WO2002046518A2

WO2002046518A2 - Reagent-modified particulate polymers for treatment of the surface of textile and non-textile materials

Info

Publication number: WO2002046518A2
Application number: PCT/EP2001/014172
Authority: WO
Inventors: Christoph Hamers; Dieter Boeckh; Jürgen Detering; Bernhard Schlarb
Original assignee: Basf Aktiengesellschaft
Priority date: 2000-12-05
Filing date: 2001-12-04
Publication date: 2002-06-13
Also published as: EP1343934A2; CN1484719A; JP2004515660A; DE10060373A1; MXPA03004964A; CA2430682A1; US20040025262A1; AU2002229606A1; WO2002046518A3; BR0115945A

Abstract

The invention relates to a method for the treatment of the surface of textile and non-textile materials, whereby reagent-modified, particulate polymers with a particle size of from 10 nm to 100 νm are applied to the surface of the materials from an aqueous dispersion and the materials dried.

Description

Reactively modified, particle-shaped polymers for the treatment of the surfaces of textile and non-textile materials

The invention relates to a process for treating the surfaces of textile and non-textile materials with reactively modified particulate polymers, the use of the reactively modified, particulate polymers, agents for anti-itching and detergents, dishwashing detergents, care and textile treatment agent formulations containing the reactively modified particulate polymers.

Textiles containing cellulose are easy to care for, for example, by treatment with condensation products made from urea, glyoxal and formaldehyde. The equipment takes place during the manufacture of the textile materials. Other additives such as plasticizing compounds are often used in the finishing. The textiles finished in this way have the advantage over the untreated cellulose textiles after the washing process that they have fewer creases and folds, are easier to iron and are softer and smoother.

A method for pretreating textile materials is known from WO 98/04772, in which a mixture of a polycarboxylic acid and a cationic plasticizer is applied to the textile materials. Anti-crease is achieved.

EP-A 0 978 556 describes a mixture of a plasticizer and a crosslinking component with cationic properties as an agent for providing textiles with anti-crease and wrinkle protection, and a method for anti-wrinkle finishing of textiles.

Washing, rinsing, cleaning and maintenance processes in aqueous media are usually carried out in a highly diluted liquor, the ingredients of the formulation used generally not remaining on the substrate, but rather being disposed of with the waste water. A sustainable modification of the The surface of cellulose-containing materials with dispersed particles in the processes mentioned below is only unsatisfactory.

No. 5,476,660 discloses the principle of using polymeric retention agents for cationic or zwitterionic dispersions of polystyrene or wax, which contain an active substance embedded in the dispersed particles. These dispersed particles act as carrier particles because they adhere to the treated surface and there an active substance, e.g. when used in formulations containing surfactants.

It is known from US Pat. No. 3,993,830 to apply a non-permanent finish for dirt repellency to a textile material by treating the textile material with a dilute aqueous solution which contains a polycarboxylate and a water-soluble salt of a polyvalent metal. Water-soluble copolymers of ethylenically unsaturated monocarboxylic acids and alkyl acrylates are mentioned as preferred polycarboxylates. The blends are released in the washing of household washing items in the washing machine.

The object of the present invention is to provide a further method for modifying surfaces of textile and non-textile materials.

In particular, it is the object of the present invention to provide a method for the anti-crease treatment of cellulose-containing textiles.

Another object of the present invention is to provide a method for improving the detachment of dirt from textile and non-textile surfaces.

The object is achieved according to the invention by a process for treating textile materials, in which reactively modified, particulate polymers having a particle size of 10 nm to 100 μm are applied from an aqueous dispersion to the surface of the textile materials and the textile materials are dried.

The object is further achieved by using the reactively modified, particulate polymers as a surface-modifying additive for rinsing, care or detergents and by detergent, care product and textile treatment agent formulations containing the particulate polymers.

For the purposes of the invention, reactively modified polymers are particulate polymers which contain reactive, crosslinking groups. The reactively modified polymers can contain anionic and / or cationic monomers in copolymerized form and have anionic, cationic or amphoteric protective colloids or emulsifiers on their surface. The reactively modified polymers can contain monomers containing reactive groups in copolymerized form and / or have protective colloids or emulsifiers which contain reactive groups on their surface. Reactively modified polymers which have an anionic character, ie which contain anionic groups in copolymerized form and / or are dispersed with anionic protective colloids or emulsifiers, can have cationic polymers coated on their surface.

The reactive groups can also have a crosslinking action, ie only have a crosslinking effect when the treated textile surfaces are heated or dried.

The reactively modified, particulate polymers can be obtained by copolymerization of ethylenically unsaturated monomers which do not contain crosslinking reactive groups with ethylenically unsaturated monomers which contain such crosslinking reactive groups. However, the reactive groups can also be introduced into the polymer by coating the surfaces of the polymer particles with colloids which have crosslinking reactive groups.

According to one embodiment of the invention, the reactively modified polymers used according to the invention can be obtained by copolymerizing ethylenically unsaturated monomers containing no reactive groups with ethylenically unsaturated monomers containing reactive groups.

Suitable monomers containing no reactive groups are, for example, alkyl esters of C ₃ -C ₅ - monoethylenically unsaturated carboxylic acids with monohydric C ₁ -C ₂₂ alcohols, hydroxyalkyl esters of C ₃ - C ₅ - monoethylenically unsaturated carboxylic acids with dihydric C ₂ -C ₄ alcohols Vinyl esters of saturated CrC ₁₈ carboxylic acids, ethylene, propylene, isobutylene, C ₄ -C ₂ -alpha olefins, butadiene, styrene, alpha-methylstyrene, Acrylonitrile, methacrylonitrile, tetrafluoroethylene, vinylidene fluoride, fluoroethylene, chlorotrifluoroethylene, hexafluoropropene or mixtures thereof.

Monomers which are preferably used are methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate,

Hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate, vinyl acetate, vinyl propionate, styrene, ethylene, propylene, butylene, isobutene, diisobutene and tetrafluoroethylene, particularly preferred monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, styrene, methyl methacrylate and vinyl acetate.

Suitable reactive, crosslinking groups are, for example, azetidinium, glycidyl ether, halohydrin, carboxylic anhydride, carboxylic acid chloride, isocyanate, vinyl sulfone, N-methylol, aldehyde and imine groups.

Preferred, reactive group-containing unsaturated monomers are N-methylol- (meth) acrylamide, glycidyl methacrylate, methacryloxypropyltrimethylsilane, vinyl trimethoxysilane, m-isopropenylbenzyl isocyanate, acrolein, isobutoxymethylacrylamide, isobutoxymethylacrylamide, hydroxymethylethyl allyl amyllamyl acrylate, hydroxymethylethyl allyl amylamyl acrylate, hydroxymethyl methyl allyl amylamyl acrylate, hydroxymethyl methyl diacyl amyl amyl acrylate, -acryloxymethylene diamine, ga-methylacryloxypropyltrimethoxysilane, methacryloxyethoxytrimethylsilane,

Epithiopropyl methacrylate, vinyl chloride, 2-chloroethyl acrylate, 4-chlorobutyl acrylate, 3-chloro-2-hydroxypropyl acrylate, methyl l- (chloromethyl) acrylate, 2- (bromomethyl) acrylonitrile, 2- (chloromethyl) acrylamide, 6-bromo-2-napthylenyl acrylate , 2- (4-chloro-2-nitroanilino) ethyl acrylate, 6-chloro-5- (trichloromethyl) -2-norbony acrylate, 3-chloro-2- [(dimethylphosphinyl) oxy] propyl acrylate, 3-chloro-2 - [( l-oxo-3-phenyl-2-propenyl) oxy] propyl methacrylate, 2-phenylallyl bromide, p-chloromethylstyrene, vinyl monochloroacetate and 2- (4-ethoxyphenyl) 2-oxazolinylmethacrylate.

The reactively modified polymers used according to the invention can be prepared by the processes of solution, precipitation, suspension or emulsion polymerization known per se, as described, for example, in P. Lovell and MS El-Aaser, Emulsion Polymerization and Emulsion Polymers, Wiley, New York, 1997. The reactively modified, particulate polymers used according to the invention are preferably obtained by emulsion polymerization, the process being carried out in an aqueous medium. The polymerization is carried out in the presence of polymerization initiators, which decompose either thermally or photochemically, or redox initiators. Of the thermally disintegrating polymerization initiators, preference is given to those which disintegrate between 20 and 180 ° C., in particular between 50 and 90 ° C.

Preferred polymerization initiators for emulsion polymerization are water-soluble organic peroxides such as peresters, percarbonates, perketals, hydroperoxides, inorganic peroxides such as HO ₂ , salts of peroxosulfuric acid and peroxodisulfuric acid, azo compounds, boralkyl compounds and homolytically decomposing hydrocarbons.

The polymerization initiators, which are used in amounts between 0.01 and 15% by weight, based on the monomers, can be used individually or in combination.

Dispersion aids are generally used in the preparation of the polymers by emulsion polymerization.

Water-soluble, high molecular weight organic compounds with polar groups, such as polyvinylpyrrolidone, copolymers of vinyl propionate or

-acetate and vinyl pyrrolidone, expensive saponified copolymers of an acrylic ester and

Acrylonitrile, polyvinyl alcohols with different residual acetate content, cellulose ether,

Gelatin, block copolymers, modified starch, low molecular weight, carboxyl and / or

Polymers containing sulfonic acid groups or mixtures thereof are used. Suitable natural protective colloids are water-soluble proteins, partially degraded proteins, water-soluble cellulose ethers, native starches, degraded starches and / or chemically modified starches. Water-soluble cellulose esters are, for example

Hydroxyethyl cellulose and methyl cellulose. These come in as natural strengths

Consideration that can be obtained by heating in an aqueous medium to temperatures above the gelatinization temperature of the starches. Dismantled are also suitable

Starches that can be obtained through hydrolytic, oxidative or enzymatic degradation. Particularly preferred protective colloids are polyvinyl alcohols with a residual acetate content of 0 to 39, in particular 5 to 39 mol% and vinylpyrrolidone / vinyl propionate copolymers with a vinyl ester content of up to 35, in particular 5 to 30% by weight.

Nonionic or ionic emulsifiers and mixtures thereof can also be used as dispersants. Preferred emulsifiers are optionally ethoxylated or propoxylated longer chain alkanols or alkylphenols with different degrees of ethoxylation or propoxylation, e.g. Adducts with 0 to 50 mol of alkylene oxide, and their neutralized, sulfated, sulfonated or phosphated derivatives. Neutralized dialkyl sulfosuccinic acid esters or alkyl diphenyl oxide disulfonates are particularly suitable.

₂₅ alkylamines, N, N-Dimemyl-N- (C ₇ -C ₂₅ hydroxyalkyl) ammonium salts, quaternized with alkylating agents of mono- and di- (C ₇ to C ₂₅ -C - are also suitable cationic emulsifiers based on C ₇ -alkyl) dimethylammonium compounds, ester quats, such as quaternary esterified mono-, di- or trialkanolamines, which are esterified with C ₇ -C ₂₂ -carboxylic acids, and imidazoline quats, such as 1-alkylimidazolinium salts.

The polymers have, for example, molecular weights of 1,000 to 2 million, preferably 5,000 to 500,000, and the molecular weights of the polymers are usually in the range of 10,000 to 150,000.

To limit the molar masses of the polymers, customary regulators can be added during the polymerization. Examples of typical regulators are mercapto compounds such as mercaptoethanol or thioglycolic acid.

In order to increase the density of the reactive groups on the surface of the polymer particles, the monomers containing the reactive groups can be added gradually and separately from the other monomers. It is preferred to add the majority of the monomers containing the reactive groups only towards the end of the total feed time of all monomers. In a variant of the preparation of the polymers used according to the invention, 70% of the monomers containing the reactive groups are added in the last third of the total feed time. In addition to the polymerization processes mentioned, other processes for the production of the particulate polymers used according to the invention are also suitable. So you can z. B. particulate polymers fail by lowering the solubility of the polymers dissolved in a solvent. For example, a copolymer containing an acidic group can be dissolved in a suitable water-miscible solvent and the solution can be metered into an excess of water such that the pH in the initial charge is at least 1 lower than the equivalent pH of the copolymer. Equivalence pH is the pH at which 50% of the acidic groups of the copolymer are neutralized. In this process it may be necessary to use a dispersing aid, pH regulators and / or salts in order to obtain stable, finely divided aqueous dispersions.

The reactively modified polymers used according to the invention have a particle size of 10 nm to 100 μm, preferably 30 nm to 3 μm, in particular 50 nm to 800 nm.

The reactively modified polymers used according to the invention can have anionic, cationic, amphoteric or nonionic character.

Reactively modified polymers with an anionic character can be obtained by copolymerizing anionic monomers such as acrylic acid, methacrylic acid, styrenesulfonic acid, acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid and maleic acid, maleic acid semiesters with -Cs-alkanols and / or their salts, in the presence of emulsifiers and protective colloids can be worked. Anionic monomers are also understood here to mean monomers with acidic groups which can be converted into their salts, even if these are not present in ionic form during the polymerization.

The anionic character of the polymers can also be achieved by carrying out the copolymerization in the presence of anionic protective colloids and / or anionic emulsifiers.

However, the anionic character of the polymers can also be achieved by emulsifying or dispersing the finished polymers in the presence of anionic protective colloids and / or anionic emulsifiers. Reactively modified polymers with a cationic character can be obtained by copolymerizing cationic monomers, it being possible to work in the presence of emulsifiers and protective colloids. Cationic monomers here also mean monomers with basic groups which can be converted into their salts, even if these are not present in ionic form during the polymerization. Suitable cationic monomers are nitrogen-containing, basic ethylenically unsaturated monomers in the form of the free bases, the salts with organic or inorganic acids or in quaternized form. Suitable nitrogen-containing, basic ethylenically unsaturated compounds are, for example, N, N'-dialkylaminoalkyl (meth) acrylates, for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylate,

Dimethylaminoneopentyl. Further suitable basic monomers of this group are N, N'-dialkylaminoalkyl (meth) acrylamides, for example NjN'-di- -Cralkylamino-C -C ₆ -alkyl (meth) acrylamides, such as dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, dipropylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamethylamylamylamylamylamylamylamylamylamylamethylamylamylamylamylamylamylamylamylamylamylaminoamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamylamino, , Dimethylaminopropylacrylamid, Dimethylaminopropylmethacrylamid, Diethylaminopropylacrylamid, Diethylaminopropylmethacrylamid, Dimethylaminoneopentylacrylamid, Dimethylaminoneopentylmethacrylamid and Dialkylaminobutylacrylamid.

Other suitable monomers in this group are 4-vinylpyridine, 2-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole and / or diallyl (di) alkylamines in which the alkyl group has 1 to 12 carbon atoms. The above-mentioned basic monomers are used in the copolymerization in the form of the free bases, the salts with organic or inorganic acids or in quaternized form. For salt formation, for example, carboxylic acids with 1 to 7 carbon atoms are suitable, for example formic acid, acetic acid or propionic acid, benzenesulfonic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid or inorganic acids such as hydrohalic acids, for example hydrochloric acid or hydrobromic acid. The basic monomers exemplified above can also be used in quaternized form. For quaternization, for example, alkyl halides with 1 to 18 carbon atoms in the Alkyl group, for example methyl chloride, methyl bromide, methyl iodide, ethyl chloride, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, in particular benzyl chloride in benzyl bromide. The quaternization of the nitrogen-containing basic monomers can also be carried out by reacting these compounds with dialkyl sulfates, in particular diethyl sulfate or dimethyl sulfate. Examples of monomers of this group are quaternized trimethylammonium ethyl methacrylate chloride, and Dimethylethylammoniumethylmethacrylatethylsulfat Dimethylethylammom ^{'environmentally} ethylmethacrylamidethylsulfat, 3-methyl-1 -vinyl-imidazolinimchlorid.

The cationic character of the polymers can also be achieved by carrying out the copolymerization in the presence of cationic protective colloids and / or cationic emulsifiers.

However, the cationic character of the polymers mentioned can also be achieved by emulsifying or dispersing the finished polymers in the presence of cationic protective colloids and / or cationic emulsifiers.

An overview of a selection of suitable cationic surfactants can be found in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 1999, Electronic Release, Chapter "Surfactants", Chapter 8, Cationic Sürfactants.

Reactively modified polymers with an amphoteric character can be obtained by copolymerizing both cationic and anionic monomers. Suitable monomers are, for example, the aforementioned cationic and anionic monomers.

The amphoteric character of the polymers can also be achieved by carrying out the copolymerization in the presence of amphoteric protective colloids and / or amphoteric emulsifiers.

However, the amphoteric character of the polymers can also be achieved by emulsifying or dispersing the finished polymers in the presence of amphoteric protective colloids and / or amphoteric emulsifiers.

Reactively modified polymers can be obtained, for example, by copolymerization of (a) 40 to 99.9% by weight, preferably 50 to 90% by weight, particularly preferably 60 to 75% by weight of at least one sparingly water-soluble or water-insoluble nonionic monomer,

(b) 0 to 60% by weight, preferably 1 to 55% by weight, particularly preferably 5 to 50% by weight, in particular 15 to 40% by weight, of monomers containing carboxyl groups or salts thereof,

(c) 0 to 25% by weight, preferably 0 to 15% by weight, of monomers containing sulfonic acid and / or phosphonic acid groups or their salts,

(d) 0 to 30% by weight, preferably 0 to 15% by weight, of cationic monomers,

(e) 0 to 55% by weight, preferably 0 to 40% by weight, of water-soluble nonionic monomers,

(f) 0 to 30% by weight, preferably 0 to 10% by weight, of polyethylenically unsaturated monomers, and

(g) 0.1 to 30% by weight, preferably 0.25 to 15% by weight, particularly preferably 0.5 to 10% by weight, of at least one reactive, crosslinking group-containing ethylenically unsaturated monomer.

Polymers which contain at least one anionic monomer b) or c) in copolymerized form can be used without additional anionic emulsifiers or protective colloids. Polymers that contain less than 0.5% anionic monomers are mostly used together with at least one anionic emulsifier or protective colloid.

Monomers a) which are preferably used are methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate, vinyl acetate, vinyl propionate, styrene, ethylene, ethylene, isyrene, ethylene, ethylene, isyrene, ethylene, styrene, ethylene, ethylene and tetrafluoroethylene, particularly preferred monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, styrene, methyl methacrylate and vinyl acetate. Monomers b) normally used are acrylic acid, methacrylic acid, maleic acid or maleic acid semiesters with Cj-Cs-alkanols.

Suitable monomers c) are, for example, acrylamido-2-methylpropanesulfonic acid, ninylsulfonic acid, methallylsulfonic acid, and their alkali and ammonium salts.

Suitable monomers d) are, for example, dimethylaminoethyl methacrylate, dimethyl laminopropylacrylamide, 1-vinylimidazole, 3-methyl-1-vinylimidazolinium chloride and 4-vinyl pyridine.

Suitable monomers e) are, for example, acrylamide, methacrylamide, Ν-vinylformamide, Ν-vinyl acetamide, Ν-vinylpyrrolidone, Ν-vinyloxazolidone,

Methyl polyglycol acrylates, methyl polyglycol methacrylates, methyl polyglycol acrylamides and vinyl caprolactam.

Suitable polyunsaturated monomers f) are, for example, acrylic esters, methacrylic esters, allyl ethers and vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols can be completely or partially etherified or esterified. Crosslinkers contain at least two ethylenically unsaturated groups. Examples are butanediol diacrylate, hexanediol diacrylate and trimethylolpropane triacrylate. Further unsaturated monomers e) are e.g. Allyl esters of unsaturated carboxylic acids, divinylbenzene, methylenebisacrylamide and divinylurea.

Preferred reactive Gmppen containing unsaturated monomer g), which have a crosslinking effect but mostly post-crosslinking are Ν-methylol (meth) acrylamide, glycidyl methacrylate, methacryloxypropyl-trimethylsilane, vinyltrimethoxysilane, m- isopropenyl benzyl isocyanate, acrolein, isobutoxymethyl acrylamide, hydroxymethyl diacetone acrylamide, allyl-N-methylolcarbamat , N-formyl-N'-acryloxymethylene diamine, gamma-methylacryloxypropyltrimethoxy silane, methacryloxyethoxytrimethylsilane,

Epithiopropyl methacrylate, vinyl chloride, 2-chloroethyl acrylate, 4-chlorobutyl acrylate, 3-chloro-2-hydroxypropyl acrylate, methyl l- (chloromethyl) acrylate, 2- (bromomethyl) acrylonitrile, 2- (chloromethyl) acrylamide, 6-bromo-2-napthylenyl acrylate , 2- (4-chloro-2-nitroanilino) ethyl acrylate, 6-chloro-5- (trichloromethyl) -2-norbony acrylate, 3-chloro-2- [(dimethylphosphinyl) oxy] propyl acrylate, 3-chloro-2 - [( l-oxo-3-phenyl-2- propenyl) oxy] propyl methacrylate, 2-phenylallyl bromide, p-chloromethylstyrene, vinyl monochloroacetate and 2- (4-ethoxyphenyl) 2-oxazolinylmethacrylate.

In one embodiment of the invention, reactively modified, particulate polymers are used which have an anionic character, that is to say contain anionic groups in copolymerized form and / or are dispersed with anionic protective colloids or emulsifiers, and which have coating on their surface with cationic polymers.

These cationically modified, reactively modified, particulate polymers can be obtained by covering the surface of the anionically dispersed, particulate polymers with cationic polymers. All natural or synthetic cationic polymers which contain amino and / or ammonium groups and are water-soluble can be used as cationic polymers. Examples of such cationic polymers are polymers containing vinylamine units, polymers containing vinylimidazole units, polymers containing quaternary vinylimidazole units, condensates of imidazole and epichlorohydrin, crosslinked polyamidoamines, crosslinked polyamidoamines grafted with ethyleneimine, polyethylenimines, alkoxylated polyethyleneimines, crosslinked polyethylenimineimines, amidated polyethylenimines, amine Amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines,

Polydimethyldi-dlylammonium chlorides, polymers containing basic (meth) acrylamide or ester units, polymers containing basic quaternary (meth) acrylamide or ester units, and / or lysine condensates.

Cationic polymers are also understood to mean amphoteric polymers which have a net cationic charge, i.e. the polymers contain both anionic and cationic monomers copolymerized, but the molar proportion of the cationic units contained in the polymer is greater than that of the anionic units.

Polymers containing vinylamine units are prepared, for example, from open-chain N-vinylcarboxamides of the formula (I)

from in which R ¹ and R ^{2 may be the} same or different and represent hydrogen and - to C ₆ alkyl. Suitable monomers are, for example, N-vinylformamide (R ^{1 =} R ² = H in formula I) N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethylacetamide, N -Vinyl-N-methylpropionamide and N-ninylpropionamide. To prepare the polymers, the monomers mentioned can be polymerized either alone, as a mixture with one another or together with other monoethylenically unsaturated monomers. Homopolymers or copolymers of Ν-vinylformamide are preferably used as starting materials. Polymers containing vinylamine units are known, for example, from US Pat. No. 4,421,602, EP-A-0 216 387 and EP-A-0 251 182. They are obtained by hydrolysis of polymers which contain the monomers of the formula I in copolymerized form with acids, bases or enzymes.

Suitable monoethylenically unsaturated monomers which are copolymerized with the Ν-vinylcarboxamides are all compounds which can be copolymerized therewith. Examples include vinyl esters of saturated carboxylic acids with 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as C ₁ -C ₆ -alkyl vinyl ether, for example methyl or ethyl vinyl ether. Further suitable comonomers are ethylenically unsaturated C ₃ - to C ₆ -carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl ester acid and their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate and ethyl acrylate ethyl methacrylate.

Other suitable monoethylenically unsaturated monomers which are copolymerized with the N -ninylcarboxamides are carboxylic esters which are derived from glycols or polyalkylene glycols, only one OH group being esterified in each case, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyl acrylate methacrylate, hydroxyl butyl acrylate, hydroxyl acrylate and hydroxyl butyl acrylate, and onoesters of polyalkylene glycols with a molecular weight of 500 to 10,000. Further suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylammopropyl methacrylate, diethylaminopropyl acrylate, dimethyl acrylate and diethyl acrylate and diethyl aminobutyl acrylate. The basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form. Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.

Other suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide,

N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylamides, e.g. Dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.

Also suitable as comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as e.g. N-vinyl-2-methylimidazole, N-vinyl-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl -2-ethylimidazoline. In addition to the free bases, N-vinylimidazoles and N-vinylimidazolines are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Diallyldialkylammonium halides such as e.g. Di-dlyldimemyl - n - moniumchloride.

In addition, monomers containing sulfo groups such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid,

Styrene sulfonic acid, the alkali metal or ammonium salts of these acids or acrylic acid 3-sulfopropyl esters in question, the content of cationic units in the amphoteric copolymers exceeding the content of anionic units, so that the polymers as a whole have a cationic charge.

The copolymers contain, for example

99.99 to 1 mol%, preferably 99.9 to 5 mol% of N-vinylcarboxamides of the formula I and

- 0.01 to 99 mol%, preferably 0.1 to 95 mol% of other monoethylenically unsaturated monomers copolymerizable therewith

in polymerized form.

In order to prepare polymers containing vinylamine units, one preferably starts from homopolymers of N-vinylformamide or from copolymers which are obtained by copolymerizing

N-vinylformamide with

Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinyl caprolactam, N-vinyl urea, acrylic acid, Ν-vinyl pyrrolidone or Ci to C ₆ alkyl vinyl ethers

and subsequent hydrolysis of the homo- or of the copolymers to form vinylamine units from the polymerized Ν-vinylformamide units, the degree of hydrolysis being z. B. is 0.1 to 100 mol%.

The polymers described above are hydrolysed by known processes by the action of acids, bases or enzymes. The resulting polymerized monomers of the formula I given above are formed by splitting off the grouping

where R ^{2 has} the meaning given for it in formula I, polymers which

Vinylamine units of the formula (III)

CH.— CH-

(III)

N \ 1 H R

contain in which R ^{1 has} the meaning given in formula I. If acids are used as the hydrolysis agent, units III are present as the ammonium salt.

The homopolymers of N-vinylcarboxylic acid amides of the formula I and their copolymers can be hydrolyzed to 0.1 to 100, preferably 70 to 100, mol%. In most cases, the degree of hydrolysis of the homo- and copolymers is 5 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the vinylamine units in the polymers. In the case of copolymers which contain vinyl esters in copolymerized form, in addition to the hydrolysis of the N-vinylformamide units, hydrolysis of the ester groups can occur with formation of vinyl alcohol units. This is particularly the case when the copolymers are hydrolysed in the presence of sodium hydroxide solution. Polymerized acrylonitrile is also chemically changed during the hydrolysis. This creates, for example, amide groups or carboxyl groups. The homo- and copolymers containing vinylamine units can optionally contain up to 20 mol% of amidine units, which e.g. by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with a neighboring amide group e.g. of polymerized N-vinylformamide. The molar masses of the polymers containing vinylamine units are, for example 1000 to 10 million, preferably 10,000 to 5 million (determined by light scattering). This molar mass range corresponds, for example, to K values of 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight).

The polymers containing vinylamine units are preferably used in salt-free form. Salt-free aqueous solutions of polymers containing vinylamine units can be obtained, for example, from the salt-containing ones described above Polymer solutions can be produced with the aid of ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons. The aqueous solutions of other polymers containing amino and / or ammonium groups described below can also be obtained with the aid of ultrafiltration in a salt-free form.

Polyethyleneimines are also suitable as cationic polymers. Polyethyleneimines are produced, for example, by polymerizing ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids. Polyethyleneimines have, for example, molecular weights of up to 2 million, preferably from 200 to 500,000. Polyethyleneimines with molecular weights of 500 to 100,000 are particularly preferably used. Also suitable are water-soluble crosslinked polyethylenimines which can be obtained by reacting polyethyleneimines with crosslinkers such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units. Amidic polyethyleneimines are also suitable, which can be obtained, for example, by amidating polyethyleneimines with - to C ₂₂ -monocarboxylic acids. Other suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. In alkoxylation, 1 to 5 ethylene oxide or propylene oxide units are used, for example, per NH unit in polyethyleneimine.

Suitable polymers containing amino and / or ammonium groups are also polyamidoamines, which can be obtained, for example, by condensing dicarboxylic acids with polyamines. Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids with 4 to 10 carbon atoms with polyalkylene polyamines which contain 3 to 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. Mixtures of dicarboxylic acids can also be used in the preparation of the polyamidoamines, as can mixtures of several polyalkylene polyamines. Suitable polyalkylene polyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bis-aminopropylethylenediamine. The dicarboxylic acids and polyalkylene polyamines are heated to higher temperatures to produce the polyamidoamines, for example to temperatures in the range from 120 to 220, preferably 130 to 180 ° C. The water generated during the condensation is removed from the system. In the Condensation can optionally also use lactones or lactams of carboxylic acids with 4 to 8 carbon atoms. For example, 0.8 to 1.4 moles of a polyalkylene polyamine are used per mole of a dicarboxylic acid.

Other polymers containing amino groups are polyamidoamines grafted with ethyleneimine. They can be obtained from the polyamidoamines described above by reaction with ethyleneimine in the presence of acids or Lewis acids such as sulfuric acid or boron trifluoride etherates at temperatures of, for example, 80 to 100.degree. Compounds of this type are described for example in DE-B-24 34 816.

The optionally crosslinked polyamidoamines, which are optionally additionally grafted with ethyleneimine before crosslinking, are also suitable as cationic polymers. The crosslinked polyamidoamines grafted with ethyleneimine are water-soluble and have e.g. an average molecular weight of 3000 to 1 million daltons. Common crosslinkers are e.g. Epichlorohydrin or bischlorohydrin ether of alkylene glycols and polyalkylene glycols.

Further examples of cationic polymers containing amino and / or ammonium groups are polydiallyldimethylammonium chlorides. Polymers of this type are also known.

Other suitable cationic polymers are copolymers of, for example, 1 to

99 mol%, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol% of cationic monomers such as

Dialkylaminoalkyl acrylamide, ester and / or methacrylamide and / or methacrylic ester.

The basic acrylamides and methacrylamides are also preferably included

Acids neutralized or in quaternized form. Examples include N-

Trimethyl-u-nmoniumethyl acrylamide chloride, N-trimethylammoniumethyl methacrylamide chloride,

N-trimethyl - mmoniι - methylmethacrylesterchlorid,

N-Trimemylammoniumethylacrylesterchlorid,

Trimethylammoniumetliylacrylamidmethosulfat,

Trimethyl- --- noniumethylmethacrylamide methosulfate, N-ethyldimethyl - mmoniumethylacrylamidethosulfat, N-Ethyldimemyl - mmoniumethylmethacryl _-- midethosulfat, Trimethyl-u-nmonixm propylacrylamide chloride, Trimethyl-uι - moniumpropylmethacrylamidchlorid, Trimethyl - π - moniumpropylacrylamidmethosulfat, Trimethyl - mmomιιmpropylmethacrylamidmethosulfat and

N-El-hylcümethyl --- n - momumpropylacrylamidethosulfat. Trimethyl-mmom ^' umpropyl methacrylamide chloride is preferred.

Other suitable cationic monomers for the production of (meth) acrylamide polymers are diallyldimethylammonium halides and basic (meth) acrylates. Suitable are e.g. Copolymers of 1 to 99 mol%, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol% of dialkylaminoalkyl acrylates and / or methacrylates such as copolymers of acrylamide and N, N -Dimethylaminoethyl acrylate or copolymers of acrylamide and dimethylaminopropyl acrylate. Basic acrylates or methacrylates are preferably in a form neutralized with acids or in quaternized form. The quaternization can take place, for example, with methyl chloride or with dimethyl sulfate.

Polyallylamines are also suitable as cationic polymers which have amino and / or ammonium groups. Polymers of this type are obtained by homopolymerizing allylamine, preferably in acid-neutralized or quaternized form, or by copolymerizing allylamine with other monoethylenically unsaturated monomers described above as comonomers for N-vinylcarboxamides.

The cationic polymers have e.g. K values from 8 to 300, preferably 100 to 180 (determined according to H. Fikentscher in 5% aqueous saline solution at 25% and a polymer concentration of 0.5% by weight). At a pH of 4.5, for example, they have a charge density of at least 1, preferably at least 4 meq / g polyelectrolyte.

Examples of preferred cationic polymers are polydimethyldiallylammonium chloride, polyethyleneimine, polymers containing vinylamine units, copolymerized basic monomers containing copolymerized acrylamide or methacrylamide, polymers containing lysine units or mixtures thereof. Examples of cationic polymers are: • Copolymers of 50% vinyl pyrrolidone and 50%

Trimethyl _-- ammonium ethyl methacrylate methosulfate, M _w 1000 to 500 000;

Copolymers of 30% acrylamide and 70% trimethyl-ammonium ethyl methacrylate methosulfate, M _w 1000 to 1 000 000;

Copolymers of 70% acrylamide and 30% dimethylaminoethyl methacrylamide, M _w 1000 to 1,000,000;

• Copolymers of 50% hydroxyethyl methacrylate and 50% 2-dimethylaminoethyl methacrylamide, M _w 1000 to 500 000;

• copolymer of 70% hydroxyethyl methacrylate and 50% 2-dimethylaminoethyl methacrylamide; 30% vinylimidazole methochloride copolymer, 50%

Dimethylaminoethyl acrylate, 15% acrylamide, 5% acrylic acid;

Polylysines with M _w of 250 to 250,000, preferably 500 to 100,000, and lysine co-condensates with molecular weights M _w of 250 to 250,000, where, for example, amines, polyamines, ketene dimers, lactams,

Uses alcohols, alkoxylated amines, alkoxylated alcohols and / or non-proteinogenic amino acids,

Vinylamine homopolymers, 1 to 99% hydrolyzed polyvinylformamides, copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or acrylamide with molecular weights of 3,000-500,000,

Vinylimidazole homopolymers, vinylimidazole copolymers with vinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate with molecular weights from 5,000 to 500,000 and their quaternary derivatives,

Polyethyleneimines, crosslinked polyethyleneimines or amidated polyethyleneimines with molecular weights of 500 to 3,000,000, Amine-epichlorohydrin polycondensates which contain imidazole, piperazine, -Cs-alkylamines, Ci-Cs-dialkylamines and / or dimemylaminopropylamine as amine component and which have a molecular weight of 500 to 250,000,

• Polymers containing basic (meth) acrylamide or ester units, polymers containing basic quaternary (meth) acrylamide or ester units with molecular weights of 10,000 to 2,000,000.

Furthermore, it is also possible to polymerize in to a minor extent (<10% by weight) of anionic comonomers, e.g. Acrylic acid, methacrylic acid, vinyl sulfonic acid or alkali salts of the acids mentioned.

In order to cationically modify anionically dispersed, particulate, reactively modified polymers, they can optionally be treated with polyvalent metal ions and / or cationic surfactants in addition to treatment with cationic polymers. A coating of the particles with polyvalent metal ions is achieved, for example, by adding an aqueous solution of at least one water-soluble polyvalent metal salt to an aqueous dispersion of anionically dispersed reactively modified polymers or by dissolving a water-soluble polyvalent metal salt therein, the modification of the anionically dispersed reactively modified Particles with cationic polymers either before, simultaneously, or after this treatment. Suitable metal salts are, for example, the water-soluble salts of Ca, Mg, Ba, Al, Zn, Fe, Cr or mixtures thereof. Other water-soluble heavy metal salts derived, for example, from Cu, Ni, Co and Mn can also be used in principle, but are not desired in all applications. Examples of water-soluble metal salts are calcium chloride, calcium acetate, magnesium chloride, aluminum sulfate, aluminum chloride, barium chloride, zinc chloride, zinc sulfate, zinc acetate, iron (II) sulfate, iron (III) chloride, chromium (III) sulfate, copper sulfate, nickel sulfate , Cobalt sulfate and manganese sulfate. The water-soluble salts of Mg, Ca, Al and Zn are preferably used for the cationization.

The modification of the properties of textile and non-textile surfaces with polymer dispersions is important in many commercial and technical applications in everyday domestic life. It is not always possible to modify the surfaces using impregnation, spraying and painting processes with concentrated dispersions. Often it is desirable to modify with the help of a rinse the surface to be treated with a highly diluted liquor containing an active substance. It is often desirable to combine the modification of the surface in connection with washing, cleaning and / or care or impregnation of the surface. Surfaces of textile materials such as cotton fabrics and cotton blended fabrics are particularly suitable. In addition, carpets and furniture covers can be treated according to the invention. The modification of the surfaces of textile materials can consist, for example, of hydrophobization, soil-release finishing, dirt-repellent finishing, reinforcement of the fiber composite and protection against chemical or mechanical influences and damage.

The reactively modified, particulate polymers are used to modify surfaces of the above-mentioned materials as an additive to detergents or care products, washing or cleaning agents for textile and other non-textile surfaces. In particular, applications in the washing, cleaning and aftertreatment of textiles, leather, wood, floor coverings, glass, ceramics and other surfaces in the household and in the commercial sector come into question.

The reactively modified, particulate polymers are used as a dilute, predominantly aqueous dispersion. The application is carried out by treating the surfaces in washing, cleaning and rinsing liquors, to which the polymers are added either directly or by means of a liquid or solid formulation, or by the finely divided application of a liquid formulation, e.g. by spraying.

The reactively modified, particulate polymers can, for example, be used as the sole active component in aqueous detergents and care products and, depending on the composition of the polymer, cause e.g. a facilitated detachment of dirt during a subsequent wash, less dirt adherence when using the textiles, an improvement in the maintenance of fibers, an improvement in the shape and structure of fabrics, a hydrophobization of the surface of the laundry and an improvement in the handle.

The concentration of the reactively modified, particulate polymers when used in the rinsing or care bath, in the detergent liquor or in the cleaning bath is, for example, 0.0002 to 1% by weight, preferably 0.0005 to 0.25% by weight, particularly preferably 0.002 to 0.05% by weight. In principle, all reactively modified particulate polymers can be used in the above-mentioned applications. Depending on the embodiment, it can be advantageous to select a specific monomer composition in order to achieve particularly advantageous modifications.

In a preferred embodiment of the invention, the polymers used contain polymerized cationic monomers and therefore have an increased affinity for the surfaces to be treated.

In a further preferred embodiment, the polymers used contain copolymerized anionic monomers and are used together with cationic polymers, cationic surfactants and / or polyvalent metal cations. The treatment of the surfaces, for example textile surfaces, is carried out with aqueous liquors which contain, for example, 2.5 to 300 ppm, preferably 5 to 200 ppm and in particular 10 to 100 ppm of at least one cationic polymer, up to 5 mmol / 1, preferably up to 3.5 mmol / 1 water-soluble salts of polyvalent metals, in particular salts of Ca, Mg or Zn and / or up to 2 mmol / 1, preferably up to 0.75 mmol / 1 water-soluble AI salts and / or up to 600 ppm , preferably contain up to 300 ppm of cationic surfactants.

In a further preferred embodiment, alkali-swellable, particularly preferably alkali-soluble, reactive modified polymers are used. Such polymers are used particularly advantageously, for example, to improve the detachment of dirt from textile and non-textile surfaces. Suitable reactively modified alkali-soluble polymers contain, for example

(a) 30 to 80% by weight, preferably 40 to 75% by weight, particularly preferably 50 to 70% by weight of at least one sparingly water-soluble or water-insoluble nonionic monomer,

(b) 20 to 70% by weight, preferably 25 to 60% by weight, particularly preferably 30 to 50% by weight, of at least one monomer containing carboxyl groups or salts thereof, (c) 0 to 25% by weight, preferably 0 to 15% by weight, of one or more sulfonic acid and / or phosphonic acid groups containing monomers or their salts,

(d) 0 to 30% by weight, preferably 0 to 15% by weight, of one or more cationic monomers,

(e) 0 to 55% by weight, preferably 0 to 40% by weight, of one or more water-soluble nonionic monomers,

(f) 0 to 30% by weight, preferably 0 to 10% by weight, of one or more polyethylenically unsaturated monomers, and

(g) 0.1 to 30% by weight, preferably 0.1 to 10% by weight of at least one ethylenically unsaturated monomer containing reactive groups.

Surface treatment agents can have, for example, the following composition:

(a) 0.05 to 40% by weight of reactively modified, particulate polymers, the particle size of which is 10 nm to 100 μm,

(b) 0 to 10% by weight of one or more cationic polymers,

(c) 0 to 30% by weight of one or more water-soluble salts of Mg, Ca, Zn or Al and / or one or more cationic surfactants,

(d) 0 to 80% by weight of one or more conventional additives such as acids or bases, inorganic builders, organic cobuilders, further surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes Silicone oils

Light stabilizers, dyes, solvents, hydrotropes, thickeners and / or alkanolamines.

The invention also relates to laundry aftertreatment and laundry care compositions and to solid and liquid detergent formulations which contain the reactively modified, particulate polymers. Laundry after-treatment and laundry care products contain, for example

(a). 0.1 to 40% by weight of reactively modified, particulate polymers which have a particle size of 10 nm to 100 μm and are dispersed in water,

(b) 0 to 20% by weight of one or more organic acids such as formic acid, citric acid, adipic acid, succinic acid, oxalic acid or mixtures thereof,

(c) 0 to 10% by weight of cationic polymers,

(d) 0 to 30% by weight of one or more water-soluble salts of Mg, Ca, Zn or Al and / or one or more cationic surfactants,

(e) 0 to 30% by weight of one or more nonionic surfactants,

(f) 0 to 30% by weight of other conventional ingredients such as perfume, silicone oils, other lubricants, film-forming polymers, stabilizers, anti-corrosion additives, preservatives, bactericides, light stabilizers, colorants, complexing agents, graying inhibitors, soil-release polyesters, color transfer inhibitors, non-aqueous solvent, hydrotropes, thickeners and / or alkanolamines and

(g) water to make up to 100% by weight.

Preferred cationic surfactants are selected from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoamine esters and imidazolium salts. These are preferably contained in the laundry detergent in an amount of 3 to 30% by weight. Examples are quaternary diesterammonium salts which have two C _π to C ₂₂ alk (en) yl carbonyloxy (mono- to pentamethylene) residues and two C _r to C ₃ alkyl or hydroxyalkyl residues on the quaternary N atom and as Counterion, for example, wear chloride, bromide, methyl sulfate or sulfate.

Quaternary diester ammonium salts are furthermore, in particular, those which have a C _n - to C ₂₂ -alk (en) ylcarbonyloxytrimethylene radical which is attached to the middle carbon atom of the trimethylene

Grouping carries a C _π - to C ₂₂ alk (en) ylcarbonyloxy radical, and three C _j - bis Have alkyl or hydroxyalkyl residues on the quaternary N atom and carry, for example, chloride, bromide, methyl sulfate or sulfate as counterion.

Quaternary tetraallylammonixim salts are in particular those which have two C _r to C ₆ alkyl radicals and two C ₈ to C ₂₄ alk (en) yl radicals on the quaternary N atom and, for example, chloride, bromide, methyl sulfate as counterion or carry sulfate.

Quaternary diamidoammonium salts are in particular those which have two C ₃ - to C ₂₄ -alk (en) ylcarbonylaminoethylene radicals, a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene with up to 5 oxyethylene units and as the fourth radical a methyl group on the quaternary Have N atom and wear, for example, chloride, bromide, methyl sulfate or sulfate as counterion.

Amidoamino esters are, in particular, tertiary amines which, as substituents on the N atom, have a C _u to C ₂₂ alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C _n to C ₂₂ alk (en) ylcarbonyloxy (mono - to trimethylene) residue and a methyl group.

Imidazolinium salts are in particular those which have a C _{] 4} - to C ₁₈ -alk (en) yl radical in the 2-position of the heterocycle and a C ₁₄ - to C ₁₈ -alk (en) ylcarbonyl (oxy or amino) on the neutral N atom ) carry the ethylene radical and hydrogen, methyl or ethyl on the N atom carrying the positive charge; counterions here are, for example, chloride, bromide, methyl sulfate or sulfate.

Solid detergent formulations according to the invention contain

(a) 0.05 to 20% by weight of reactively modified, particulate polymers, the particle size of which is 10 nm to 100 μm,

(b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

(c) 0 to 50% by weight of one or more inorganic builders, ^"

(d) 0 to 20% by weight of one or more organic cobuilders, (e) 0 to 60% by weight of other customary ingredients, such as cationic surfactants, adjusting agents,

Enzymes, perfume, complexing agents, corrosion inhibitors, bleach,

Bleach activators, bleach catalysts, dye transfer inhibitors, graying inhibitors, soil-release polyesters, dyes, dissolution improvers and / or disintegrants,

the sum of components (a) to (e) being 100% by weight.

The solid detergent formulations according to the invention are usually in the form of powder, granules, extrudate or in tablet form.

Contain liquid detergent formulations according to the invention

(a) 0.05 to 20% by weight of reactive-modified, particulate polymers, the particle size of which is 10 nm to 100 μm,

(b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

(c) 0 to 20% by weight of one or more inorganic builders,

(d) 0 to 10% by weight of one or more organic cobuilders,

(e) 0 to 40% by weight of other customary ingredients, such as cationic surfactants, soda,

Enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, color transfer inhibitors, graying inhibitors, target release polyesters, dyes, non-aqueous solvents

Hydrotropes, thickeners and / or alkanolamines and

(f) 0 to 99.85% by weight of water,

the sum of components (a) to (f) being 100% by weight.

Suitable anionic surfactants are in particular:

- (Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ - to Cπ-alcohol sulfates, C ₁₂ - to 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 C ₈ to C ₂₂ alcohols (alkyl ether sulfates); Compounds of this type are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, for example a fatty alcohol, and the like

Alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation; linear Cg to C ₂ Q alkyl benzosulfonates (LAS), preferably linear C ₉ to C ₁₃ alkyl benzene sulfonates and alkyl toluenesulfonates, alkane sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₈ alkanesulfonates

Soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

The anionic surfactants mentioned are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) anιmonium.

Suitable nonionic surfactants are in particular:

- Alkoxylated C ₈ - to C ₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These can be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of one of the above-mentioned alkylene oxides added can be used as surfactants. Here, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. The nonionic surfactants generally contain 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide per mole of alcohol. These preferably contain ethylene oxide as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the production, the

Alkoxylates have a broad or narrow alkylene oxide homolog distribution; Alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 alkylene oxide units; Alkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5, glucoside units; N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

Suitable inorganic builders are in particular:

crystalline or amorphous aluminosilicates with ion-exchanging properties such as, in particular, zeolites. Suitable zeolites are in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium; - Crystalline silicates such as, in particular, disilicates or layered silicates, for example δ-Na Si ₂ O ₅ or ß-Na ₂ Si ₂ O ₅ . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates; amorphous silicates such as sodium metasilicate or amorphous disilicate; Carbonates and hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferred; Polyphosphates such as pentasodium triphosphate;

Suitable organic cobuilders are in particular low molecular weight, oligomeric or polymeric carboxylic acids.

Suitable low molecular weight carboxylic acids are, for example, citric acid, hydrophobically modified citric acid such as. B. agaricinic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid,

Oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as e.g. Nitrilotriacetic acid, ß-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic acid;

Suitable oligomeric or polymeric carboxylic acids are, for example, homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid, C ₂ -C ₂₂ olefins such as isobutene or long-chain α-olefins, vinyl alkyl ethers with -Cs alkyl groups, vinyl acetate, vinyl propionate, (meth ) acrylic esters of -Cs alcohols and styrene. It is preferred to use the

Homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. Polyaspartic acids are also suitable as organic cobuilders. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.

If there is a cationic modification of the reactively modified, particulate polymers, this is preferably carried out before use in the aqueous treatment agents, but it can also be used in the preparation of the aqueous treatment agents or the use of anionically dispersed, particulate polymers with a particle size of 10 nm up to 100 μm by using e.g. aqueous dispersions of the particulate polymers in question are mixed with the other constituents of the respective treatment agent in the presence of cationic polymers and optionally of water-soluble salts of polyvalent metals and / or cationic surfactants.

In a special embodiment, it is also possible to reactively modified polymers with anionic character or formulations containing them directly from the rinse,

Add washing or cleaning liquor if it is ensured that sufficient amounts of cationic polymers and possibly polyvalent ones are present in the liquor

Metal ions and / or cationic surfactants are present in dissolved form. For example, it is possible to use anionic polymers or formulations containing them in liquors with a cationic polymer content of 2.5 to

300 ppm and optionally of water-soluble salts of Ca, Mg or Zn of over

0.5 mmol / 1, preferably over 1 mmol / 1, particularly preferably over 2 mmol / 1.

If cationic surfactants are used, they are used, for example, in

Concentrations of 50 to 100 ppm, preferably 75 to 500 ppm and especially 100 to 300 ppm in the aqueous liquor.

The reactive modified polymers with an anionic character or the formulations containing them can also be metered in before, after or at the same time with a formulation containing cationic polymers and optionally cationic surfactants.

With alkali-soluble or alkali-swellable reactively modified particulate polymers, a much higher soil-release effect is achieved, in particular on cotton and cellulose fibers, than with known water-soluble soil-release polymers.

The invention also relates to the use of reactively modified polymers in finishing agents for the anti-crease treatment of cellulose-containing ones Textiles. Finishing agents are any liquid formulations which contain the reactively modified polymer, in particular in the form of an aqueous polymer dispersion, for application to the textile material in dispersed form. The finishing agents according to the invention can be present, for example, as finishing agents in the narrower sense in the manufacture of the textiles or in the form of an aqueous washing liquor or as a liquid textile treatment agent. For example, it is possible to treat the textiles with the finishing agent in connection with textile production. Textiles which have not yet been treated or have been insufficiently treated with finishing agents can be treated, for example, in the home area before or after washing, for example when ironing, with a textile treatment agent which contains the polymer dispersion. However, it is also possible to treat the textiles with the reactively modified polymers in the main wash cycle or after the main wash cycle in the care or fabric softener cycle, for example using the formulations described above.

The present invention also relates to the use of the reactively modified polymers in the manufacture of the textiles, in the treatment of the textiles before and after washing, in the main wash cycle, in the fabric rinse cycle and in ironing. Different formulations are required for this. Examples are the liquid and solid detergents, laundry aftertreatment and laundry care compositions described above.

The textiles treated with the reactively modified polymers in the main wash cycle of the washing machine not only wrinkle significantly less than untreated textiles. They are also easier to iron, softer and smoother, more dimensionally and dimensionally stable and after washing several times they look less "used" due to their fiber and color protection, so they have less lint and knots and less color damage or fading.

The textiles treated with reactive modified polymers in the fabric softener or conditioner after the main wash cycle also have very good crease protection after drying on a line or preferably in a tumble dryer and are easier to iron. The anti-crease can be significantly increased by briefly ironing the textiles after drying. Treatment in a soft or conditioner cycle also has a positive effect on the shape stability of the textiles. Furthermore, the formation of knots and lint is inhibited and color damage is suppressed.

In the treatment before or after the textile washing, a textile treatment agent can be used as the finishing agent which, in addition to the reactively modified polymer, contains a surface-active agent in dispersed form. In this treatment, the cellulose-containing textiles are sprayed, for example, with the reactively modified polymers, the application amount generally being 0.01 to 10% by weight, preferably 0.1 to 7, particularly preferably 0.3 to 4% by weight, based on the Weight of the dry textile goods. The finishing agent can, however, also be applied to the textile material by immersing the textiles in a bath which is generally 0.1 to 10% by weight, preferably 0.3 to 5% by weight, based on the weight of the dry textile material. contains the reactively modified, particulate polymer in dispersed form. The textile is either only briefly immersed in the bath or can also remain there for a period of, for example, 1 to 30 minutes.

The cellulose-containing textiles, which have been treated with the finishing agent either by spraying or by immersion, are optionally pressed off and dried. Drying can be done in air or in a dryer or by hot ironing the treated textile. The finishing agent is fixed on the textile by drying. The most favorable conditions for this can easily be determined with the help of experiments. The temperature during drying, including ironing, is generally 40 to 150 ° C, preferably 60 to 110 ° C. The iron ironing program is particularly suitable for ironing. The textiles which have been treated with the reactively modified polymers in dispersed form by the process described above have excellent crease and wrinkle protection which remains after several washes. Ironing the textiles is often no longer necessary.

The invention also relates to a textile treatment composition containing

a) 0.1 to 40% by weight, preferably 0.5 to 25% by weight, of at least one reactively modified, particulate polymer,

b) 0 to 30% by weight of silicones, c) 0 to 30% by weight of one or more cationic and / or nonionic surfactants,

d) 0 to 60 wt .-% of other ingredients such as other wetting agents, plasticizers, lubricants, water-soluble, film-forming and adhesive polymers, fragrance and

Dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides, preservatives and spray aids, and

e) 0 to 99.9% by weight of water,

the sum of components a) to e) being 100% by weight.

Preferred silicones are silicones containing amino groups, which are preferably in microemulsified form, alkoxylated, in particular ethoxylated silicones, polyalkylene oxide polysiloxanes, polyalkylene oxide aminopolydimethylsiloxanes, silicones with quaternary ammonium groups (silicone quats) and silicone surfactants. Suitable plasticizers or lubricants are, for example, oxidized polyethylenes or waxes and oils containing paraffin. Suitable water-soluble, film-forming and adhesive polymers are, for example, (co) polymers based on acrylamide, N-vinylpyrrolidone, vinylformamide, N-vinylimidazole, ninylamine, Ν, Ν'-dialkylaminoalkyl (meth) acrylates, N, N '-dialkylaminoalkyl (meth) acrylamides, (meth) acrylic acid, (meth) acrylic acid alkyl esters and / or vinyl sulfonate. The basic monomers mentioned above can also be used in quaternized form.

If the textile treatment formulation is sprayed onto the textile material, the formulation can additionally contain a spraying aid. In some cases it may also be advantageous to add alcohols such as ethanol, isopropanol, ethylene glycol or propylene glycol to the formulation. Other common additives are fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives in the amounts customary for this.

The textile treatment agent can also generally be applied by spraying when the textile is ironed after washing. This not only makes ironing considerably easier, the textiles are additionally equipped with a long-lasting crease and wrinkle protection.

The invention is illustrated by the examples below.

Examples

The emulsifiers used in the examples have the following composition:

Emulsifier 1: 15% by weight solution of sodium lauryl sulfate;

Emulsifier 2: 40% by weight solution of an ethoxylated and quaternized oleylamine, (Lipamin® OK from BASF)

The particle size distribution was determined using an Autosizer® 2C from Malvem, England. The measurement was carried out at 23 ° C. Unless otherwise stated, solutions are aqueous solutions. The expression pphm used in the examples means parts by weight based on 100 parts by weight of total monomers.

Preparation of the polymers

example 1

12 g of a 0.1% strength by weight sodium persulfate solution as initiator, 6 g of a 15% strength by weight solution of emulsifier 1 and 402 g of water are placed in a glass reactor provided with an anchor stirrer, thermometer, gas inlet tube, dropping funnel and reflux condenser and heated with stirring in a heating bath, at the same time displacing the air by introducing nitrogen. As soon as the heating bath has reached a temperature of 75 ° C., the introduction of nitrogen is interrupted and 4 g of a 0.1% by weight sodium persulfate solution and an emulsion of 177 g of ethyl acrylate, 69 g of methacrylic acid, 39 g are obtained in the course of 2 hours Acrylic acid, 15 g of glycidyl methacrylate and 22 g of a 15% strength by weight solution of emulsifier 1 in 400 ml of water were added dropwise. The mixture is then polymerized at 75 ° C for 1 hour. While cooling to room temperature, 0.75 g of a 30% by weight hydrogen peroxide Solution added all at once and a solution containing 0.3 ascorbic acid and 0.3 g of iron (II) sulfate in 29.7 g of water was added over 15 minutes.

A polymer dispersion with the following properties is obtained:

Solids content: 25.8% by weight average particle size: 70 nm

Coagulum content: <1 g pH: 2.2

Example 2

In a glass reactor provided with an aluminum tube, thermometer, gas inlet tube, dropping funnel and reflux condenser, 12 g of a 0.1% by weight solution are added

Sodium persulfate solution as initiator, 2.3 g of a 40% strength by weight solution of emulsifier 2 and 402 g of water are introduced and heated with stirring in a heating bath, at the same time displacing the air by introducing nitrogen. As soon as the heating bath has reached a temperature of 85 ° C, the introduction of nitrogen is interrupted and 4 g of a 0.1% by weight sodium persulfate solution and an emulsion of 178 g of butyl acrylate, 114 g of methacrylic acid are added in the course of 2 hours. 15 g of glycidyl methacrylate and 22 g of a 15% strength by weight solution of emulsifier 1 in 400 ml of water were added dropwise.

The mixture is then polymerized at 75 ° C for 1 hour. While cooling to room temperature, 0.75 g of a 30% by weight hydrogen peroxide solution is added all at once and a solution containing 0.3 g of ascorbic acid and

0.3 g of iron (II) sulfate in 29.7 g of water were added.

A polymer dispersion with the following properties is obtained:

Solids content: 25.9% by weight average particle size: 100 nm

Coagulate content: <lg pH: 2.2 Example 3

12 g of a 0.1% strength by weight solution of 2,2'-azobis (2-amidinopropane) dihydrochloride (Wako V 50 from Wako Chemie) are placed in a glass reactor provided with an agitator, thermometer, gas inlet tube, dropping funnel and reflux condenser ) as initiator, 2.3 g of a 40% by weight solution of emulsifier 2 and 402 g of water are introduced and heated with stirring in a heating bath, the air being displaced at the same time by introducing nitrogen. As soon as the heating bath has reached a temperature of 85 ° C, the nitrogen introduction is interrupted and 4 g of the initiator solution and an emulsion of 178 g of butyl acrylate, 114 g of methacrylic acid, 15 g of glycidyl methacrylate and 8.3 g of a 40 % by weight solution of emulsifier 1 in 400 ml of water was added dropwise. The mixture is then polymerized at 85 ° C for 1 hour. While cooling to room temperature, 0.75 g of a 30% by weight hydrogen peroxide solution is added all at once and a solution containing 0.3 g of ascorbic acid and 0.3 g of iron (II) sulfate in 29.7 is added over 15 minutes g of water added.

A polymer dispersion with the following properties is obtained:

Solids content: 25.5% by weight average particle size: 120 nm

Coagulate content: <1 g pH: 4.0

Example 4

5.2 g of a 3.8% strength by weight solution of 2,2'-azobis (2-amidinopropane) dihydrochloride (Wako V 50 from Wako Chemie) as initiator, 37.5 g of a 40% by weight solution of emulsifier 2 and 370 g of water and heated with stirring in a heating bath, the air being displaced by introducing nitrogen at the same time. As soon as the heating bath has reached a temperature of 90 ° C, the introduction of nitrogen is interrupted and 46.8 g of the initiator feed, an emulsion of 265 g of n-butyl acrylate, 14.5 g of acrylic acid, 135 g of glycidyl methacrylate, are obtained over the course of 2 hours. 85.5 g of dimethylaminopropylacrylamide, 52 g of 50% by weight sulfuric acid and 37.5 g of a 40% by weight solution of emulsifier 2 in 280 ml of water dropwise. The mixture is then polymerized at 85 ° C for 1 hour. While cooling to room temperature, 25 g of a 4% strength by weight aqueous solution of nafriximformaldehyde sulfoxylate (Rongalit® C) and 25 g of a 10% strength by weight aqueous solution of tert-butyl hydroperoxide are added over a period of 90 minutes.

A polymer dispersion with the following properties is obtained:

Solids content: 40.6% by weight average particle size: 120 nm

Coagulate content: <1 g pH: 4.0

Testing the soil release properties of the polymers

Examples 5-7 and Comparative Example VI

Washing tests were carried out to test the soil release properties of the polymer dispersions:

Cotton fabrics were prewashed with the anionic polymer dispersions according to Examples 1 to 3, which contained the polymer in a concentration of 400 ppm, at a pH of 4 in water of 3.0 mmol of water hardness and then dried.

In Comparative Example VI, the fabric was prewashed at pH 4 in the absence of reactive modified particles.

In Example 7, washing was carried out with a liquor which contained the reactively modified polymers from Example 1 with a coating of polyethyleneimine with a molecular weight of 25,000. For this purpose, the polyethyleneimine was dissolved in water of 3.0 mmol hardness and a pH of 4.0 was set in the solution. A 20% by weight polymer dispersion according to Example 1 with a pH of 4.0 was added to this solution. The concentration of the polymer particles in the liquor was 400 ppm, the concentration of the polyethyleneimine was 40 ppm. After drying, the prewashed fabrics were soiled with lipstick paste and then washed with a standard commercial detergent.

Washing conditions:

Washing machine: Lauder-O-meter water hardness: 3.0 mmol / 1 Ca ²⁺ / Mg ²⁺ ratio: 3: 1

Prewash: pH of the liquor: 4.0 Prewash temperature: 20 ° C Prewash time: 15 min liquor ratio 1: 12.5

Main wash: wash temperature: 40 ° C wash time: 30 min liquor ratio 1: 12.5

After drying, the flat cotton fabrics were rated visually with the grades 1-5, the grade 1 being given for unchanged soiled fabric and the grade 5 for completely detaching the lipstick soiling.

Table 1

The results of the washing tests show that the use of commercially available heavy-duty detergents under the selected conditions produces almost no improvement in the detachment of dirt from lipstick to cotton fabric. By using the reactively modified polymers, however, there is a significant improvement in dirt removal.

Testing the hydrophobic properties of the polymers

Examples 8-10 and Comparative Example N2

To test the hydrophobizing properties of the reactively modified polymers, rinsing tests were carried out on glass.

Glass plates with an area of 2.5 x 7.5 cm were rinsed with an aqueous solution of a nonionic surfactant (200 ppm C ₁₃ / C ₁₅ oxo alcohol, alkoxylated with 7 mol ethylene oxide) at room temperature, with pure water with a hardness of 3 mmol / 1 rinsed and air-dried.

A dispersion of reactively modified polymers according to Example 1 or 2 was prepared, the polymer concentration being 200 ppm, the water hardness 3 mmol and the pH 6.0 mg.

In Example 10 there was an additional 20 ppm of polyethyleneimine with a molecular weight of 25,000.

The glass plate was immersed in this dispersion for 10 seconds, then removed and dried at 60 ° C. for 30 minutes.

A drop of deionized water was applied to each of the glass plates treated in this way and the contact angle was measured. Table 2 shows the measured contact angles. Table 2

Anti-wrinkle treatment of tissue samples

Examples 11-14 and Comparative Example N3

Sheet-like structures made of cotton (BW) of the size given in Table 3 with a weight per unit area of 160 g / m ² were sprayed on both sides with the polymers from Examples 1 to 3, so that the application amount was 2%, based on the weight of the dry textile goods, and then ironed hot in a slightly damp state.

The tissue samples treated in this way were washed for comparison with untreated tissue samples of the same size and in the presence of ballast tissue with a liquid detergent at 40 ° C. in an automatic household machine (load between 1.5 and 3.0 kg) and then dried in a drum dryer. A standard washing or standard dry program was used (40 ° C colored wash program or cupboard dry program). After drying, the flat tissue samples were rated visually in accordance with the AATCC test method 124, where the grade 1 means that the fabric is very creased and has many folds, while the grade 5 is given for crease-free and wrinkle-free fabric. The tissue samples pretreated with the finishing agents (Examples 1 to 3) received grades between 2.5 and 3.5. In contrast, the untreated tissue samples were given a grade of 1. Table 3

Claims

claims

Process for treating the surface of textile and non-textile materials, in which reactively modified, particulate polymers with a particle size of 10 nm to 100 μm are applied to the surface of the materials from an aqueous dispersion and the materials are dried.

2. The method according spoke 1, characterized in that the polymers are applied to the surface from an aqueous dispersion with a polymer content of <1 wt .-%.

3. The method according spoke 1 or 2, characterized in that the reactively modified, particulate polymers contain ethylenically unsaturated monomers in copolymerized form with reactive, crosslinking groups.

4. The method according spoke 3, characterized in that the reactive, crosslinking groups are selected from the group consisting of

Glycidyl ether, halohydrin, carboxylic anhydride, carboxylic acid chloride,

Carboxylic acid ester, isocyanate, vinyl sulfone, N-methylol, aldehyde and

Imine groups.

5. The method according spoke 4, characterized in that the monomers with reactive crosslinking groups are selected from the group consisting of glycidyl (meth) acrylate, (meth) acrolein, methacrylic anhydride, 2- (4-ethoxyphenyl) -2-oxazolinyl methacrylate , Isobutoxymethylacrylamide and maleic anhydride.

6. The method according to any one of claims 1 to 5, characterized in that the reactively modified, particulate polymers contain anionic and / or cationic monomers in copolymerized form.

7. The method according to any one of claims 1 to 6, characterized in that the reactively modified, particulate polymers on their surface have anionic, cationic or amphoteric protective colloids or emulsifiers.

8. The method according to any one of claims 1 to 7, characterized in that the reactively modified, particulate polymers on their surface

Protective colloids or emulsifiers that contain reactive groups.

9. The method according to any one of claims 1 to 8, characterized in that the reactively modified, particulate polymers contain copolymerized anionic groups and / or with anionic protective colloids or

Emulsifiers are dispersed and coated on their surface with cationic polymers.

10. Use of reactively modified, particulate polymers, as defined in one of claims 1 to 9, as surface-modifying additives to washing, rinsing, care or cleaning agents.

11. Use of reactively modified, particulate polymers according to spoke 10 as a fiber and color protection additive.

12. Use of reactively modified, particulate polymers according to spoke 10 as an anti-crease additive for cellulose-containing textiles.

13. Use of reactively modified, particulate polymers, as defined in one of claims 1 to 9, for the hydrophobization of surfaces of textile materials.

14. Use of reactively modified, particulate polymers, as defined in one of claims 1 to 9, to improve the dirt repellency of surfaces of textile materials.

15. Finishing agent for anti-creasing of cellulose-containing textiles containing reactively modified, particulate polymers as defined in one of claims 1 to 9.

16. Use of finishing agents containing reactively modified, particulate polymers, as defined in one of claims 1 to 9, in the manufacture of the textiles, in textile treatment, in the main wash cycle, in the wash cycle, and in ironing.

17. Surface treatment compositions containing

(b) 0 to 10% by weight of one or more cationic polymers,

(d) 0 to 80% by weight of one or more customary additives, such as acids or bases, inorganic builders, organic cobuilders, further surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils , Light stabilizers, dyes, solvents, hydrotropes,

Thickeners and / or alkanolamines,

the sum of components (a) to (d) being 100% by weight.

18. Containing laundry aftertreatment and laundry care products

(a) 0.1 to 40% by weight of reactively modified, particulate polymers with a particle size of 10 nm to 100 μm, which are dispersed in water,

(c) 0 to 10% by weight of cationic polymers, (d) 0 to 30% by weight of one or more water-soluble salts of Mg, Ca, Zn or Al and / or one or more cationic surfactants,

(e) 0 to 30% by weight of one or more nonionic surfactants,

(f) 0 to 30% by weight of other conventional ingredients such as perfume, silicone oils, other lubricants, wetting agents, film-forming polymers, stabilizers, corrosion protection additives, preservatives, bactericides, light stabilizers, colorants, complexing agents, graying inhibitors, soil-release polyesters, color transfer inhibitors , non-aqueous

Solvents, hydrotropes, thickeners and / or alkanolamines and

(g) water to make up to 100% by weight.

19. Solid detergent formulation containing

(a) 0.05 to 20% by weight of reactively modified, particulate polymers with a particle size of 10 nm to 100 μm,

(b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

(c) 0 to 50% by weight of one or more inorganic builders.

(d) 0 to 20% by weight of one or more organic cobuilders,

(e) 0 to 60% by weight of other customary ingredients, such as cationic surfactants,

Adjusting agents, enzymes, perfume, complexing agents, corrosion inhibitors,

Bleaching agents, bleach activators, bleaching catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes,

Resolution improvers and / or disintegrants,

the sum of components (a) to (e) being 100% by weight.

20. Liquid detergent formulation containing

(a) 0.05 to 20% by weight of reactive-modified, particulate polymers with a particle size of 10 nm to 100 μm,

(b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

(c) 0 to 20% by weight of one or more inorganic builders,

(d) 0 to 10% by weight of one or more organic cobuilders,

(e) 0 to 40% by weight of other conventional ingredients such as cationic surfactants, soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, non-aqueous solvents, hydrotropes , Thickeners and / or alkanolamines and

(f) 0 to 99.85% by weight of water,

the sum of components (a) to (f) being 100% by weight.

21. Textile treatment agent containing

a) 0.1 to 40% by weight of at least one reactively modified, particulate polymer,

b) 0 to 30% by weight of silicones,

c) 0 to 30% by weight of cationic and / or nonionic surfactants,

d) 0 to 60% by weight of further ingredients such as further wetting agents,

Plasticizers, lubricants, water-soluble, film-forming and adhesive polymers, fragrances and dyes, stabilizers, fiber and

Color protection additives, viscosity modifiers, soil release additives, Corrosion protection additives, bactericides, preservatives and spray aids, and

e) 0 to 99.9% by weight of water,

the sum of components a) to e) being 100% by weight.