylenically unsaturated C4-C6 dicarboxylic acids, eg. For example, maleic anhydride; - unsaturated nitriles, eg. For example, acrylonitrile and methacrylonitrile; and the salts of said acids, the derivatives thereof and mixtures thereof; and monoethylenically unsaturated compounds having a poly-C2-C6-alkylene oxide group

The monoethylenically unsaturated compounds having a P0IV-C2-C6-alkylene oxide group, which are also referred to below as polyalkylene oxide monomers, are typically compounds which have a polyether group and a moiety having an ethylenically unsaturated double bond, the polyether group being composed of alkylene oxides derived recurring units (polyalkylene oxide group). These include in particular the monomers of the general formula X. in which the variables have the following meaning: X is -CH ₂ - or -CO-, when Y is -O-;

-CO- when Y is -NH-; R ^{1 is} hydrogen or methyl;

R ^{2 are} identical or different C 2 -C 6 -alkylene radicals which may be linear or branched and which may be arranged blockwise or randomly, in particular identical or different blockwise or randomly arranged linear or branched C 2 -C 4 -alkylene radicals, preferably ethylene, 1, 2 or 1,3 propylene or mixtures thereof, more preferably ethylene;

R ^{3 is} hydrogen or C 1 -C ₄ -alkyl, in particular hydrogen or methyl; n is an integer from 3 to 50, in particular 5 to 30, and mixtures thereof, where n has on average a value in the range from 3 to 50 (number average). Of these, preference is given to those compounds in which at least 50 mol% of the groups R ^{2 are} CH ² -CH ² . Of these, particular preference is given to those compounds in which X is CH 2 or CO. Of these, particular preference is given to those compounds in which Y is O.

The requirements of certain applications may influence the choice of the type and amount of monomers (c). Thus, it may be desirable to further react the polymers of the invention in a selective manner prior to use, e.g. As by targeted alcoholysis, aminolysis or hydrolysis. Thus, in particular units corresponding to vinyl alcohol units of vinyl ester units and units corresponding to vinylamine units can be formed from vinylformamide units.

In a preferred embodiment, the monomer (c) is selected from monoethylenically unsaturated polyalkylene oxide monomers, in particular from the monomers of the formula X.

The monomers (C) are, for example, according to formula X:

Reaction products of (meth) acrylic acid with polyalkylene glycols, which are not end-capped, end-capped on one side by alkyl radicals, aminated on one side or end-capped on one side by alkyl radicals and unilaterally aminated. Allyl ethers of polyalkylene glycols which are not end-capped or end-capped by alkyl, phenyl or alkylphenyl radicals.

Preferred monomers of the formula X are the (meth) acrylates and the allyl ethers, the acrylates and especially the methacrylates being particularly preferred. Particularly suitable examples of the monomers (C) which are described by the formula X are:

Methylpolyethylene glycol (meth) acrylate and - (meth) acrylamide, methylpolypropylene glycol (meth) acrylate and - (meth) acrylamide, methylpolybutylene glycol (meth) acrylate and - (meth) acrylamide, methylpoly (propylene oxide-co-ethylene oxide) (meth) acrylate and

(meth) acrylamide, ethylpolyethylene glycol (meth) acrylate and (meth) acrylamide, ethylpolypropylene glycol (meth) acrylate and (meth) acrylamide, ethylpolybutylene glycol (meth) acrylate and (meth) acrylamide and ethylpoly (propylene oxide-co-ethylene oxide) (meth) acrylate and - (meth) acrylamide, each having 3 to 50, preferably 3 to 30 and particularly preferably 5 to 30 alkylene oxide units, with methyl polyethylene glycol acrylate being preferred and methyl polyethylene glycol methacrylate being particularly preferred;

Ethylene glycol allyl ethers and methyl ethylene glycol allyl ethers, propylene glycol allyl ethers and methylpropylene glycol allyl ethers having in each case 3 to 50, preferably 3 to 30 and particularly preferably 5 to 30 alkylene oxide units.

In a first preferred embodiment of copolymers according to the invention, the proportion of monomers (c) is less than 5% by weight, in particular less than 1% by weight, based on the total weight of the monomers M. used to prepare the copolymer. Such polymers are preferably used in Presence of a graft base made.

In a further preferred embodiment of copolymers according to the invention, the proportion of monomers (c) is 1 to 40% by weight, in particular 5 to 30% by weight, based on the total weight of the copolymer used for the preparation of the copolymer

Monomers M. Such polymers are preferably not prepared in the presence of a grafting base.

The copolymers can be prepared in the presence of a grafting base. The graft is typically a water-soluble polymer (at 20 ⁰ C), which may optionally also have a LCST. The grafting base is preferably selected from poly-C 2 -C 4 -alkylene ethers and poly-C 2 -C 4 -alkyleneimines.

The number-average molecular weight M _{n of} the grafting base is typically in the range from 300 to 100,000, in particular in the range from 500 to 50,000.

The graft base of the copolymers of the invention preferably forms a P0IV-C2-C4-alkylene ether. The term "copolymer" is intended to include also oligomeric compounds. Preferably, the polyethers have a number average molecular weight M _n of at least 300 and have the general formula IIIa

R ¹ -f (R-O) - (R-O) - (R ⁴ -O) -A- (R ² -O) - (R ³ -O) - (R ⁴ -O) -R ⁵ ) ( purple) n

or INb

(IIIb)

on, in which the variables have the following meaning:

R ^{1 is} hydroxy, amino, C ₁ -C 4 -alkoxy, R ^{7 is} -COO-, R ^{7 is} -NH-COO-, polyalcohol radical;

R ² , R ³ , R ^{4 are} identical or different and selected from - (CHb) ₂ -, - (CH 2) 3, - (CHb) ₄ -, -CH ₂ -CH (CH ₃ ) -, -CH ₂ - CH (CH ₂ -CH ₃ ) -, -CH ₂ -CHOR ⁸ -CH ₂ -;

R ^{5 is} hydrogen, amino-C ₁ -C ₆ -alkyl, C ₁ -C ₂₄ -alkyl, R ⁷ -CO-, R ⁷ -NH-CO-;

R ⁶ Ci-C ₂ o-alkylene, whose carbon chain may be interrupted by 1 to 10 oxygen atoms in ether function;

R ^{7 is} C 1 -C ₂₄ -alkyl;

R ^{8 is} hydrogen, C 1 -C ₂₄ -alkyl, R ⁷ -CO-;

A is a chemical bond, -CO-O-, -CO-B-CO-O-, -CO-NH-B-NH-CO-O-, - (CH ₂ ) _t -, optionally substituted arylene;

B is - (CH ₂ ) t-, optionally substituted arylene;

n is 1 or, when R ^{1 represents} a polyalcohol radical up to 8;

s 0 to 500;

t 1 to 12;

u is the same or different and each is 1 to 5,000; v are the same or different and each 0 to 5,000;

w is the same or different and each 0 to 5000.

The sum of n, u, v and w is selected such that the specific molecule or the molecule mixture has a molecular weight in the ranges indicated above.

Preferred graft base are the polyethers of the formula IIIa.

The graft base comprises polyethers from the group of polyalkylene oxides based on ethylene oxide, propylene oxide and butylene oxides, polytetrahydrofuran and polyglycerol.

Depending on the type of monomer building blocks, polymers having the following structural units are obtained: - (CH ₂ J ₂ -O-, - (CH ₂ ) SO-, - (CH ₂ J ₄ -O-, -CH ₂ -CH (CHs) -O -, CH ₂ -CH (CH ₂ -CHs) -O-, -CH ₂ -CHOR ⁸ -CH ₂ -O-.

Both homopolymers and copolymers are suitable, the copolymers being able to be randomly distributed or present as block polymers.

The terminal primary hydroxyl groups of the polyethers prepared on the basis of alkylene oxides or glycerol and the secondary OH groups of polyglycerol can both be free as etherified ₂ 4-alcohols, esterified with Ci-C ₂ 4-carboxylic acids with Ci-C, or with Isocyanates be converted to urethanes. Suitable alcohols for this purpose are, for. For example: primary aliphatic alcohols, such as methanol, ethanol, propanol and butanol, primary aromatic alcohols, such as phenol, isopropylphenol, tert-butylphenol, octylphenol, nonylphenol and naphthol, secondary aliphatic see alcohols, such as isopropanol , tertiary aliphatic alcohols, such as tert. Butanol, and polyhydric alcohols, e.g. Diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol and butanediol, and triols such as glycerol and trimethylolpropane. However, the hydroxyl groups can also be exchanged by reductive amination with hydrogen-ammonia mixtures under pressure for primary amino groups or converted by cyanethylation with acrylonitrile and hydrogenation in Aminopropylenendgruppen. The closure of the hydroxyl end groups can be done not only subsequently by reaction with the alcohols or with alkali metal, amines and hydroxylamines, but these compounds can be such as Lewis acids, eg. B. boron trifluoride, are also used at the beginning of the polymerization as a starter.

Finally, the hydroxyl groups can also be closed by reaction with alkylating agents, such as dimethyl sulfate. The alkyl radicals in the formulas IIIa and INb can be branched or unbranched C 1 -C 24 -alkyl radicals, preference being given to C 1 -C 12 -alkyl radicals and C 1 -C 6 -alkoxy radicals being particularly preferred. Examples are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl-propyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , 2,2-dimethylpropyl, 1-ethyl-propyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl , 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-butyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl , 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl , n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

The number average molecular weight M _{n of} the polyethers is at least 300 and is generally less than 100,000. It is preferably 500 to 50,000, more preferably 500 to 10,000, and most preferably 500 to 5,000.

It is advantageous to use homo- and copolymers of ethylene oxide, propylene oxide, butylene oxide and isobutylene oxide, which may be linear or branched, as the graft base. According to the invention, the term homopolymers should also include those polymers which, in addition to the polymerized alkylene oxide unit, also contain the reactive molecules which were used to initiate the polymerization of the cyclic ethers or to close the end groups of the polymer.

Branched polyethers can be prepared by, for example, low molecular weight polyols (radicals R7 in formulas IIIa and INb), z. B. pentaerythritol, glycerol and sugar or sugar alcohols, such as sucrose, D-sorbitol and D-mannitol, Disaccharide, ethylene oxide and, if desired, propylene oxide and / or butylene oxides or polyglycerol attached.

In this case, it is possible to form polymers in which at least one, preferably one to eight, particularly preferably one to five of the hydroxyl groups present in the polyhydric alcohol molecule can be linked in the form of an ether bond to the polyether radical of the formula IIIa or INb.

Four-armed polymers can be obtained by attaching the alkylene oxides to diamines, preferably ethylenediamine.

Other branched polymers can be prepared by reacting alkylene oxides with higher-value amines, eg. B. triamines, or in particular polyethylene imines. Polyethyleneimines suitable for this purpose generally have average molecular weights Mn of 300 to 20,000, preferably 500 to 10,000 and more preferably 500 to 5,000. The weight ratio of alkylene oxide to polyethyleneimine is usually 100: 1 to 0.1: 1, preferably 20: 1 to 0.5: 1.

Particular preference is given to using homopolymers and copolymers of ethylene oxide and / or propylene oxide as the graft base, which may be end-capped on one or both sides.

The particular advantage of polypropylene oxide and copolymeric alkylene oxides with high propylene oxide content is that the grafting is easy. The particular advantage of polyethylene oxide and copolymeric alkylene oxides having a high proportion of ethylene oxide is that the weight ratio of side chain to backbone is greater when grafting is carried out and the graft density is the same as in polypropylene oxide.

The K values of the copolymers according to the invention are usually from 10 to 150, preferably from 10 to 80 and more preferably from 15 to 60 (determined by H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 and 71 to 74 ( 1932) in water or aqueous sodium chloride solutions at 25 ° C (concentration NaCl 0.1 to 7.0 wt .-%) and polymer concentrations, depending on the K value range at 0.1 wt .-% to 5 wt. -% lie). The respective desired K value can be adjusted by the composition of the starting materials.

The copolymers according to the invention can be prepared by reacting (a) at least one ethylenically unsaturated monomer whose homo- or copolymers exhibit thermosensitive behavior, and (b) at least one ethylenically unsaturated monomer having a dye affinity group and optionally with monomers (c) different therefrom, optionally radically polymerized in the presence of a graft.

The free-radical polymerization of the monomers can be carried out by any known method, such as solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization, preferably the methods of solution polymerization and bulk polymerization, very particularly preferably solution polymerization.

Advantageously, a solution polymerization is carried out, ie the polymerization takes place in an organic solvent or solvent mixture, in water or in mixtures of water with organic solvents as the reaction medium. According to a preferred embodiment, the reaction medium contains predominantly organic solvents (mixtures), ie the proportion of water is less than 30% by volume, in particular less than 10% by volume, based on the total amount of solvent. Examples of suitable organic solvents are alkyl acetates, for example ethyl acetate, aliphatic and cycloaliphatic monohydric C 1 -C 4 -alcohols, eg. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol; polyhydric alcohols, such as C 1 -C 4 -glycols, eg. Ethylene glycol, propylene glycol and butylene glycol and glycerol; Mono- and dialkyl ethers of polyhydric alcohols, such as C 1 -C 4 -alkyl ethers of said polyhydric alcohols, eg. Monomethylethyleneglycol, monoethylethyleneglycol, dimethylethyleneglycol and dimethylpropyleneglycol; Ether alcohols, eg. For example, diethylene glycol and triethylene glycol; and cyclic ethers, e.g. Eg dioxane. Preferred organic solvents are alkyl acetates and alcohols.

Suitable radical initiators are, in particular, peroxo compounds, azo compounds, redox initiator systems and reducing compounds. Of course you can also use mixtures of radical starters.

Among the thermally activatable polymerization initiators, preference is given to initiators having a decomposition temperature ("10 h half-life decomposition temperature") in the range from 20 to 180 ^° C., in particular from 50 to 120 ^° C. Examples of preferred thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (Ammonium and alkali metal sulfates, preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide, organic peroxo compounds such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide tert-butyl peracetate, tert-butyl per-maleate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl pernodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy 2-ethylhexanoate and diisopropyl peroxydicarbamate; azo compounds such as 2,2'-azobis; isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidinopropane) dihydrochloride.

These initiators can be used in combination with reducing compounds as starter / regulator systems. Examples of such reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine. For example, the combinations tert-butyl hydroperoxide / sodium disulfite and tert-butyl

Butyl hydroperoxide / sodium hydroxymethanesulfinate; furthermore systems with addition of small amounts of redox metal salts such as iron salts, e.g. Ascorbic acid / ferrous sulfate / sodium peroxodisulfate.

Preferred initiators are soluble in the amount used in the polymerization medium. Therefore, particularly water-soluble initiators are preferred. Especially preferred Initiators are the aforementioned diazo compounds, in particular water-soluble diazo compounds such as azobis (2-amidinopropane) dihydrochloride.

Also suitable are photoinitiators; e.g. Benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and their derivatives.

Depending on the requirements of the material to be polymerized, the polymerization initiators are usually used in amounts of from 0.01 to 15% by weight, preferably from 0.25 to 8% by weight, based in each case on the monomers to be polymerized, and can be used individually or to utilize beneficial synergistic effects in combination.

To limit the molecular weights of the copolymers according to the invention, it is possible to use regulators conventional in the polymerization, e.g. Mercapto compounds, such as mercaptoethanol, thioglycollic acid, 1,4-bismercaptobutane-2,3-diol; Alkali metal sulfites and hydrogen sulfites such as sodium sulfite; Alkali metal phosphites and hypophosphites such as sodium hypophosphite, etc. are added. Suitable amounts of regulator are generally in the range of 0.01 to 5 wt .-%, based on the monomers to be polymerized.

The polymerization temperature is usually in the range of 30 to 200 ⁰ C, preferably from 50 to 150 ⁰ C, particularly preferably from 60 to 90 ° C.

The polymerization can be carried out under atmospheric pressure, if appropriate, it can also be carried out in a closed system under the developing intrinsic pressure.

Frequently, the production of the copolymers is followed by a chemical and / or physical deodorization, ie removal of unreacted monomers. In physical deodorization, the monomers are mixed with water vapor, e.g. B. by distilling off a portion of the aqueous polymerization medium and / or by passing hot steam, removed from the polymerization mixture. In chemical deodorization, unreacted monomers in the reaction mixture are removed by use of more severe polymerization conditions, e.g. B. by the addition of further polymerization, often by addition of the above-mentioned redox initiators and especially by the addition of hydroperoxides, such as hydrogen peroxide and alkyl hydroperoxides, z. For example, tert-butyl hydroperoxide, in combination with reducing agents, in particular sulfur-containing reducing agents such as hydrogen sulfite, dithionite, adducts of hydrogen sulfite with ketones, such as the acetone-bisulfite adduct, hydroxymethanesulfinate and the like, optionally in the presence of traces of transition metals, eg Fe ^{2 +} or Fe ³⁺ . The reaction mixtures obtained in the solution polymerization typically contain the copolymer in a concentration of 10 to 70% by weight, preferably 20 to 60% by weight (solids content of the polymerization solution).

The copolymers of the invention are preferably used in the form of their aqueous solution. In this case, preference is given to those copolymers which preferably have a neutral or basic pH in the form of their aqueous solution or emulsion. For mixing with the other components in the detergent composition, the copolymer solution may either be used directly or the pH adjusted by base or acid addition. The copolymer content of the aqueous solutions is typically in the range of 10 to 70% by weight, preferably 20 to 60% by weight.

A preferred pH range for mixing is as a rule from 5 to 11, preferably from 6 to 10 and particularly preferably from 6.5 to 9, very particularly preferably from 7 to 8.9.

The copolymers of the invention can also be used in powder or granular form.

The color transfer inhibitors are water-soluble below the LCST and can be used in solid and liquid detergents and in laundry after-treatment agents. They are characterized by a high compatibility with conventional detergent ingredients, in particular with the components of liquid detergents.

The color transfer to mitgeschaschenes tissue and the associated undesirable discoloration of these tissues is effectively inhibited. Already at concentrations of 10 to 150 ppm in the washing or rinsing liquor, good to very good color transfer-inhibiting effects are achieved.

The solid detergent formulations according to the invention also contain in particular the following components:

(a) 0.05 to 20% by weight of at least one thermosensitive polymer,

(b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,

(c) 0.5 to 50% by weight of an inorganic builder,

(d) 0 to 10% by weight of an organic cobuilder and (e) from 0.1% to 60% by weight of other conventional ingredients such as sizing agents, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, other color protective additives and dye transfer inhibitors, grayness inhibitors, soil release polyesters, fiber protection additives, Silicones, dyes, bactericides and preservatives, dissolution improvers and / or disintegrants, water,

wherein the sum of components (a) to (e) gives 100 wt .-%.

The solid detergent formulations according to the invention can be in powder, granule, extrudate or tablet form.

The liquid detergent formulations according to the invention preferably have the following composition:

(a) 0.05 to 20% by weight of at least one thermosensitive polymer,

(b) 0.5 to 70% by weight of at least one nonionic, anionic and / or cationic surfactant,

(c) 0 to 20% by weight of an inorganic builder,

(d) 0 to 10% by weight of an organic cobuilder,

(e) from 0.1% to 60% by weight of other conventional ingredients, such as soda, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, other color protective additives and dye transfer inhibitors, grayness inhibitors, soil release polyesters, fiber protective additives, silicones, Dyes, bactericides and preservatives, organic solvents, solubilizers, hydrotropes, thickeners and / or alkanolamines and

(f) 0 to 99.35% by weight of water.

The laundry aftertreatment agents according to the invention, in particular laundry care rinse agents, preferably contain

(a) 0.05 to 20% by weight of at least one thermosensitive polymer,

(b) 0.1 to 40% by weight of at least one cationic surfactant,

(c) 0 to 30% by weight of at least one nonionic surfactant, (D) 0.1 to 30 wt .-% of other conventional ingredients, such as silicones, other lubricants, wetting agents, film-forming polymers, fragrances and dyes, stabilizers, fiber-protective additives, other color protective additives and Farbübertragungsinhibito- ren, complexing agents, viscosity modifiers, soil release Additives, solubilizers, hydrotropes, anticorrosion additives, bactericides and preservatives, and

(e) 0 to 99.75% by weight of water.

Suitable nonionic surfactants (B) are, in particular:

Alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol ethoxylates: The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide per mole of alcohol. Preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms;

Alkylphenol alkoxylates, especially alkylphenol ethoxylates containing Ce-Cu alkyl chains and 5 to 30 moles of alkylene oxide / mole; - Alkylpolyglucoside containing C8-C22, preferably Cio-Ci8-alkyl chains and usually 1 to 20, preferably 1, 1 to 5, glucoside units; N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, long chain amine oxides, polyhydroxy (alkoxy) fatty acid derivatives, e.g. Polyhydroxy fatty acid amides, gemini surfactants and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide; as well as their mixtures.

Suitable anionic surfactants are, for example:

Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular C 1 -C 5 -alcohol sulfates, C 12 -C 14 -alcohol sulfates, C 12 -C 18-

Alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate, and tallow fatty alcohol sulfate;

Sulfated alkoxylated Cs-C22 alcohols (alkyl ether sulfates): Compounds of these

Are prepared, for example, by first obtaining a C8-C22, preferably a Cio-Cis alcohol, e.g. a fatty alcohol, alkoxylated and that

Alkoxylation then sulfated. For the alkoxylation is preferably used ethylene oxide;

Linear C8-C2o-alkylbenzenesulfonates (LAS), preferably linear C9-C13

Alkylbenzenesulfonates and alkyltoluenesulfonates; Alkanesulfonates, especially C8-C24, preferably Cio-Cis-alkanesulfonates;

olefin;

Fatty acid and fatty acid ester sulfonates; Soaps, such as the Na and K salts of C8-C24 carboxylic acids; as well as their mixtures.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts are e.g. Alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Particularly suitable cationic surfactants which may be mentioned are: C ₇ -C ₂ 5-alkylamines;

N, N-dimethyl-N- (hydroxy-C7-C25-alkyl) ammonium salts; niumverbindungen quaternized with alkylating agents mono- and di- (C7-C ₂ 5-alkyl) dimethylammonium;

Esterquats, especially quaternary esterified mono-, di- and trialkanolamines esterified with C8-C22 carboxylic acids;

Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas II or III

in which the variables have the following meaning:

R ^{9 is} C ₁ -C ₂₅ alkyl or C ₂ -C ₂ 5 alkenyl;

R ^{10 is} C ₁ -C ₄ -alkyl or hydroxy-C ₁ -C ₄ -alkyl;

R ^{11 is} C ₁ -C ₄ -AIk ^, hydroxy-Ci-C ₄ alkyl or a group R ¹ - (CO) -X- (CH ₂₎ _m - (X: -O- or -NH-; m: 2 or 3), wherein at least one R ^{9 is} C 7 -C ₂₂ -alkyl.

Suitable amphoteric surfactants are e.g. Alkyl betaines, alkyl amide betaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds.

Suitable inorganic builders are, in particular:

Crystalline and amorphous aluminosilicates with ion-exchanging properties, in particular zeolites: Various types of zeolites are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na partially opposes other cations such as Li, K, Ca, Mg or ammonium is exchanged; Crystalline silicates, such as, in particular, disilicates and sheet silicates, for example δ- and β-Na 2 Si 2 O 5. The silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference being given to the Na, Li and Mg silicates; Amorphous silicates such as sodium metasilicate and amorphous disilicate; Carbonates and bicarbonates: These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li and Mg carbonates and hydrogencarbonates, in particular sodium carbonate and / or sodium bicarbonate; and polyphosphates, such as pentasodium triphosphate.

As organic cobuilders are particularly suitable:

Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, e.g. As agaric, malic, tartaric, gluconic, glutaric, succinic, imidodisuccinic, oxydisuccinic, propanetricarboxylic, butanetetracarboxylic, cyclopentanetetracarboxylic, alkyl and

Alkenyl succinic acids and aminopolycarboxylic acids, e.g. Nitrilotriacetic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserine diacetic acid, N- (2-hydroxyethyl) iminoacetic acid, ethylenediamine disuccinic acid, and methyl and ethyl glycine diacetic acid or their alkali metal salts; Oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or C 2 -C 22 olefins, e.g. Isobutene or long-chain α-olefins, vinyl-C 1 -C 8 -alkyl ethers, vinyl acetate, vinyl propionate, (meth) acrylic esters of C 1 -C 8 -alcohols and styrene. Preference is given to the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid.

The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt;

Phosphonic acids, e.g. 1-hydroxyethylene (1, 1-diphosphonic acid), aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid) and their alkali metal salts.

Suitable grayness inhibitors are, for example, carboxymethyl cellulose and graft polymers of vinyl acetate on polyethylene glycol.

Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.

Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile-methyl sulfate. Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.

Suitable further color transfer inhibitors are, for example, homopolymers, copolymers and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.

Detergent ingredients are otherwise well known. Detailed descriptions are for. In WO-A-99/06524 and 99/04313; in Liquid Detergents, Editor: Kuo- Yann Lai, Surfactant Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, to find.

Application of LCST polymers according to the invention

Selected colored fabric (EMPA 130 EMPA 132 EMPA 133 or EMPA 134) was washed in the presence of white test of cotton and ballast fabric of cotton / polyester and polyester with a detergent at 60 ⁰ C with the addition of the LCST polymers. After the wash, the fabrics were rinsed, spun and dried. To determine the Farbübertragunsinhibierende effect, the staining of the white test tissue was determined photometrically (photometer: Elrepho ^® 2000 Fa. Datacolor). The color strength of the staining was determined from the remission values measured on the test fabric according to the method described in A. Kud, Seifen, Ole, Fette, Wachse, Volume 1 19, pages 590-594 (1993). From the color intensity for the test with the respective test substance, the color intensity for the test without test substance and the color strength of the test fabric before washing the color transfer inhibiting effect of the test substance according to the following formula in% was determined.

Color strength (without polymer) - Color intensity (with polymer)

FUI effect [%] = - x 100 Color strength (without polymer) - Color intensity (before washing)

The washing conditions are given in Table 1.

The composition of the detergents A and B used are shown in Tables 2 and 3.

The color transfer inhibition test results are shown in Table 4. Table 1

Table 2 Adjust to pH 9 with sodium hydroxide solution. Table 3

Preparation of the novel copolymers

Polymer 1:

In a 2L polymerization apparatus with anchor stirrer and internal thermometer was a

Mixture of 210 g of polyethylene glycol monomethyl ether (MW 1500), gassed 12 g of ethyl acetate and 4 g of feed 2 with nitrogen and heated to 77 ⁰ C. After 4 minutes of stirring at 77 ⁰ C were feed 1, consisting of 300 g of vinylcaprolactam, 90 g of 1-vinylimidazole and 180 g of ethyl acetate in 5 hours and feed 2, consisting of 5.85 g of t-butyl perpivalate (75%) and 50 g Vinegar, dosed in 5.5 hours. Then, feed 3, consisting of 5.2 g of t-butyl perpivalate (75%) and 44 g of ethyl acetate, was added. The reaction mixture was stirred for a further 4 hours at 77 ⁰ C, and then a steam distillation at 93 to 100 ⁰ C was carried out. , A yellow, clear polymer solution was obtained.

Polymer 2:

In a 2L polymerization apparatus with anchor stirrer and internal thermometer, a mixture of 210 g of polyethylene glycol monomethyl ether (MW 1500), 12.0 g of ethyl acetate and 4 g of feed 2 was gassed with nitrogen and heated to 77 ⁰ C. After stirring for 4 minutes, feed 1, consisting of 240 g of vinylcaprolactam, 75 g of vinylpyrrolidone, 75 g of vinylimidazole and 180 g of ethyl acetate in 5 hours and feed 2, consisting of 5.85 g of t-butyl perpivalate (75%) and 50 g of ethyl acetate, added in 5.5 hours. Feed 3, consisting of 5.2 g of t-butyl perpivalate (75%) and 44 g of sigester added. It was stirred for a further 4 hours at 77 ⁰ C. Subsequently, a steam distillation at 93 to 100 ⁰ C. A yellow, clear polymer solution was obtained.

Polymer 3:

In a 2LPolymerisationsapparatur with anchor stirrer and internal thermometer, a mixture of 120 g of polyethyleneimine (MW 2000), 12.0 g of ethyl acetate and 4 g of feed 2 was gassed with nitrogen and heated to 77 ⁰ C. After stirring for 4 minutes, feed 1, consisting of 240 g of vinylcaprolactam, 120 g of vinylpyrrolidone, 120 g of vinylimidazole and 180 g of ethyl acetate in 5 hours and feed 2, consisting of 7.2 g of

Butyl perpivalate (75%) and 50 g of ethyl acetate, dosed in 5.5 hours. Then, feed 3, consisting of 6.4 g of t-butyl perpivalate (75%) and 44 g of ethyl acetate was added. It was stirred for a further 4 hours at 77 ⁰ C. Subsequently, a steam distillation at 93 to 100 ⁰ C. A yellow, clear polymer solution was obtained.

Polymer 4:

Mixture of 120 g of polyethylene glycol monomethyl ether (MW 6000), 95 g of ethyl acetate and 4 g of feed 2 gassed with nitrogen and heated to 77 ⁰ C. After 4 minutes, with stirring, feed 1, consisting of 300 g of vinylcaprolactam, 180 g of vinylimidazole and 100 g of ethyl acetate in 5 hours and feed 2, consisting of 7.2 g of t-butyl perpivalate (75%) and 50 g of ethyl acetate, in 5.5 hours added. Then, feed 3, consisting of 6.4 g of t-butyl perpivalate (75%) was added. It was stirred for a further 4 hours at 77 ⁰ C. Subsequently, a steam distillation at 93 to 100 ⁰ C. A yellow, clear polymer solution was obtained.

Polymer 5:

In a 2L polymerization apparatus with anchor stirrer and internal thermometer 200 g of ethyl acetate were gassed with nitrogen and heated to 77 ⁰ C. After reaching this temperature, feed 3, consisting of 20.4 g of t-butyl perpivalate (75%) in 140 g of ethyl acetate, started, and added in 5.5 hours. After 4 minutes of stirring at 77 ⁰ C were feed 1, consisting of 53.9 g of polyethylene glycol monomethyl ether monoacrylate (MW 1000) (83.5% in toluene) in 130 g of ethyl acetate, and feed 2, consisting of 150 g vinylcaprolactam and 105 g Vinylimidazole, dosed in 5 hours. To

Termination of feed 3 was added feed 4, consisting of 3.4 g of t-butyl perpivalate (75%) in 20 g of ethyl acetate. The reaction mixture was stirred at 77 ^° C. for a further 4 hours. Subsequently, a steam distillation at 93 to 100 ⁰ C was carried out. A yellow, clear polymer solution was obtained. Table 4: Analytical values Polymer 1-5

The determination of the stated K values was carried out according to H. Fikentscher, Cellulose Chemistry, Volume 13, pages 58-64 and 761-774 (1932) as 1 wt .-% solution in water at 25 ⁰ C.

The cloud points (or LCST) of the polymers were determined to be 1% in water. (Temperature range 20 to 80 ⁰ C, heating rate of 1 degree Celsius per minute, both during heating and cooling)

Table 5: Application of liquid detergent A

PVP = polyvinylpyrrolidone with K value 30

Table 6: Application of solid detergent B

Claims

claims

1. Use of thermosensitive polymers having a lower critical solubility temperature (LCST) as color transfer inhibitors in laundry detergent compositions for textiles.

2. Use according to claim 1, wherein the LCST of the thermosensitive polymer is in the range of 20 to 80 ⁰ C.

3. Use according to claim 1 or 2, wherein the thermosensitive polymer is a copolymer of ethylenically unsaturated monomers M, the at least one monoethylenically unsaturated monomer (a), the homo- or copolymers show thermosensitive behavior, and (b) at least one monoethylenically unsaturated Monomer (b) having a dye affinity group.

4. Use according to claim 3, wherein the monomers M, based on the total amount of the monomers M, i. From 20 to 80% by weight of at least one monomer (a) and ii. From 5 to 50% by weight of at least one monomer (b) and iii. up to 40% by weight of one or more of the monomers (a) and (b) of different monomers (c).

5. Use according to claim 4, wherein the monomer (a) is N-vinyllactams having a ring size of at least 6 atoms, N-mono-C 1 -C 8 -alkyl (meth) acrylamides, N, N-di-C 1 -C 8 alkyl (meth) acrylamides, hydroxy-C 2 -C 4 -alkyl (meth) acrylates, vinyl alcohol and C 1 -C 5 -alkyl vinyl ethers.

6. Use according to claim 5, wherein the monomer (a) is selected from N-vinylcaprolactam, N-isopropylacrylamide, hydroxypropyl acrylate, vinyl alcohol and vinyl methyl ether.

Use according to claim 6, wherein the monomer (a) is N-vinylcaprolactam.

8. Use according to any one of claims 3 to 7, wherein the dye affinity group in the monomer (b) is a 5- or 6-membered nitrogen-containing heterocycle, which is optionally fused.

9. Use according to claim 8, wherein the monomer (b) is N-vinylimidazole, quaternized N-vinylimidazole, N-vinylpyrrolidone, N-vinyltriazole, N-vinylbenzimidazole, hydroxyethylpyrrolidone (meth) acrylate and hydroxyethylimidazole (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine and derivatives thereof.

10. Use according to claim 9, wherein the monomer (b) is N-vinylimidazole.

1 1. Use according to one of the preceding claims, wherein the monomers M comprise at least one monomer (c), which is selected from monoethylenically unsaturated compounds having a poly-C2-C6-alkylene oxide group.

12. Use according to one of the preceding claims, wherein the copolymer is obtainable by copolymerization of the monomers M in the presence of a graft base.

13. Use according to claim 12, wherein the graft base is selected from P0IV-C 2 -C 4 -alkylene ethers and poly-C 2 -C 4 -alkyleneimines.

14. Use according to claim 12 or 13, wherein the weight ratio of graft to the total amount of ethylenically unsaturated monomers

M is in the range of 1:10 to 1: 1.

15. A process for washing dyed textiles, in which

(a) contacting the fabrics with a thermosensitive polymer according to any one of claims 1 to 14 and at least one surfactant in a wash liquor,

(b) raising the temperature of the wash liquor to the LCST of the thermosensitive polymer or a higher temperature, and

(C) separates the thermosensitive polymer with the wash liquor from the textiles.

16. A copolymer consisting of unsaturated monomers M and optionally one

Grafting base is constructed, wherein the monomers M comprise at least one monoethylenically unsaturated monomer (a), whose homo- or copolymers thermositiv behave, and (b) at least one monoethylenically unsaturated monomer (b) having a dye affinity group.

17. A copolymer according to claim 16, wherein the monomer (a) is selected from N-vinylcaprolactam, N-isopropylacrylamide, hydroxypropyl acrylate, vinyl alcohol and vinyl methyl ether, the dye affinity group in the monomer (b) is a 5- or 6-membered nitrogen-containing heterocycle which optionally fused.

A copolymer according to claim 16 or 17, wherein the monomers M comprise at least one monomer (c) selected from monoethylenically unsaturated compounds having a poly-C 2 -C 6 -alkylene oxide group.

19. A copolymer according to any one of claims 16 to 18, wherein the graft base is selected from polyalkylene oxides and polyalkyleneimines.

20. A detergent formulation comprising at least one copolymer according to any one of claims 16 to 19, at least one surfactant and at least one typical detergent ingredient, the inorganic builders, organic co-builders, adjusting agents, soda, enzymes, perfume, complexing agents, corrosion inhibitors , Bleaching agents, bleach activators, bleach catalysts, other color protective additives and color transfer inhibitors, grayness inhibitors, Zn release polyesters, fiber protective additives, silicones, dyes, bactericides, preservatives, dissolution improvers and disintegrants.