EP1294843A1

EP1294843A1 - Washing active preparation

Info

Publication number: EP1294843A1
Application number: EP01947356A
Authority: EP
Inventors: Roman Benedikt Raether; Sylke Haremza; Susanne Brinkmann-Rengel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2000-06-16
Filing date: 2001-06-11
Publication date: 2003-03-26
Also published as: JP2004503664A; US20030109414A1; KR20030007968A; US6710024B2; AU2001269064A1; WO2001096515A1; MXPA02012192A; DE10029696A1; CN1436229A

Abstract

The invention relates to a washing active preparation containing a water-soluble or water-dispersible block copolymer which can be produced by controlled radical polymerisation, to a method for producing a washing active preparation of this type and to the use of water-soluble or water-dispersible block copolymers produced by controlled radical polymerisation for producing washing active preparations.

Description

Wash-active preparation

The present invention relates to wash-active substances which contain water-soluble block copolymers. Furthermore, the present invention relates to a method for producing such wash-active substances and the use of special block copolymers in wash-active substances.

Wash-active preparations are usually used to clean soiled textiles, in particular soiled clothing. However, it can be problematic here that textiles of all kinds, in particular, however, such textiles as are used for the production of clothing, usually contain a large number of different fabrics, which, moreover, have been provided with different colors by a wide variety of dyeing processes.

In addition, there are also textiles which have not been subjected to a special dyeing process, but which have been converted, for example by bleaching processes, into a colorless, ie, white state and in this form of their intended use become.

The cleaning of textiles by means of washing-active substances should expediently remove dirt from the textiles without, however, significantly changing the original appearance of the textiles in terms of color and structure. While this task for monochrome textiles, which ideally consist of only one material, is relatively easy to solve, problems arise with regard to the cleaning of multicolored textiles or a mixture of textiles of different colors. The cleaning of textiles or textile mixtures which have light colors and dark colors, for example white and blue or white and black, is particularly problematic. Here, when using conventional detergent substances, there is often a color transition from the dark textiles or textile components to the lighter ones, so that a before the washing process For example, a white piece of textile may have a darker color after washing.

However, such color transitions are unpopular with the users of wash-active substances, since the appearance of the textiles is usually changed disadvantageously.

A variety of attempts to solve this problem have been proposed in the past.

For example, DE-A 2 232 353 describes a detergent and cleaning agent mixture with an improved inhibitory effect on dye transfer. To inhibit the color transition, it is proposed here to add a proportion of a water-soluble polymer component based on polyvinylpyrrolidone to a detergent and cleaning agent mixture. For example, a copolymer of polyvinyl pyrrolidone with acrylonitrile or maleic anhydride is described as advantageous. However, the copolymers mentioned have no block structure.

DE-A 28 14 287 also describes a detergent containing discoloration-inhibiting additives. To prevent discoloration occurring during the washing process, it is proposed to add a water-soluble or dispersible homopolymer or copolymer of N-vinylimidazole to a washing and cleaning agent. However, the polymers described also have no block structure.

The present invention is therefore based on the object of providing wash-active preparations which largely prevent dye transfer during the washing process.

The object on which the invention is based is achieved by means of a wash-active preparation, as described in the context of the text below.

In the context of the present invention, a “block copolymer” is understood to mean a polymer which is distinguished by at least two different ones Has monomer composition labeled polymer blocks. In the context of the present invention, a “different monomer composition” means the finding that at least two regions of the block copolymer have a different monomer composition. It is possible in the context of the present invention that the transition between two blocks runs continuously, that is to say that between two blocks there is a zone which has a statistical or regular sequence of the monomers constituting the blocks, but it is also contemplated within the scope of the present invention that the transition between two blocks is essentially discontinuous. A "substantially discontinuous transition" understood a transition zone that has a significantly shorter length than at least one of the blocks separated by the transition zone. It is possible for a block to be based on only one type of monomer. However, it is also contemplated that a block be constructed from two or more monomers. In a preferred embodiment of the present invention, the chain length of such a transition zone is less than 1/10, preferably less than 1/20, of the block length of at least one of the blocks separated by the transition zone.

In the context of the present invention, a “different monomer composition” is further understood to mean that the monomers constituting the respective block differ in at least one feature, for example in their interlinking, in their conformation or constitution. If, as already described above, If a block is constructed from more than one type of monomer, different blocks of the block copolymer may differ in the present context, for example, also by different concentrations of the monomers constituting a block, preferably block copolymers which have at least two blocks are used in the context of the present invention whose monomer composition differs at least through the constitution of the monomers.

The present invention therefore relates to a wash-active preparation, at least containing 0.01 to 50% by weight of a water-soluble or water-dispersible block copolymer A with a molecular weight of more than 1000, which can be prepared by a process comprising the following steps (i) and (ii):

(i) Reaction under radical conditions of a reaction mixture. comprising at least one radically convertible monomer (a) in the presence of at least one radical of the formula (III)

-R2 (III)

R3

where R 1 to R ₃ each independently of one another are hydrogen, methyl or a radical-stabilizing and / or sterically demanding group selected from an unsubstituted or substituted, linear or branched-chain alkyl having two or more carbon atoms, cycloalkyl, alcohol, ether, Polyether, amine, aralkyl, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom (shark), a substituted or unsubstituted, linear or branched chain alkenyl or alkynyl group, -C (O) R ₅ , - C (O ) OR ₅ , -CR _J R _Ö -O ^, -OC (O) R ₅ , -CN, -O-CN, -S-CN, -O- C = NR ₅ , -SC = NR ₅ , -O -CR ₅ R _Ö -CR ₇ R ₈ NR ₉ RI _O , -N = CO, -C = NR ₅ , - CRsRg-Hal, -C (S) R ₅ , -CR ₅ R ₆ -P (O) R ₇ R ₈ , -CR ₅ R ₆ -PR ₇ R ₈ , -CR ₅ R ₆ -NR ₇ R ₈ , -CR ₅ R ₆ (OR ₇ ) (OR ₈ ), -CR ₅ R ₆ (OR ₇ ) ( NR ₈ ),

-CR ₅ R _Ö (NR ₇ ) (NR ₈ ), an acid anhydride, acetal or ketal group, -SO ₂ R ₅ , an amidine group -NR ₅ C (S) NR ₆ , - NR ₅ C (S) -OR _Ö , -N = C = S, -NO2, -C = N-OH, -N (R ₅ ) = NR ₆ , -PRsReR _? , -OSiR ₅ R _δ R, or -SiR ₅ ReR, where R ₅ to R _{10 are} each independently defined as R] _^ to R ₄ , or two of the

Residues Ri to _t a C - to C ring which in turn is substituted or may be unsubstituted and may optionally contain one or more heteroatoms, with the proviso that at least two of the radicals R 1 to R _{3 are} a radical-stabilizing and / or sterically demanding group as defined above and

(ii) reaction of the reaction product obtained in step (i) under radical conditions in the presence of at least one radical-homo- or copolymerizable monomer (b) and

b) 50 to 99.99% by weight of an anionic, cationic, zwitterionic or nonionic surfactant with a molecular weight of less than 1000.

The radical of the formula (III) is preferably derived from at least one compound of the formula (I).

where R 1 to R ₄ each independently of one another are hydrogen, methyl or a radical-stabilizing and / or sterically demanding group selected from an unsubstituted or substituted, linear “or branched-chain alkyl having two or more carbon atoms, cycloalkyl, alcohol, ether or , Polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom, a substituted or unsubstituted, linear or branched chain alkenyl or alkynyl group, -C (O) R ₅ ,

-C (O) OR ₅ , -CR ₅ R ₆ -OR ₇ , -OC (O) R ₅ , -CN, -O-CN, -S-CN, -OC = NR ₅ , -S- C = NR ₅ , -N = C = O, -C = NR ₅ , -CRgRe-Hal, -C (S) R ₅ , - -CR ₅ R ₆ -NR ₇ R ₈ , -CR ₅ R ₆ (OR ₇ ) (OR ₈ ), -CR ₅ R ₆ (OR ₇ ) (NR ₈ ),

-CR ₅ R ₆ (NR ₇ ) (NR ₈ ), an acid anhydride, acetal or ketal group, -SO R ₅ , an amidine group -NR ₅ C (S) NRe, -NR ₅ C (S) -OR ₆ , -N = CHS, -NO2, -C = N-OH, -

-OSiR ₅ R _δ R, or -SIR ₅ R ₆ R ₇ , where R ₅ to R _{10 are} each independent from each other are defined as Ri to t, or two of the radicals R to R _{4 form} a C - to C ring which in turn can be substituted or unsubstituted and can optionally contain one or more heteroatoms, with the proviso that at least two of the Ri to R _{4 are} a radical stabilizing and / or sterically demanding group as defined above, or diphenylethylene, dinaphthaleneethylene, 4,4'-vinylidene bis (N, N'-dimethylaniline), 4,4'-vinylidene bis (aminobenzene), ice - and trans-stilbene and or of at least one compound of the formula (II)

and Ri to R _t and Rπ and _R12 are each independently hydrogen, methyl or a radical stabilizing and / or bulky group selected from an in each case unsubstituted or substituted, linear or branched chain alkyl with two or more carbon atoms, cycloalkyl, Alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heteroeyclic or olefinic hydrocarbon, a halogen atom, a substituted or unsubstituted, linear or branched chain alkenyl or AKkinylgruppe, -C (O) R ₅ , - C (O) OR ₅ , -CR ₅ Rö-OR ₇ , -OC (O) R ₅ , -CN, -O-CN, -S-CN, -OC = NR ₅ , -S- C = NR ₅ , -O-CR ₅ R6-CR ₇ R ₈ NR ₉ Rιo, -N = CO, -C = NR ₅ , -CRjR _δ -Hal, -C (S) R ₅ , - CR ₅ R ₆ -P (O) R ₇ R ₈ , -CR ₅ R ₆ -PR ₇ R ₈ , -CR ₅ R ₅ -NR ₇ R ₈ , -CR ₅ R ₆ (OR ₇ ) (OR ₈ ), -CR ₅ R ₆ (OR ₇ ) (NR ₈ ),

-CR ₅ R ₆ (NR ₇ ) (NR ₈ ), an acid anhydride, acetal, ketal group, -SO ₂ R ₅ , an amidine group -NR ₅ C (S) NRe, -NR ₅ C (S) -OR ₆ , -N = C = S, -NO2, -C = N-OH, - N (R5) = NR6, -PR ₅ ReR ₇ ,

-OSiR ₅ R _ö R ₇ , or -SiR ₅ R _ö R, where R to Rio are each independently defined as Ri to i, or two of the radicals Ri to j form a C ₄ to C ₇ ring which in turn may be substituted or unsubstituted and may optionally contain one or more heteroatoms, provided that at least two of the R _t to j are a radical-stabilizing and / or sterically demanding group, as defined above. In the course of the preparation of the copolymer used according to the invention, all radical-convertible monomers can be used as monomer (a).

Mixtures of different monomers can of course also be used as monomers (a) in the context of the present invention.

In addition, mixtures of at least one hydrophilic monomer and at least one hydrophobic monomer can also be polymerized in accordance with the above-mentioned process.

The following are specifically mentioned as monomers (a):

Dienes, such as butadiene, isoprene, myrcene and pentadiene, and also C 1 -C ₂₀ -alkyl and hydroxyalkyl esters of monoethylenically unsaturated C ₃ -C ₁₀ -monocarboxylic acids or C ₄ -C ₈ -dicarboxylic acids, e.g. methyl methacrylate, ethyl methacrylate, propyl methacrylate (all Isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, benzyl acrylate, stearyl acrylate, phenyl acrylate, acrylate, phenyl acrylate, acrylate, phenyl acrylate, acrylate, phenyl acrylate, acrylate, phenyl acrylate, phenyl acrylate, , Hydroxybutylacrylat, further (meth) acrylic esters of alkoxylated Ci to Cι ₈ alcohols, which are reacted with 2 to 50 mol of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; Benzyl methacrylate, phenyl methacrylate, stearyl methacrylate, methacrylonitrile, acrylonitrile, functionalized methacrylates; Acrylates and styrenes, selected from glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), cyclohexyl methacrylate,

Cyclohexyl acrylate, hexyl methacrylate and hexyl acrylate (all isomers in each case), diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl methacrylate,

Diethylaminoethyl acrylate, triethylene glycol acrylate, methacrylamide, N-tert-butyl methacrylamide, Nn-butyl methacrylamide, N-methylol-methacrylamide, N-ethylol methacrylamide, N-tert-butylacrylamide, N-butylacrylamide, N-methylolacrylamide, N-ethyloloestersacrylic acid, vinylbenzene all vinylbenzene , Diethylaminostyrene (all isomers), α-methylvinylbenzoic acid (all isomers), Diethylamino-α-methylstyrene (all isomers), p-methylstyrene, p-vinylbenzenesulfonic acid, indene, trimethoxysilylpropyl methacrylate,

Triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate,

Diethoxymethylsilylpropylmethacrylat, Dibutoxymethylsilylpropylmethacrylat, Diisopropox3nmethylsilylpropylmethacrylat, Dimethoxysilylpropylmethacrylat, Diethoxysilylpropylmethacrylat, Dibutoxysilylpropylmethacrylat, Diisopropoxy- silylpropyl methacrylate, trimethoxysilylpropyl acrylate lat, Triethoxysilylpropylacry-, Tributoxysilylpropylacrylat, Dimethoxymethylsilylpropylacrylat, diethoxy methylsilylpropylacrylat, Dibutoxymethylsilylpropylacrylat, Diisopropoxymethyl- silylpropyl acrylate, Dimethoxysilylpropylacrylat, Diethoxysilylpropylacrylat, Dibutoxysilylpropylacrylat, Diisopropoxysilylpropylacrylat, vinyl acetate and vinyl butyrate, vinyl chloride, Vinyl fluoride, vinyl bromide, vinyl alcohol, vinyl ethers of Ci to -C ₈ alcohols, vinyl ethers of alkoxylated Ci to C ₁₈ alcohols and vinyl ethers of polyalkylene oxides such as polyethylene oxide, polypropylene oxide or polybutylene oxide, monoethylenically unsaturated C ₃ - to C ₁₀ - monocarboxylic acids, their alkali metal salts and / or ammonium salts, ex for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid or vinyl acetic acid, furthermore monoethylenically unsaturated C ₄ - to C ₈ dicarboxylic acids, their half esters, anhydrides, alkali metal salts and / or ammonium salts, for example maleic acid, fumaric acid, itaconic acid, malic acid, malacidic acid, mesaconic acid , Itaconic anhydride or methylmalonic anhydride; furthermore sulfonic acid groups or their salts, for example their monoethylenically unsaturated monomers containing alkali metal or ammonium salts, for example allylsulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), methallylsulfonic acid, vinyl sulfonic acid, acrylic acid 3-sulfopropyl ester or 3-sulfopropyl methacrylic acid, furthermore phosphonic acid groups or their salts, for example their monoethylenically unsaturated monomers containing alkali metal or ammonium salts, for example vinylphosphonic acid, allylphosphonic acid or

Acrylamidoethyl propanephosphonic acid, furthermore amides and N-substituted amides of monoethylenically unsaturated C ₃ - to Cio-monocarboxylic acids or C - to C ₈ -dicarboxylic acids, for example acrylamide, N-alkylacrylamides or N, N-dialkylacrylamides, each with 1 to 18 C atoms in the Alkyl group such as N-methacrylamide, N, N-dimethylacrylamide, N-tert-butylacrylamide or N-octadecylacrylamide, maleic acid monomethylhexylamide, Maleic acid monodecylamide, diethylaminopropyl methacrylamide or

acrylamido; further alkylamidoalkyl (meth) acrylates, for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate or dimethylaminopropyl methacrylate; furthermore vinyl esters, vinyl formate, vinyl acetate or vinyl propionate, which may also be saponified after the polymerization; furthermore N-vinyl compounds, for example N-vinylpyrrolidone, N-vinylcaprolactam, N-ninylformamide, Ν-ninyl-Ν-methylformamide, 1-ninylimidazole or 1-ninyl-2-methylimidazole; furthermore vinyl ethers of - to C ₁₈ alcohols, vinyl ethers of alkoxylated Ci- to Cι ₈ - alcohols and vinyl ethers of polyalkylene oxides such as polyethylene oxide, polypropylene oxide or polybutylene oxide, indene, dicyclopentadiene, monomers, the amino or imino groups such as dimethylaminoethyl methacrylate, diethylaminoethyl amyl acrylamyl amyl acrylamyl amyl acrylate, Monomers which carry quaternary ammonium groups, such as, for example, in the form of salts, as are obtained by reacting the basic amino functions with acids such as hydrochloric acid, sulfuric acid, nitric acid, formic acid or acetic acid, or in quaternized form (examples of suitable quaternizing agents are dimethyl sulfate, diethyl sulfate, methyl chloride , Ethyl chloride or benzyl chloride), such as, for example, dimethylaminoethyl acrylate hydrochloride,

Diallyldimemylammonium chloride, dimethylaminoethyl acrylate methyl chloride, dimethylaminoethylaminopropyl methacrylamide methosulfate, vinyl pyridinium salts or 1-vinylimidazolium salts; Monomers in which the amino groups and / or ammonium groups are only released after the polymerization and subsequent hydrolysis, such as, for example, Ν-vinylformamide or Ν-vinylacetamide and mixtures of two or more of the abovementioned monomers.

As a first monomer, preference is given to (a) styrenes, (meth) acrylates or their free acid, dienes or Ν-vinyl compounds, preferably the representatives of this group, which have already been mentioned above, or mixtures of two or more thereof, optionally with at least another radically homo- or copolymerizable monomer (a), use.

Furthermore, according to the invention, in the preparation of the block copolymer A, a compound of the formula (I)

or the formula (II)

used to arrive at the radical of formula (III).

In principle, all connections of the above are also here Formulas can be used according to the invention, provided that they correspond to the above definition or the definition given in the claims.

It is particularly important that at least two of the radicals R 1 to R 1 or R 1 to R ₃ in formula (III) represent a radical-stabilizing and / or sterically demanding group. The term "sterically demanding group" as used in the context of the present invention means that it is a group whose dimension in the reaction according to the invention under radical conditions is greater than or equal to the dimension of an isopropyl radical is. The term "radical-stabilizing group" used according to the invention denotes groups of the type defined in claim 1, the element structure of which enables radicals to be stabilized.

The following groups of the above type are to be mentioned in detail: branched-chain alkyl groups with three or more carbon atoms, in particular isopropyl and tert-butyl; Cycloalkyl groups, for example unsubstituted or substituted cyclophentyl or cyclohexyl; Alcohol groups, for example residues of branched alcohols such as isopropyloxy tert-butyloxy; aralkyl; substituted or unsubstituted aromatic or heterocyclic hydrocarbons such as phenyl, pyridyl; Halogen; cyano; nitro; Ester groups of the structure -C (O) OR ₅ , in which R _{5 can represent,} for example, a linear or branched optionally substituted alkyl, aralkyl or aromatic group. Further preference is given to using compounds of the formula (I) which have the following combinations of groups as radical-stabilizing groups: at least one substituted or unsubstituted phenyl and C (O) R ₅ ; at least one substituted or unsubstituted phenyl and CN; at least one substituted or unsubstituted phenyl and C (O) OR ₅ ; independently of one another at least two substituted or unsubstituted phenyl groups; independently of one another at least two C (O) OR ₅ ; and independently of one another at least two CN.

In particular, as a compound of the formula (I) or (II)

1, 1, 4,4-tetraphenyl-1, 3-butadiene; 1,4-bis (2-methylstyryl) benzene 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene

1, 2,3,4-tetraphenyl-1,3-cyclopentadiene

acenaphthylene

Cis- and trans-alpha-methylstilbene cis- and trans-4,4'-diphenylstilbene, diphenylethylene, dinaphthalenetylene,

4,4'-vinylidene-bis (N, N'-dimethylaniline), 4,4'-vinylidene-bis (aminobenzene), cis- and trans-stilbene,

Trans, trans and trans, cis and cis-cis-l, 4-diphenyl-1,3-butadiene

Alpha-omega-tetraphenylpolyethine diphenylfulven

triphenylethene

tetraphenylethene

1-cyano-1-phenylethylene; 1-alkoxycarbonyl-l-phenylethylene; 1,1-

Dialkoxycarbonyl-2-ethyl ethylene; 1, 1 -dialkoxycarbonyl-2-phenylethylene, 1,1 -dialkoxycarbonyl-2,2-dimethylethylene; 1, 1-Dialkoxycarbonylmethyl- ethylene; 9-Methylenxanthen; 9-methylenedioxanthene, 9-methylene-10-H-acridine or mixtures of two or more thereof.

The radical formation can take place according to the invention by different methods. So is a thermal, photo-chemical, electro-chemical or Electron transfer-induced generation is possible, as is the use of oxidizing or reducing agents to generate radicals.

In addition, the method described herein can be carried out in the presence of at least one radical initiator. Furthermore, thermally, electrochemically or photochemically initiating monomers can also be used as initiators. In general, however, all azo and / or peroxo compounds and / or compounds with homolytically cleavable CC bonds which are conventionally used in free-radical polymerization can be used. Suitable initiators are described, for example, in WO 98/01478 on p. 10, lines 17 to p. 11, line 15, which in this regard is included in full in the context of the present application. In addition, 3,4-dimethyl-3, 4-diphenylhexane or 2,3-dimethyl-2,3-diphenyl-butane can be used. Initiators are preferably used which are soluble in the reaction system used in each case. When reacting in the aqueous phase, oxidizing free radical initiators, such as, for example, potassium, sodium and ammonium peroxodisulfate, or a combination of a conventional, ie a non-oxidizing, initiator with H ₂ O ₂ are preferably used. Dicumyl peroxide, dibenzoyl peroxide, dilauryl peroxide and AIBN can also be used.

In a preferred embodiment of this process, a comparatively large amount of free radical initiator is added, the proportion of free radical initiator in the reaction mixture preferably being 0.1 to 50% by weight, more preferably 0.5 to 20% by weight, based in each case the total amount of monomer (a) and initiator. The molar ratio of initiator to compound (I) is preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2, and in particular 1.5: 1 to 1: 1.5.

If the reaction described in stage (i) is carried out in the aqueous phase, the term “aqueous phase” in the context of the present text is understood to mean a phase which contains 10 to 100% by weight of water. If the water content of the aqueous phase is included less than 10%, it is preferred in the context of the present invention if the aqueous phase is a mixture of water and one or more water-miscible solvents such as THF, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone or contains the like. However, it is also possible to carry out the reaction in step (i) in the presence of a mixture of water and a water-immiscible solvent, such as an aromatic solvent, for example toluene.

In a further embodiment, the above reaction in step (i) is carried out in the presence of at least one base. In principle, all low-molecular bases are to be used as low-molecular bases, NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- or triethylamine, dimethylethanolamine, or a mixture of two or more thereof being preferred, and ammonia and di- and triethanolamine are particularly preferred.

However, it is also possible to carry out the reaction according to step (i) in an organic solvent or solvent-free (“in bulk”), for example in the melt. If, in the context of the present invention, the reaction is carried out in an organic solvent or solvent-free is understood to mean a reaction procedure which takes place in the presence of less than 10% by weight, preferably less than 5% by weight or less than 1% by weight, of water in the composition of the invention, at least one block copolymer is used, in the preparation of which step (i) was carried out in an organic solvent or solvent-free, the water content of the reaction mixture being less than 0.5% by weight, for example less than 0.3% by weight or less than 0.1% by weight In a further embodiment of the present invention, the ReaMon guide stage (i) is carried out anhydrous, that is to say with a water content of less than 0.001% by weight. Such water contents can be achieved, for example, by using commercially available solvents, as are usually used as organic solvents in radical polymerizations.

Suitable solvents in the context of the present invention are in principle all polar and non-polar organic solvents in which the corresponding and preferably also the resulting polymers are soluble, if appropriate at elevated temperature. Suitable solvents are, for example, C ₃ to Cio alkanes, cyclohexane, decalin, acetone, methylethyl ketone. diisobutyl ketone, Tetrahydrofuran, dioxane, benzene, toluene, glycols such as ethylene glycol, triethylene glycol, partially or completely end-capped glycol ethers such as ethylene glycol monomethyl ether, ethyl acetate, methanol or ethanol or the higher homologues of the alkanols with up to 18 C atoms (optionally as cosolvent) or mixtures of two or more of that.

The reaction in stage (i) is generally carried out at temperatures above room temperature and below the decomposition temperature of the monomers, a temperature range from 50 to 150 ° C., more preferably 70 to 120 ° C. and in particular 80 to 110 ° C. being chosen.

The reaction in step (i) is generally carried out at pressures from 1 to 300 bar, for example from about 1.5 to 100 or about 2 to about 20 bar.

Although there are no restrictions with regard to the molecular weight distribution, a reaction product can be obtained in the reaction according to (i) which has a molecular weight distribution M _w / M _n measured using gel permeation chromatography using polystyrene as the standard of <4, preferably <3, more preferably < 2, in particular <1.5 and in some cases also <1.3. The molecular weights of the reaction product (A) by selecting the ratio of monomers (a) to give compounds (I) to free-radical initiator in wide limits controllable _^ In particular, the content of compound (I), determines the molecular weight in such a manner that the larger the proportion of compound (I), the lower the molecular weight obtained.

The reaction in step (i) can also be carried out in the presence of a surface-active substance.

The reaction product obtained in the reaction according to (i) can be directly processed further, or can be used as a macroinitiator for the further reaction according to step (ii), as defined further below. It is also possible to isolate the reaction product according to stage (i) as a solid and then to further react it. At least one freely selectable, radically homo- or copolymerizable monomer (b) can be reacted in the reaction according to stage (ii), the monomers already mentioned in the context of the explanation of the monomers (a) being suitable as monomers (b).

Monomer (b) can be the same or different from the monomer (a) used in step (i). Mixtures of two or more monomers can of course also be used as monomer (a) or monomer (b). In principle, the selection of the monomer (b) takes place according to the desired structure of the polymer produced in stage (ii) and thus depending on the intended use of this polymer.

The following monomers (b) are preferably used: N-vinylpyrrolidone, N-vinylimidazole, hydroxyethyl acrylate,

Hydroxyethyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, styrene or vinyl acetate.

The reaction in step (ii) is in principle carried out according to the usual conditions for free-radical polymerization, it being possible for suitable solvents to be present. In addition, stage (ii) is usually carried out under conditions as already described for stage (i) above. If appropriate, compounds of the formula I or II can be added again to carry out stage (ii).

Steps (i) and (ii) can be carried out separately from one another both spatially and temporally within the scope of the method described here, step (i) and then step (ii) then being carried out, of course. In addition, however, steps (i) and (ii) can also be carried out in succession in one reactor, ie first the compound of the formula (I) with at least one monomer (a) is wholly or partly dependent on the desired application or desired properties, implemented and then at least one monomer (b) added and radically polymerized or else from the start a monomer mixture comprising at least one monomer (a) and at least one monomer (b) and reacted with the compound (I). It is assumed that the compound (I) first reacts with the at least one monomer (a) and then the reaction product (A) formed therefrom also reacts with the monomer (b) above a certain molecular weight. In this regard, it should be noted in particular that the co (polymerisation) according to the invention can be continued after a possible interruption without renewed addition of initiator by heating to a temperature at which the macroinitiator formed according to the reaction product decomposes again after the first stage (i).

The polymer formed after the first stage (i) can be isolated or reheated in situ to start the (further) polymerization in stage (ii). Additional monomer (b) can be added directly. The monomer (b) can be the same or different from the monomer (a). You can also use monomer mixtures from the start. Step (ii) can be repeated any number of times.

Depending on the implementation, it is possible according to the invention to produce functionalized polymers, segmented polymers, block or multiblock and gradient (co) polymers, star-shaped (co) polymers, graft copolymers and branched and hyperbranched (co) polymers on the end groups.

As is evident from the above, the present invention also relates to the use of the copolymers described in the context of the present invention, which can be prepared by the process defined above, for the production of detergent preparations.

In the preparation of the copolymers, it is possible to provide block copolymers, which have, for example, a hydrophilic block, for example a (meth) acrylic acid block, a methyl (meth) acrylate block, a hydroxyethyl, in a simple manner using an easily accessible compound (I) (meth) acrylate block, or an N-vinylpyrrolidone block and a further, preferably hydrophobic polymer block, for example a block based on vinyl aromatic monomers, such as styrene or substituted styrenes, and non-aromatic vinyl compounds such as vinyl acetate, and higher (> C ₂ ) alkyl (meth) acrylates. In the context of the present invention, preference is given to using polymers of the following classification:

Poly (acrylic acid-b-styrene), poly (methyl methacrylate-b-styrene), poly (styrene-b-vinyl acetate), poly (methacrylic acid-b-hydroxyethyl acrylate), poly (methacrylic acid methyl ester-bN-vinyl pyrrolidone), poly (methacrylic acid methyl ester) -bN-vinyl-formamide), poly (methacrylic acid methyl ester-b-hydroxyethyl acrylate).

The following block copolymers should also be mentioned:

Poly (styrene-b-acrylic acid), poly (styrene-b-acrylic acid methyl ester), poly (styrene-b-methacrylic acid), poly (styrene-b-methacrylic acid methyl ester), poly (hydroxyethyl acrylate b-methacrylic acid), poly (N -vinylpyrrolidone-b-methyl acrylate), poly (N-vinylpyrrolidone-b-acrylic acid ethyl ester), poly (N-vinylpyrrolidone-b-methacrylic acid methyl ester), poly (N-vinylpyrrolidone-b-methacrylic acid ethyl ester), poly (N-vinylpyrrolidone) -b-styrene), poly (N-vinylpyrrolidone-b-vinyl acetate), poly (N-vinylpyrrolidone-b-α-methylstyrene), poly (N-vinylformamide-b-methacrylic acid methyl ester), poly (N-vinylformamide-b -Methacrylic acid ethyl ester), poly (N-vinylformamide-b-vinyl acetate), poly (N-vinylformamide-b-acrylic acid methyl ester) or poly (N-vinylformamide-b-acrylic acid ethyl ester). The following can also be used according to the present invention:

Poly (styrene-b-vinyl pyrrolidone) and poly (styrene-stat-acrylonitrile-vinyl pyrrolidone).

In the case of the above-mentioned block copolymers, the distribution of the blocks with regard to length and monomers involved in the block construction must be selected such that the block copolymers obtained are water-soluble or water-dispersible.

The block copolymers A described here can be used in amounts of 0.01 to 50% by weight in powder detergents. Their proportion of powdered textile detergents is usually 0.05 to about 25 or about 0.1 to about 15% by weight.

In a preferred embodiment, the detergent formulations according to the invention contain up to 49.99% by weight of additives. In addition to the polymers mentioned, the agents according to the invention also contain anionic and / or nonionic surfactants as well as structural substances which increase washing power or bind alkaline earth metal ions. Suitable further constituents are washing alkalis, neutral salts, bleaching agents, anti-graying agents, optical brighteners, enzymes and stabilizers as well as further auxiliaries and additives usually used in detergents.

Suitable anionic detergent active substances are those of the sulfonate or sulfate type, for example alkylbenzenesulfonates, in particular n-dodecylbenzenesulfonate, furthermore olefin sulfonates, α-sulfofatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.

Other compounds of this class that may be present in the detergents are the higher molecular weight sulfated partial ethers and

Partial esters of polyhydric alcohols such as the alkali salts of monoalkyl ethers. or the monofatty acid ester of glycerol monosulfuric acid ester or the 1,2-

Dioxypropansulfonsäure. Sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isothionates are also suitable. Other suitable anionic washing raw materials are

Alkaline soaps of fatty acids of natural or synthetic origin, e.g. the

Sodium soaps from coconut, palm kernel or tallow fatty acids.

The anionic raw materials for washing can be in the form of the sodium, potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine. If the anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 hydrocarbon atoms. In the compounds having an analiphatic hydrocarbon radical, the preferably unbranched alkyl chains contain on average 6 to 15 carbon atoms.

First come as nonionic surface-active detergent substances

Line polyglycol ether derivatives of alcohols, fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the

Contain hydrocarbon residue. Are particularly suitable Polyglycol ether derivatives in which the number of ethylene glycol ether groups is 5 to 15 and whose hydrocarbon residues are derived from straight-chain, primary alcohols with 12 to 18 carbon atoms or from alkylphenols with a straight-chain alkyl chain having 6 to 14 carbon atoms.

Further suitable nonionic washing raw materials are the water-soluble polyethylene oxide adducts with polypropylene glycol containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups,

Ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Nonionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated, can also be used.

Zwitterionic detergent active substances can also be used, such as alkyl betaines and alkyl sulfobetaines, e.g. the 3- (N, N-dimethyl-N-alkylanmonium) propane-l-sulfonate and 3- (TSr, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1 sulfonate.

Phosphates such as pentasodium triphosphate and its mixtures with its hydrolysis products, i.e. Sodium pyro- and orthophosphates or the acidic and neutral potassium pyrophosphates particularly suitable for the production of liquid detergents.

Other suitable framework substances are complexing aminopolycarboxylic acids. These include in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. The salts of diethylenetriamineopentaacetic acid and the higher homologs of the aminopolycarboxylic acid mentioned are also suitable. These homologs can be prepared, for example, by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to give carboxylic acid salts or by reacting polyethyleneimine with chloroacetic acid or bromoacetic acid salts in an alkaline medium. More suitable

Aminopolycarboxylic acids are poly (N-succinic acid) -ethyleneimine, poly- (N-tricarballylic acid) -ethyleneimine and poly- (N-butane-2,3,4-tricarboxylic acid) - ethyleneimine, which are obtainable analogously to the N-acetic acid derivatives. Furthermore, complexing polyphosphonic acid salts can be present, for example the alkali salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1, 1-disphosphonic acid, methylene diphosphonic acid, ethylene diphosphonic acid and salts of the higher homologues of the polyphophonic acids mentioned. Mixtures of the aforementioned complexing agents can also be used.

Of particular importance are the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions, which also include polymers containing carboxyl groups. Citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid are suitable. Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxydisuccinic acid and polyhydric alcohols partially or completely etherified with glycolic acid or hydroxy carboxylic acids, for example triscarboxymethylglycerol, biscarboxymethylglyceric acid and carboxymethylated or oxidized polysaccharides. The polymeric carboxylic acids with a molecular weight of at least 350 are also suitable in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly-α-hydroxyacrylic acid, polymaleic acid,

Polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.

Water-insoluble complexing agents can also be used. These include phosphorylated cellulose and graft polymers of acrylic acid or methacrylic acid on cellulose, which can be in the form of woven or non-woven fabrics. Also suitable are spatially crosslinked and thereby water-insoluble copolymers of acrylic, methacrylic, crotonic and maleic acids and other polymerizable polycarboxylic acids, optionally with other ethylenically unsaturated compounds in the form of the sodium or potassium salts as sequestering agents. These insoluble copolymers can be in the form of nonwovens, sponges or also in the form of finely ground, specifically light foams with an open-cell structure. Also suitable as water-insoluble builders are alkali aluminum silicates and alkali borosilicates, which may contain bound water and have a calcium binding capacity of at least 50 mg CaO / g active substance. These include in particular compounds of the formula (Na ₂ O) _x Al ₂ O ₃ (SiO ₂ ) where x is a number from 0.7 to 1.5 and y is a number from 1.3 to 4. Mixtures of the aforementioned water-soluble and water-insoluble builders can also be used.

Suitable washing alkalis are the carbonates, bicarbonates, borates and silicates of sodium and potassium, in particular sodium carbonate and sodium silicates with a ratio of Na ₂ O: SiO ₂ such as 1: 1 to 1: 3.5.

Oxygen-releasing bleaching agents such as alkali perborates, percarbonates, perpyrophosphates and persilicates and urea perhydrate are suitable as substances having a bleaching effect. Sodium perborate in anhydrous form or tetrahydrate is preferably used. To stabilize the per-compounds, the agents can contain magnesium silicate, for example in amounts of 3 to 20% by weight, based on the amount of perborate. Agents to be used for textile washing at temperatures below 70 ° C., so-called cold detergents, can contain bleach activators from the class of N- or O-acyl compounds, which react with hydrogen peroxide in aqueous solution to form peracids. Preferred bleach activators are tetraacetylmethylene diamine, tetraacetylethylene diamine and tetraacetylglycol uril. The powder particles consisting of the bleach activator or the per-compound can be coated with coating substances, such as water-soluble polymers or fatty acids, in order to avoid an interaction between the per-compound and the activator during storage.

Instead of the bleaching per-compounds and their mixtures with bleach activators, bleaches containing active chlorine, for example sodium hypochlorite, littaiim hypochlorite, sodium or potassium dichloroisocyanurate or trichloroisocyanuric acid, or else mixtures of alkali persulfates and alkali chlorides, which combine when used to form hypochlorite, can react with the detergents according to the invention become. This combination can take place during the manufacture of the detergents or also immediately before or during use. To avoid Losses can also be encased or granulated by the active chlorine compounds with inorganic or organic coating substances.

The detergents can also contain optical brighteners, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are for example salts of ^4,4-bis (-2 "-anilino-4" -morpholino-l, 3,5-triazinyl-6 "-amino) - stilbene-2,2'-disulfonic acid or compounds of similar structure, which carry a diethanolamino group, a methylamino group or a ß-memoxyethylamino group instead of the morpholino group Furthermore, brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1 - (- p-sulfonamidophenyl) -3- (p-chlorophenyl) -Δ ² -pyrazoline and compounds of the same structure which carry a carboxymethyl or acetylamino group instead of the sulfonamido group It is also possible to use substituted aminocoumarins, for example 4-methyl-7-dimethylamino- or 4-methyl-7-ylaminocoumarin Compounds 1 - (2-benzimidazolyl) -2- (1-hydroxy-ethyl-2-benzimidazolyl) - ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril are useful as brighteners for polyester and polyamide fibers 2,5-di- (2-benzoxazolyl) thio phen, 2- (2-benzoxazolyl) -naphtho- [3,4-n] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable. Brighteners of the substituted diphenylstyrile type may also be present. Mixtures of the aforementioned brighteners can also be used.

Suitable graying inhibitors are, in particular, carboxymethyl cellulose, methyl cellulose, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines, which have free carboxyl groups, betaine groups or sulfobetaine groups capable of salt formation, and polymers or copolymers of vinyl alcohol, vinyl pyrrolid, which are colloidally water-soluble in water and acrylonitrile.

The agents can also contain enzymes from the class of proteases, lipases and amylases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Neutral salts, in particular sodium sulfate, and bioeides, such as halogenated diphenylmethanes, salicylanilides, carbanilides and phenols, are suitable as further constituents. Liquid agents can also contain hydrotropic substances and solvents, such as alkali salts of benzene, toluene or xylene sulfonic acid, urea, glycerin, polyglycerin, di- or triglycol, polyethylene glycol, ethanol, i-propanol and ether alcohols.

If necessary, known foam inhibitors, such as saturated fatty acids and their alkali soaps with 20 to 24 carbon atoms, trialkylmelamines, hydrocarbons and silicones, may also be present.

The quantitative composition of the detergents according to the invention can vary within wide limits, preferably within the following (in percent by weight):

0.1-10% preferably 0.2-5% polymer according to the invention 0.5-30%, preferably 1-20% soap and / or sulfate or sulfonate surfactant, 0.5-30%, preferably 1st - 20% nonionic surfactant, 0 - 60%, preferably 5 - 50% builders,

0 - 25%, washing alkalis,

0 - 30%, preferably 10 - 25% of oxygen-releasing bleaching agents, in particular Na perborate and its combination with bleach activators and stabilizers, 0 - 3%, preferably 0.5 - 2% of anti-graying agents

Substances, 0-1%, optical brighteners, dyes and fragrances, and antimicrobial substances, 0-3%, preferably 0.2-2%, of foam inhibitors.

The present invention also relates to a method for producing a detergent substance according to one of claims 1 to 6, characterized in that at least 0.01 to 50% by weight of a block copolymer A with a molecular weight of more than 1000, which can be prepared by a process comprising the following steps (i) and (ii):

(i) reaction under radical conditions of a reaction mixture comprising at least one radical-convertible monomer (a) in the presence of at least one radical of the formula (III)

• C -R2

I (III)

R3

where R 1 to R ₃ each independently of one another are hydrogen, methyl or a radical-stabilizing and / or sterically demanding group selected from an unsubstituted or substituted, linear or branched-chain alkyl having two or more carbon atoms,

Cycloalkyl, alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom (shark), a substituted or unsubstituted, linear or branched chain alkenyl or alkynyl group, -C ( O) R ₅ , -

C (O) OR ₅ , -CR ₅ R _Ö -OR ₇ , -OC (O) R ₅ , -CN, -O-CN, -S-CN, -O- C = NR ₅ , -SC = NR ₅ , -O-CR ₅ R ₆ -CR ₇ R ₈ NR ₉ R ₁₀ , -N = C = O, -C = NR ₅ , - CR ₅ R ₆ -Hal, -C (S) R ₅ , -CR ₅ Rs-P (O) R ₇ R ₈ . -CRsRg-PR ^, -CR ₅ R ₆ -NR ₇ R ₈ , -CR ₅ R ₆ (OR ₇ ) (OR ₈ ), -CR ₅ R ₆ (OR ₇ ) (NR ₈ ), -CR ₅ R ₆ (NR ₇ ) (NR ₈ ), an acid anhydride, acetal or

Ketal group, -SO ₂ R ₅ , an amidine group -NR ₅ C (S) NR ₆ , - NR ₅ C (S) -OR ₆ , -N = C = S, -NO2, -C = N-OH, -N (R ₅ ) = NR ₆ , -PR ₅ R ₅ R ₇ , -OSiR ₅ ReR ₇ , or -SiRsR _ö Rz, where R ₅ to R _{10 are} each independently defined as Ri to t, or two of the radicals R 1 to R _{4 form} a C to C ₇ ring which in turn can be substituted or unsubstituted and can optionally contain one or more hetero atoms, with the proviso that at least two of the radicals R 1 to R _{3 are} a radical-stabilizing and / or sterically demanding group, as defined above, and (ii) reaction of the reaction product obtained in step (i) under radical conditions in the presence of at least one radical homo - or copolymerizable monomers (b) and

b) 50 to 99.99% by weight of an anionic, cationic or nonionic surfactant with a molecular weight of less than 1000

be mixed.

The present invention also relates to the use of a block copolymer A with a molecular weight of more than 1000, which can be prepared by means of a process described above comprising steps (i) and (ii), for the production of detergent preparations.

Examples:

100 g of N-vinylpyrrolidone, 0.8 g of 1,1-diphenylethene and 0.49 g of azodiisobutyronitrile are heated to 85 ° C. for 6 hours. Then 5 g of styrene are added and the mixture is heated at 110 ° C. for a further 6 h without stirring. A solid, water-soluble substance is obtained.

Application tests:

The influence of a polymer prepared according to the invention on the stability of liquid detergents was shown in the following

Liquid detergent composition tested:

30 parts of adduct of 7 moles of ethylene oxide from 1 mole of C ₁₃ / C ₁₅ -

oxo alcohol

8 parts of dodecylbenzenesulfonic acid, 15 parts of coconut fatty acid

5 parts of monoethanolamine 3 parts of polypropylene glycol with a molecular weight of 600 7 parts of 1,2-propylene glycol and 15 parts of a modified polycarboxylate (reaction product from

Maleic anhydride-isobutene copolymer with 8-fold ethoxylated C ₂ / C ₄ oxo alcohol according to EP-A 0 367 049)

I part of the polymer acting as a dye transfer inhibitor 16 parts of water

The prior art polymer dye inhibitor polymer in the liquid detergent formulation described above was tested for polyvinyl pyrrolidone with a K value of 17.

According to the invention, the poly (N-vinylpyrrolidone-b-styrene) prepared according to Example 1 was used as the dye transfer inhibitor.

The effectiveness of polymers prepared according to the invention with regard to dye transfer inhibition was determined by washing tests in which the dye was added to the liquor in dissolved form. Basilen brown E-4-R (C.J. Reaktivbraun 32) was used as the dye and Persil Color liquid was used as the detergent, to which 1% of the polymers shown in Table 2 was added, based on the amount of detergent. The washing conditions are summarized as dye inhibition.

Table 1:

Table 2: Dye surveying

As can be seen from Table 2, the addition of 1% of one of the polymers to be used according to the invention prevents the dye transfer to cotton and polyester / cotton in a very pronounced manner. In addition, the polymer has a more color transfer inhibiting effect at the same concentration than commonly known color transfer inhibiting polymers.

Claims

claims

Wash-active preparation, at least containing

a) 0.01 to 50% by weight of a water-soluble or water-dispersible block copolymer A with a molecular weight of more than 1000, which can be prepared by a process comprising the following steps (i) and (ii):

• C R2 (III)

R3

where R 1 to R ₃ each independently of one another are hydrogen, methyl or a radical-stabilizing and / or sterically demanding group selected from an unsubstituted or substituted, linear or branched-chain alkyl having two or more carbon atoms, cycloalkyl, alcohol, ether, Polyether, amine, aralkyl, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom (shark), a substituted or unsubstituted, linear or branched chain alkenyl or alkynyl group, -C (O) R ₅ , - C (O ) OR ₅ , -CRsRe-OR _? , -OC (O) R ₅ , -CN, -O-CN, -S-CN, - OC = NR ₅ , -SC = NR ₅ , -N = C = O, - C = NR ₅ , -CRsRe-Hal, -C (S) R ₅ , -CR ₅ Re-P (O) R ₇ R ₈ , -CR ₅ Re-

-CRsRs-NR ^ s, -CR ₅ R ₆ (OR ₇ ) (OR ₈ ), -CR ₅ R ₆ (OR ₇ ) (NR ₈ ), -CR ₅ R ₆ (NR ₇ ) (NR ₈ ), an acid anhydride, acetal or ketal group, -SO ₂ R ₅ , an amidine group -NR ₅ C (S) NRg, - NR ₅ C (S) -ORe, -N = C = S, -NO2, -C = N-OH, -N (R ₅ ) = NR _Ö , -

PR ₅ R ₆ R ₇ , -OSiR ₅ R ₆ R ₇ , or -SiR R ₆ R ₇ , where R ₅ to Rio are each independently defined as Ri to R_ι, or two of the radicals Ri to R _{4 are} C to form a C ₇ ring which in turn may be substituted or unsubstituted and may optionally contain one or more hetero atoms, with the proviso that at least two of the radicals R 1 to R _{3 form} a radical-stabilizing and / or sterically demanding group, as defined above , and (ii) reaction of the reaction product obtained in step (i) under radical conditions in

Presence of at least one radically homo- or copolymerizable monomer (b) and

b) 50 to 99.99 wt .-% of an anionic, cationic, zwitterionic or nonionic surfactant with a

Molecular weight less than 1000.

2. Wash-active preparation according spoke 1, characterized in that it contains up to 49.99 wt .-% additives.

3. active washing preparation according to claim 1 or 2, characterized in that builder substances are included as additives.

4. wash-active preparation according to one of claims 1 to 3, characterized in that it contains anionic and nonionic surfactants as surfactants.

5. active detergent preparation according to one of claims 1 to 4, characterized in that the block copolymer A has 2 to 6 blocks.

6. active detergent preparation according to one of claims 1 to 5, characterized in that at least one block in the block copolymer A has a polyvinyl pyrrolidone structure.

7. A method for producing a detergent preparation according to one of claims 1 to 6, characterized in that at least

(i) reaction under radical conditions of a

Reaction mixture comprising at least one radically convertible monomer (a) in

Presence of at least one radical of the formula (III)

• C R2 (Tu)

j * 3

where Ri to R _{3 are} each independently

Hydrogen, methyl or a radical stabilizing and / or sterically demanding group selected from an unsubstituted or substituted, linear or branched chain alkyl with two or more C-

Atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom (shark), a substituted or unsubstituted, linear or branched chain alkenyl or alkynyl group, C (O) R ₅ , -C (O) OR ₅ , -CR ₅ R ₆ -OR ₇ , -OC (O) R ₅ , - CN, -O-CN, -S-CN, -OC = NR ₅ , -SC = NR ₅ , -O- CR ₅ R ₆ -CR ₇ R ₈ NR ₉ Rιo, -N = C = O, -C = NR ₅ , -CR ₅ RÖ- Hal, -C (S) R ₅ , -CR ₅ R ₆ -P (O) R ₇ R ₈ , -CR ₅ R, ₃ -PR ₇ R ₈ , -CR ₅ R ₅ -NR ₇ R ₈ , -CR ₅ R ₆ (OR ₇ ) (OR ₈ ), CR ₅ R ₆ (OR ₇ ) (NR ₈ ),

-CR ₅ R, ₅ (NR ₇ ) (NR ₈ ), an acid anhydride, acetal or ketal group, -SO ₂ R ₅ , an amidine group - NR ₅ C (S) NR ₆ , -NR ₅ C (S) - OR ₆ , -N = C = S, -NO2, - C = N-OH, -N (R _S ) = NR6, -PRsReR ?, -OSiRsR _ö R- ₇ , or -SiR ₅ ReR ₇ , where R ₅ to R _{10 are} each independently defined as Ri to _t , or two of the radicals Ri to R ₄ . form a C ₄ - to C-ring which in turn may be substituted or unsubstituted and optionally contain one or more hetero atoms, with the proviso that at least two of the radicals R 1 to R _{3 form} a radical-stabilizing and / or sterically demanding group, such as defined above are and (ii) implementation of the "obtained in step (i)"

Implementation product under radical

Conditions in the presence of at least one radically homo- or copolymerizable monomer (b) and

b) 50 to 99.99% by weight of an anionic, cationic, zwitterionic or nonionic surfactant with a molecular weight of less than 1000

be mixed.

8. Use of a water-soluble or water-dispersible block copolymer A with a molecular weight of more than 1000, which can be prepared by a process comprising the following steps (i) and (ii): Reaction under radical conditions of a reaction mixture comprising at least one radical-convertible monomer (a) in the presence of at least one radical of the formula (III)

• c - R2 _(II i)

R3

where R 1 to R ₃ each independently of one another are hydrogen, methyl or a radical-stabilizing and / or sterically demanding group selected from an unsubstituted or substituted, linear or branched-chain alkyl having two or more carbon atoms, cycloalkyl, alcohol, ether, Polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocychic or olefinic hydrocarbon, a halogen atom (shark), a substituted or unsubstituted, linear or branched chain alkenyl or alkynyl group, -C (O) R ₅ , - C (O ) OR ₅ , -CR _S R _Ö -OR ?, -OC (O) R ₅ , -CN, -O-CN, -S-CN, -O- C = NR ₅ , -SC = NR ₅ , -O -CR _S R ₆ -CR ₇ R ₈ NR ₉ R ₁₀ , -N = C = O, -C = NR ₅ , - CRgRe-Hal, -C (S) R ₅ , -CR ₅ Re-P (O) R ₇ R ₈ , -CR ₅ R ₆ -PR ₇ R ₈ , -CR ₅ R6-NR ₇ R ₈ , -CR ₅ R ₆ (OR ₇ ) (OR ₈ ), -CR ₅ R ₆ (OR ₇ ) ( NR ₈ ),

-CR5Rö (NR ₇ ) NR ₈ ), an acid anhydride, acetal or ketal group, -SO ₂ R ₅ , an amidine group -NR ₅ C (S) NR ₆ , - NR ₅ C (S) -OR ₆ , -N = C = S, -NO2, -C = N-OH, -N (R ₅ ) = NR ₆ , -PRsReR ?, -OSiR ₅ RöR ₇ , or -SiRsR _θ R _/ , where R ₅ to R ₁₀ are each independently defined as Ri to ₄ , or two of the

Ri to R _{4 form} a C ₄ to C ₇ ring which in turn can be substituted or unsubstituted and optionally contain one or more hetero atoms, with the proviso that at least two of the Ri to R ₃ radicals stabilize a radical and / or sterically demanding group, as defined above, and (ii) reaction of the reaction product obtained in step (i) under free radical conditions in the presence of at least one free radically homo- or copolymerizable monomer (b)

in detergent preparations.