EP1287104B1 - Use of cationically modified, particle-shaped, hydrophobic polymers as addition agents in textile rinsing or care products and as addition agents in detergents - Google Patents

Abstract

The invention relates to the use of cationically-modified, particle-shaped, hydrophobic polymers as addition agents in rinsing, care, detergent, and cleaning products. The surface of said polymers is cationically modified by means of a coating of cationic polymers and the particle size of said polymers ranges from 10 nm to 100 mum.

Description

The invention relates to the use of cationically modified, particulate, hydrophobic polymers as an additive to rinse or care products and as an additive to detergents and rinse, care and detergent containing the cationically modified, particulate, hydrophobic polymers.

Dispersions of particles of hydrophobic polymers, especially aqueous dispersions of synthetic polymers and waxes, are used in the art to modify the properties of surfaces. For example, one uses aqueous dispersions of finely divided hydrophobic polymers as binders in paper coating slips for the coating of paper or as a paint. The in each case on a substrate according to common methods, e.g. by knife coating, brushing, impregnating or impregnating, applied dispersions are dried. In the process, the dispersed particles on the respective surface form a coherent film.

Aqueous washing, rinsing, cleaning and care processes, however, are usually carried out in a highly diluted liquor, the ingredients of each applied formulation does not remain on the substrate, but rather be disposed of with the wastewater. The modification of surfaces with dispersed hydrophobic particles succeeds in the abovementioned processes only to a completely unsatisfactory extent. For example, from US-A-3 580 853 a detergent formulation is known which contains a water-insoluble finely divided substance such as biocides and certain cationic polymers which increase the deposition and retention of the biocides on the surfaces of the laundry.

US-A-5 476 660 also discloses the principle of using polymeric retention aids for cationic or zwitterionic dispersions of polystyrene or wax containing an active substance embedded in the dispersed particles. These dispersed particles are referred to as "carrier particles", because they adhere to the treated surface and there release the active substance, for example when used in surfactant-containing formulations.

It is known from US-A-3 993 830 to apply a non-permanent soil release finish to a fabric by treating the fabric with a dilute aqueous solution containing a polycarboxylate polymer and a water-soluble polyvalent metal salt. Suitable polycarboxylate polymers are preferably water-soluble copolymers of ethylenically unsaturated monocarboxylic acids and alkyl acrylates. The blends are used in the textile washing in the household in the rinse cycle of the washing machine.

The present invention has for its object to provide a further method for the modification of textile surfaces available.

The object is achieved with the use of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by occupancy with cationic polymers and whose particle size is 10 nm to 100 microns, as an additive to rinse or care products for textiles and as an additive to detergents.

The cationically modified particulate hydrophobic polymers are obtainable, for example, by treating aqueous dispersions of particulate hydrophobic polymers having a particle size of 10 nm to 100 μm with an aqueous solution or dispersion of a cationic polymer. This is most easily done by combining an aqueous dispersion of particulate hydrophobic polymers having a particle size of 10 nm to 100 μm with an aqueous solution or dispersion of a cationic polymer. The cationic polymers are preferably used in the form of aqueous solutions, but it is also possible to use aqueous dispersions of cationic polymers whose dispersed particles have an average diameter of up to 1 μm. Most often, the two components are mixed at room temperature, but mixing at temperatures of e.g. 0 ° to 100 ° C, provided that the dispersions do not coagulate when heated.

The dispersions of the particulate hydrophobic polymers can be stabilized with the aid of an anionic emulsifier or protective colloid. Other dispersions which can be used with equal success, are free of protective colloids and emulsifiers and contain as hydrophobic polymers copolymers which contain at least one anionic monomer in copolymerized form. Such dispersions of anionic group-containing copolymers may optionally additionally contain an emulsifier and / or a protective colloid. Preferably anionic emulsifiers and / or protective colloids are used.

In the treatment of the anionic dispersions of the hydrophobic polymers with an aqueous solution of a cationic polymer, the originally anionically dispersed particles are reloaded so that they preferably carry a cationic charge after the treatment. Thus, for example, cationically modified dispersions of particulate hydrophobic polymers in 0.1% by weight aqueous dispersion have an interfacial potential of -5 to +50 mV, preferably from -2 to +25 mV, in particular from 0 to +15 mV. The interfacial potential is determined by measuring the electrophoretic mobility in dilute aqueous dispersion and the pH of the intended application liquor.

The pH of the aqueous dispersions of the cationically modified, particulate, hydrophobic polymers is for example 1 to 12 and is preferably in the range of 2 to 10, in particular in the range of 2.5 to 8. In the case of using particles of polymers with a Content of more than 10 wt .-% of anionic monomers, the pH of the aqueous dispersions is from 1 to 7.5, preferably from 2 to 5.5, in particular from 2.5 to 5.

The hydrophobic polymers to be used according to the invention are insoluble in water at the pH of the application. They are present therein in the form of particles having an average particle size of 10 nm to 100 .mu.m, preferably 25 nm to 20 .mu.m, more preferably 40 nm to 2 microns and especially 60 to 800 nm and can be obtained from the aqueous dispersions as a powder. The mean particle size of the hydrophobic polymers may be e.g. be determined under the electron microscope or by means of light scattering experiments.

In a preferred embodiment, the particles of the hydrophobic polymers to be used according to the invention exhibit a pH-dependent solubility and swelling behavior. At pH values below 6.5, especially below 5.5 and in particular below 5, the particles are water-insoluble and retain their particulate character during dispersion in concentrated and in dilute aqueous media. In contrast, carboxyl-containing hydrophobic polymer particles swell in water under neutral and alkaline conditions. This behavior of hydrophobic polymers having anionic groups is known from the literature, cf. M. Siddiq et al., In Colloid. Polym. Sci. 277, 1172-1178 (1999) on the behavior of particles report from methacrylic acid / ethyl acrylate copolymers in an aqueous medium.

Hydrophobic polymers for example, are obtainable by polymerization of monomers from the group of alkyl esters of monoethylenically unsaturated C ₃ -C ₅ -carboxylic acids and monohydric C ₁ -C ₂₂ alcohols, hydroxyalkyl esters of monoethylenically unsaturated C ₃ -C ₅ carboxylic acids and divalent C ₂ - C ₄ -alcohols, vinyl esters of saturated C ₁ -C ₁₈ -carboxylic acids, ethylene, propylene, isobutylene, C ₄ -C ₂₄ -α-olefins, butadiene, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, tetrafluoroethylene, vinylidene fluoride, fluoroethylene, Chlorotrifluoroethylene, hexafluoropropene, esters or amides of C ₃ -C ₅ monoethylenically unsaturated carboxylic acids with perfluoroalkyl-containing alcohols or amines, alkyl and vinyl esters of perfluoroalkyl-containing carboxylic acids or mixtures thereof. These may be homo- or copolymers.

Examples of hydrophobic copolymers are copolymers of ethyl acrylate and vinyl acetate, copolymers of butyl acrylate and styrene, copolymers of (meth) acrylic acid esters of perfluoroalkyl-substituted alcohols of the formula CF ₃ - (C ₂ F ₄ ) _n - (CH ₂ ) _m -OH or C ₂ F. ₅ - (C ₂ F ₄ ) _n - (CH ₂ ) _m -OH (n = 1-10, m = 0-10) with (meth) acrylic esters and / or (meth) acrylic acid, copolymers of ethylene and tetrafluoroethylene and copolymers from butyl acrylate and vinyl acetate. The copolymers mentioned may contain the monomers in copolymerized form in any ratio.

The anionic character of the polymers mentioned can be achieved, for example, by reacting the monomers on which the copolymers are present in the presence of small amounts of anionic monomers such as acrylic acid, methacrylic acid, styrenesulfonic acid, acrylamido-2-methylpropanesulfonic acid, vinylsulfonate and / or maleic acid and optionally Presence of emulsifiers and / or protective colloids copolymerized.

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

• (a) 40 bis 100 Gew.-%, vorzugsweise 50 bis 90 Gew.-%, besonders bevorzugt 60 bis 75 Gew.-%, mindestens eines wasserunlöslichen nichtionischen Monomeren,
• (b) 0 bis 60 Gew.-%, vorzugsweise 1 bis 55 Gew.-%, besonders bevorzugt 5 bis 50 Gew.-%, insbesondere 15 bis 40 Gew.-%, mindestens eines Carboxylgruppen enthaltenden Monomeren oder dessen Salze,
• (c) 0 bis 25 Gew.-%, vorzugsweise 0 bis 15 Gew.-%, eines Sulfonsäure- und/oder Phosphonsäuregruppen enthaltenden Monomeren oder dessen Salze,
• (d) 0 bis 55 Gew.-%, vorzugsweise 0 bis 40 Gew.-%, mindestens eines wasserlöslichen nichtionischen Monomeren und
• (e) 0 bis 10 Gew.-%, vorzugsweise 0 bis 5 Gew.-%, mindestens eines mehrfach ethylenisch ungesättigten Monomers

in einpolymerisierter Form.Hydrophobic polymers include, for example

• (a) from 40 to 100% by weight, preferably from 50 to 90% by weight, particularly preferably from 60 to 75% by weight, of at least one 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 at least one carboxyl-containing monomer or its salts,
• (c) 0 to 25% by weight, preferably 0 to 15% by weight, of a monomer containing sulfonic acid and / or phosphonic acid groups or its salts,
• (D) 0 to 55 wt .-%, preferably 0 to 40 wt .-%, of at least one water-soluble nonionic monomer and
• (E) 0 to 10 wt .-%, preferably 0 to 5 wt .-%, of at least one multi-ethylenically unsaturated monomer

in copolymerized form.

Polymers containing at least one anionic monomer (b) or (c) can be used without additional anionic emulsifiers or protective colloids. Polymers containing less than 0.5% of anionic monomers are most commonly used with at least one anionic emulsifier and / or protective colloid.

Preferably used monomers (a) 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, (meth) acrylic acid esters of perfluoroalkyl-substituted alcohols CF ₃ - (C ₂ F ₄ ) _n - (CH ₂ ) _m -OH or C ₂ F ₅ - (C ₂ F ₄ ) _n - (CH ₂ ) _m -OH (n = 2-8, m 1 or 2), vinyl acetate, vinyl propionate, Styrene, ethylene, propylene, butylene, isobutene, diisobutene and tetrafluoroethylene, particularly preferred monomers (a) are methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate and vinyl acetate.

Preferably used hydrophobic polymers contain less than 75 wt .-% of a nonionic water-insoluble monomer (a) in copolymerized form, whose homopolymers have a glass transition temperature Tg of more than 60 ° C.

Preferably used monomers (b) are acrylic acid, methacrylic acid, maleic acid or maleic monoesters of C ₁ -C ₈ -alcohols.

Examples of monomers of group (c) are acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid and the alkali metal and ammonium salts of these monomers.

Examples of suitable monomers (d) are acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinyl oxazolidone, methylpolyglycol acrylates, methylpolyglycol methacrylates and methylpolyglycol acrylamides. Preferably used monomers (d) are vinylpyrrolidone, acrylamide and N-vinylformamide.

Suitable multiply ethylenically unsaturated monomers (e) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups. Examples are butanediol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate and tripropylene glycol diacrylate.

Other suitable polyethylenically unsaturated monomers (e) are e.g. Allyl esters of unsaturated carboxylic acids, divinylbenzene, methylenebisacrylamide and divinylurea.

Such copolymers can be prepared by the known methods of solution, precipitation, suspension or emulsion polymerization of the monomers using free-radical polymerization initiators. Preferably, the particulate hydrophobic polymers are obtained by the process of emulsion polymerization in water. The polymers have, for example, molecular weights of from 1 000 to 2 million, preferably from 5 000 to 500 000, in most cases the molecular weights of the polymers are in the range from 10 000 to 150 000.

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

Apart from the stated polymerization processes, other processes for the preparation of the polymer particles to be used according to the invention are also suitable. For example, polymers can be precipitated by lowering the solubility of the polymers in the solvent. Such a method consists, for example, in dissolving a copolymer containing acidic groups in a suitable water-miscible solvent and metering it in an excess of water such that the pH of the original is at least 1 lower than the equivalent pH of the copolymer. Under Equivalent pH is the pH at which 50% of the acidic groups of the copolymer are neutralized. In this method, it may be necessary to add a dispersing aid, pH regulators and / or salts to obtain stable finely divided dispersions.

In order to modify finely divided hydrophobic polymers containing anionic groups to be used according to the invention, other polymers which partially or completely react or associate with them and precipitate out can additionally be added during the dispersion. Such polymers are, for example, polysaccharides, polyvinyl alcohols and polyacrylamides.

Particulate, hydrophobic polymers may also be prepared by the controlled emulsification of a melt of the hydrophobic polymers. For this purpose, e.g. the polymer or a mixture of the polymer with further additives melted and under the action of strong shear forces, e.g. in an Ultra-Turrax, metered into an excess of water such that the pH of the template is at least 1 lower than the equivalent pH of the polymer. It may be necessary, if necessary, to add emulsifying aids, pH regulators and / or salts in order to obtain stable finely divided dispersions. In this variant of the preparation of finely divided polymer dispersions it is also possible to use additional polymers such as polysaccharides, polyvinyl alcohols or polyacrylamides, in particular if the hydrophobic polymer contains anionic groups.

Another method for preparing finely divided hydrophobic polymers containing anionic groups, is that one adds aqueous, alkaline solutions of the polymers preferably under the action of strong shear forces with an acid.

Examples of anionic emulsifiers are anionic surfactants and soaps. As anionic surfactants, alkyl and alkenyl sulfates, sulfonates, phosphates and phosphonates, alkyl and alkenyl benzene sulfonates, alkyl ether sulfates and phosphates, saturated and unsaturated C ₁₀ -C ₂₅ carboxylic acids and their salts can be used.

In addition, nonionic and / or betaine emulsifiers can be used. A description of suitable emulsifiers can be found, for example, in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

Examples of anionic protective colloids are water-soluble anionic polymers. In this case, very different types of polymers can be used. Anionically substituted polysaccharides and / or water-soluble anionic copolymers of acrylic acid, methacrylic acid, maleic acid, maleic monoesters, vinylsulfonic acid, styrenesulfonic acid or acrylamidopropanesulfonic acid with other vinylic monomers are preferably used. Suitable anionically substituted polysaccharides are e.g. Carboxymethylcellulose, carboxymethyl starch, oxidized starch, oxidized cellulose and other oxidized polysaccharides and the corresponding derivatives of the partially degraded polysaccharides.

Suitable water-soluble anionic copolymers are, for example, copolymers of acrylic acid with vinyl acetate, acrylic acid with ethylene, acrylic acid with acrylamide, acrylamidopropanesulfonic acid with acrylamide or acrylic acid with styrene.

In addition, other nonionic and / or betaine protective colloids may be used. An overview of commonly used protective colloids can be found in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 411-420.

For the preparation of particulate, hydrophobic polymers are preferably used anionic polymeric protective colloids, which lead to primary particles with anionic groups on the particle surface.

The cationically modified, particulate, hydrophobic polymers to be used according to the invention are obtainable by coating the surface of the anionically dispersed, particulate, hydrophobic polymers with cationic polymers. As cationic polymers, it is possible to use all cationic synthetic polymers which are soluble or finely dispersible in aqueous solvents and which contain amino and / or ammonium groups. Examples of such cationic polymers are polymers comprising vinylamine units, polymers containing vinylimidazole units, imidazole and epichlorohydrin condensates, crosslinked polyamidoamines, crosslinked polyamidoamines grafted with ethyleneimine, polyethyleneimines, alkoxylated polyethylenimines, crosslinked polyethylenimines, amidated polyethylenimines, alkylated polyethylenimines, polyamines, Amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines, polydimethyldiallylammonium chlorides, basic (meth) acrylamide or ester units Polymers containing basic quaternary (meth) acrylamide or ester units polymers and / or lysine condensates.

aus, in der R¹ und R² gleich oder verschieden sein können und für Wasserstoff und C₁-C₆-Alkyl stehen. Geeignete Monomere sind beispielsweise N-Vinylformamid (R¹=R²=H in Formel I), N-Vinyl-N-methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid, N-Vinyl-N-methylpropionamid und N-Vinylpropionamid. Zur Herstellung der Polymerisate können die genannten Monomeren entweder allein, in Mischung untereinander oder zusammen mit anderen monoethylenisch ungesättigten Monomeren polymerisiert werden. Vorzugsweise geht man von Homo- oder Copolymerisaten des N-Vinylformamids aus. Vinylamineinheiten enthaltende Polymerisate sind beispielsweise aus US-A-4 421 602, EP-A-0 216 387 und EP-A-0 251 182 bekannt. Sie werden durch Hydrolyse von Polymerisaten, die die Monomeren der Formel I einpolymerisiert enthalten, mit Säuren, Basen oder Enzymen erhalten.For the preparation of polymers containing vinylamine units, the procedure is, for example, open-chain N-vinylcarboxamides of the formula

from, in which R ¹ and R ^{2 may be the} same or different and are hydrogen and C ₁ -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-methylacetamide, N-vinyl-N-ethylacetamide, N- Vinyl-N-methyl-propionamide and N-vinyl-propionamide. To prepare the polymers, the monomers mentioned can be polymerized either alone, in mixture with one another or together with other monoethylenically unsaturated monomers. Preferably starting from homopolymers or copolymers of N-vinylformamide. 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 copolymerized with acids, bases or enzymes.

Suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are all compounds which can be copolymerized therewith. Examples of these are vinyl esters of saturated carboxylic acids having 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 ethers, for example methyl or ethyl vinyl ether. Further suitable comonomers are ethylenically unsaturated C ₃ -C ₆ -carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinylacetic acid and their alkali metal and alkaline earth metal salts, esters, amides and nitriles of said carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate ,

Cationic polymers are also understood as meaning amphoteric polymers which have a net-cationic charge, ie the polymers contain both anionic and cationic monomers in copolymerized form, but the molar fraction of the .alpha Polymers contained cationic units greater than that of the anionic units.

Other suitable carboxylic acid esters are derived from glycols or polyalkylene glycols, wherein in each case only one OH group is esterified, e.g. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and acrylic monoesters of polyalkylene glycols of 500 to 10,000 molecular weight. Further suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols such as dimethylaminoethyl, dimethylaminoethyl, diethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, dimethylaminopropyl, diethylaminopropyl, dimethylaminobutyl and diethylaminobutyl 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 sulfonic acids or in quaternized form. Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.

Further suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids having alkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and tert-butylacrylamide; and basic (meth) acrylamides such as dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide.

Further suitable comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and also substituted N-vinylimidazoles, such as N-vinyl-2-methylimidazole, N-vinyl-4-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. N-vinylimidazoles and N-vinylimidazolines are also used, except in the form of the free bases, in neutralized or quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.

Also suitable are diallyldialkylammonium halides, such as diallyldimethylammonium chlorides.

Also suitable as comonomers are sulfo-containing monomers such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate, the content of the amphoteric copolymers of cationic units exceeding the content of anionic units, so that the polymers have a total cationic charge.

• 99,99 bis 1 mol-%, vorzugsweise 99,9 bis 5 mol-%, N-Vinylcarbonsäureamide der Formel I und
• 0,01 bis 99 mol-%, vorzugsweise 0,1 bis 95 mol-%, andere damit copolymerisierbare monoethylenisch ungesättigte Monomere

in einpolymerisierter Form.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 copolymerized form.

• N-Vinylformamid mit
• Vinylformiat, Vinylacetat, Vinylpropionat, Acrylnitril, N-Vinylcaprolactam, N-Vinylharnstoff, Acrylsäure, N-Vinylpyrrolidon oder C₁-C₆-Alkylvinylethern

und anschließende Hydrolyse der Homo- oder der Copolymerisate unter Bildung von Vinylamineinheiten aus den einpolymerisierten N-Vinylformamideinheiten erhältlich sind, wobei der Hydrolysegrad z.B. 0,1 bis 100 mol-% beträgt.In order to prepare polymers containing vinylamine units, preference is given to homopolymers of N-vinylformamide or of copolymers obtained by copolymerizing

• N-vinylformamide with
• Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinylcaprolactam, N-vinyl urea, acrylic acid, N-vinylpyrrolidone or C ₁ -C ₆ alkyl vinyl ethers

and subsequent hydrolysis of the homopolymers or the copolymers with the formation of vinylamine units from the polymerized N-vinylformamide units are obtainable, wherein the degree of hydrolysis is, for example, 0.1 to 100 mol%.

wobei R² die dafür in Formel I angegebene Bedeutung hat, Polymerisate, die Vinylamineinheiten der Formel

enthalten, in der R¹ die in Formel I angegebene Bedeutung hat. Bei Verwendung von Säuren als Hydrolysemittel liegen die Einheiten III als Ammoniumsalz vor.The hydrolysis of the above-described polymers is carried out by known methods by the action of acids, bases or enzymes. This is formed from the copolymerized monomers of formula I above by cleavage of the moiety

wherein R ^{2 has} the meaning given in formula I, polymers, the vinylamine units of the formula

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

The homopolymers of the N-vinylcarboxamides of the formula I and their copolymers can be hydrolyzed to from 0.1 to 100, preferably from 70 to 100, mol%. In most cases, the degree of hydrolysis of the homopolymers and copolymers is 5 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the content of the polymers of vinylamine units. For copolymers containing vinyl esters in copolymerized form, in addition to the hydrolysis of the N-vinylformamide units, hydrolysis of the ester groups to form vinyl alcohol units may occur. This is especially the case when carrying out the hydrolysis of the copolymers in the presence of sodium hydroxide solution. Polymerized acrylonitrile is also chemically altered upon hydrolysis. This produces, for example, amide groups or carboxyl groups. The homo- and copolymers containing vinylamine moieties may optionally contain up to 20 mole% of amidine units, e.g. by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with an adjacent amide group, e.g. arise from copolymerized N-vinylformamide. The molecular weights of the polymers containing vinylamine units are e.g. 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% strength 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 comprising vinylamine units can be prepared, for example, from the above-described salt-containing polymer solutions by means of ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons. Also, the aqueous solutions of amino and / or ammonium groups described below containing other polymers can be obtained by means of ultrafiltration in salt-free form.

Polyethyleneimines are prepared, for example, by polymerization of 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. Particular preference is given to using polyethyleneimines having molecular weights of from 500 to 100,000. Also suitable are water-soluble crosslinked polyethyleneimines obtainable by reaction of polyethyleneimines with crosslinkers such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having from 2 to 100 ethylene oxide and / or propylene oxide units. Also suitable are amidic polyethyleneimines obtainable, for example, by amidation of polyethylenimines with C ₁ -C ₂₂ -monocarboxylic acids. Other suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. In the alkoxylation used, for example, per NH unit in polyethyleneimine 1 to 5 ethylene oxide or propylene oxide.

Suitable amino- and / or ammonium-containing polymers are also polyamidoamines, which are obtainable, for example, by condensing dicarboxylic acids with polyamines. Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids having 4 to 10 carbon atoms with polyalkylenepolyamines which contain 3 to 10 basic nitrogen atoms in the molecule. Examples of suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. In the preparation of the polyamidoamines it is also possible to use mixtures of dicarboxylic acids, as well as mixtures of several polyalkylenepolyamines. Suitable polyalkylenepolyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine. The dicarboxylic acids and polyalkylenepolyamines are heated to higher temperatures, for example to temperatures in the range from 120 to 220, preferably 130 to 180 ° C., in order to prepare the polyamidoamines. The water produced during the condensation is removed from the system. If appropriate, it is also possible to use lactones or lactams of carboxylic acids having 4 to 8 C atoms in the condensation. For example, from 0.8 to 1.4 mol of a polyalkylenepolyamine is used per mole of a dicarboxylic acid.

Other polymers containing amino groups are polyamidoamines grafted with ethyleneimine. They are obtainable 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 ° C. Compounds of this type are described for example in DE-B-24 34 816.

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

Further suitable cationic polymers are copolymers of, for example, 1 to 99 mol%, preferably 30 to 70 mol%, acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol%, of cationic monomers, such as dialkylaminoalkylacrylamide, acrylic esters and / or methacrylamide and / or methacrylic esters. The basic acrylamides and methacrylamides are also preferably present in acids neutralized or quaternized form. Examples include N-called Trimethylammoniumethylacrylamidchlorid, N-Trimethylammoniumethylmethacrylamidchlorid, N-Trimethylammoniumethylmethacrylesterchlorid, N-Trimethylammoniumethylacrylesterchlorid, Trimethylammoniumethylacrylamidmethosulfat, Trimethylammoniumethylmethacrylamidmethosulfat, N-Ethyldimethylammoniumethylacrylamidethosulfat, N-Ethyldimethylammoniumethylmethacrylamidethosulfat, Trimethylammoniumpropylacrylamidchlorid, Trimethylammoniumpropylmethacryl - amidchlorid, Trimethylammoniumpropylacrylamidmethosulfat, Trimethylammoniumpropylmethacrylamidmethosulfat and N-Ethyldimethylammoniumpropylacrylamidethosulfat. Preferred is trimethylammonium propylmethacrylamide chloride.

Further suitable cationic monomers for the preparation of (meth) acrylamide polymers are diallyldimethylammonium halides and basic (meth) acrylates. Suitable examples are copolymers of 1 to 99 mol%, preferably 30 to 70 mol%, acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol%, Dialkylaminoalkylacrylaten and / or methacrylates such as copolymers Acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and dimethylaminopropyl acrylate. Basic acrylates or methacrylates are preferably present in acids neutralized or quaternized form. The quaternization can be carried out, for example, with methyl chloride or with dimethyl sulfate.

Suitable cationic polymers which have amino and / or ammonium groups are also polyallylamines. Polymers of this type are obtained by homopolymerization of allylamine, preferably in acids 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 of 8 to 300, preferably 100 to 180 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. 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.

• Copolymere aus 50 mol-% Vinylpyrrolidon und 50 mol-% Trimethylammoniumethylmethacrylat-Methosulfat, M_w 1000 bis 500 000,
• Copolymere aus 30 mol-% Acrylamid und 70 mol-% Trimethylammoniumethylmethacrylat-Methosulfat, M_w 1000 bis 1 000 000,
• Copolymere aus 70 mol-% Acrylamid und 30 mol-% Dimethylaminoethylmethacrylamid, M_w 1000 bis 1 000 000,
• Copolymere aus 50 mol-% Hydroxyethylmethacrylat und 50 mol-% 2-Dimethylaminoethylmethacrylamid, M_w 1000 bis 500 000.

Examples of cationic polymers which may be considered are polydimethyldiallylammonium chloride, polyethylenimine, polymers containing vinylamine units, copolymers containing acrylamide or methacrylamide in copolymerized form in basic monomers, polymers containing lysine units or mixtures thereof. Examples of cationic polymers are:

• Copolymers of 50 mol% of vinylpyrrolidone and 50 mol% of trimethylammoniumethyl methacrylate methosulfate, M _w 1000 to 500 000,
• Copolymers of 30 mol% of acrylamide and 70 mol% of trimethylammoniumethyl methacrylate methosulfate, M _w 1000 to 1 000 000,
• Copolymers of 70 mol% acrylamide and 30 mol% dimethylaminoethyl methacrylamide, M _w 1000 to 1 000 000,
• Copolymers of 50 mol% of hydroxyethyl methacrylate and 50 mol% of 2-dimethylaminoethylmethacrylamide, M _w 1000 to 500,000.

Furthermore, it is also possible, to a minor extent (<10 wt .-%) to copolymerize anionic comonomers, for example acrylic acid, methacrylic acid, vinyl sulfonic acid or alkali metal salts of said acids.

Copolymer of 70 mol% hydroxyethyl methacrylate and 30 mol% 2-dimethylaminoethyl methacrylamide; Copolymer of 30 mol% vinylimidazole methochloride, 50% dimethylaminoethyl acrylate, 15 mol% acrylamide, 5 mol% acrylic acid,
Polylysines having M _w from 250 to 250,000, preferably 500 to 100,000, and lysine cocondensates having molecular weights M _w of 250 to 250,000, wherein as co-condensable component, for example amines, polyamines, ketene dimers, lactams, alcohols, alkoxylated amines, alkoxylated alcohols and / or nonproteinogenic amino acids,
Vinylamine homopolymers, 1 to 99 mol% of hydrolyzed polyvinylformamides, copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or acrylamide with molar masses of 3,000 to 500,000,
Vinylimidazole homopolymers, vinylimidazole copolymers with vinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate with molecular weights of 5,000 to 500,000 and their quaternary derivatives,
Polyethyleneimines, cross-linked polyethyleneimines or amidated polyethyleneimines having molecular weights of 500 to 3,000,000,
Amine-epichlorohydrin polycondensates containing as the amine component imidazole, piperazine, C ₁ -C ₈ -alkylamines, C ₁ -C ₈ -dialkylamines and / or dimethylaminopropylamine and having a molecular weight of 500 to 250,000,
polymers containing basic (meth) acrylamide or ester units, basic polymers containing quaternary (meth) acrylamide or ester units with molecular weights of from 10,000 to 2,000,000.

In order to cationically modify anionically dispersed, particulate, hydrophobic polymers, they may additionally be treated with polyvalent metal ions and / or cationic surfactants in addition to a treatment with cationic polymers. An occupancy of the particles with polyvalent metal ions is achieved by adding, for example, to an aqueous dispersion of anionically dispersed hydrophobic polymers an aqueous solution of at least one water-soluble polyvalent metal salt or dissolving a water-soluble polyvalent metal salt therein, wherein the modification of the anionically dispersed hydrophobic 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, are in principle usable, but 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, ferrous sulfate, ferric chloride, chromium (III) sulfate, copper sulfate, nickel sulfate , Cobalt sulfate and manganese sulfate. Preferably, the water-soluble salts of Ca, Mg, Al and Zn are used for cationization.

The transhipment of the anionically dispersed hydrophobic polymers also succeeds with cationic polymers and cationic surfactants. Potentially suitable for this purpose are cationic surfactants of very different structure. An overview of a selection of suitable cationic surfactants can be found in Ullmann's Enzyklpädie der Industrielle Chemie, Sixth Edition, 1999, Electronic Release, chapter "Surfactants", Chapter 8, Cationic Surfactants.

wobei
R¹ = C₁-C₂₅-Alkyl oder C₂-C₂₅-Alkenyl,
R² = C₁-C₄-Alkyl oder Hydroxyalkyl und
R³ = C₁-C₄-Alkyl, Hydroxyalkyl oder ein Rest R¹-CO-X-(CH₂)_n- mit
X = O oder NH und n=2 oder 3 und
wobei mindestens ein Rest R¹ = C₇-C₂₂-Alkyl oder C₇-C₂₂-Alkenyl ist.Particularly suitable cationic surfactants are, for example
C ₇ -C ₂₅ -alkylamines,
C ₇ -C ₂₅ -N, N-dimethyl-N- (hydroxyalkyl) ammonium salts,
mono- and di- (C ₇ -C ₂₅ ) -alkyldimethylammonium compounds quaternized with alkylating agents,
Esterquats such as quaternary esterified mono-, di- or trialkanolamines esterified with C ₈ -C ₂₂ -carboxylic acids,
Imidazolinquats such as 1-alkyl-imidazolinium salts of the general formulas IV or V

in which
R ¹ = C ₁ -C ₂₅ -alkyl or C ₂ -C ₂₅ -alkenyl,
R ² = C ₁ -C ₄ alkyl or hydroxyalkyl and
R ³ = C ₁ -C ₄ alkyl, hydroxyalkyl or a radical R ¹ -CO-X- (CH ₂ ) _n - with
X = O or NH and n = 2 or 3 and
wherein at least one radical R ¹ = C ₇ -C ₂₂ alkyl or C ₇ -C ₂₂ alkenyl.

In many commercial and domestic applications, modifying the properties of textiles with dispersions is important. It is not always possible to modify the surfaces by impregnating, spraying and brushing with concentrated dispersions. It is often desirable to carry out the modification by means of rinsing the textile material to be treated with a highly diluted liquor containing an active substance or by spraying a highly diluted aqueous formulation. It is often desirable to modify the surface of textiles in the context of a laundry, cleaning
and / or care or impregnation of the surface to combine. Of the textiles in particular cotton fabric and cotton blends come into consideration. In addition, carpets and furniture covers can be treated according to the invention.

The modification of the surfaces of textile materials may consist, for example, in a hydrophobing, soil release equipment, dirt-repellent finish, reinforcement of the fiber composite and protection against chemical or mechanical influences or damage.

The cationically modified, particulate, hydrophobic polymers are used to modify surfaces of the above-exemplified materials, as an additive to fabric rinse or conditioners, and as laundry detergents. They can be used, for example, as the sole active component in aqueous rinse and care products and, depending on the composition of the polymer, for example, facilitate soil removal in a subsequent wash, lower soil adhesion during use of the textiles, improve the structure retention of fibers, improve the Preservation of texture and structure of fabrics, a hydrophobing of the surface of the laundry and a handle improvement. The concentration of the cationically modified, particulate, hydrophobic polymers when used in the rinsing or care bath, in the detergent liquor or in the cleaning bath is, for example, 0.0002 to 1.0% by weight, preferably 0.0005 to 0.25% by weight. %, more preferably 0.002 to 0.05 wt .-%.

The treatment of laundry or textile surfaces is carried out with aqueous liquors, 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 and optionally additionally up to 10 mmol / l, preferably up to 5 mmol / l, particularly preferably up to 3.5 mol / l, water-soluble salts of polyvalent metals, in particular salts of Ca, Mg or Zn and / or up to 2 mmol / l, preferably up to 0.75 mmol / l, water-soluble Al salts and / or up to 600 ppm, preferably up to 300 ppm, cationic surfactants.

Agents for the treatment of laundry and textile surfaces may be liquid, gel or solid.

• (a) 0,05 bis 40 Gew.-% kationisch modifizierte, teilchenförmige, hydrophobe Polymere, deren Oberfläche durch Belegung mit kationischen Polymeren kationisch modifiziert ist und deren Teilchengröße 10 nm bis 100 µm beträgt,
• (b) 0,01 bis 10 Gew.-% mindestens eines kationischen Polymers und
• (c) 0 bis 80 Gew.-% mindestens eines üblichen Zusatzstoffs wie Säuren oder Basen, anorganische Builder, organische Cobuilder, weitere Tenside, polymere Farbübertragungsinhibitoren, polymere Vergrauungsinhibitoren, Soil Release Polymere, Enzyme, Komplexbildner, Korrosionsinhibitoren, Wachse, Silikonöle, Lichtschutzmittel, Farbstoffe, Parfum, Lösemittel, Hydrotrope, Salze, Verdicker und/oder Alkanolamine.

The agents may, for example, have the following composition:

• (a) 0.05 to 40% by weight of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by coating with cationic polymers and whose particle size is 10 nm to 100 μm,
• (b) 0.01 to 10% by weight of at least one cationic polymer and
• (c) from 0 to 80% by weight of at least one customary additive such as acids or bases, inorganic builders, organic cobuilders, other surfactants, polymeric dye transfer inhibitors, polymeric grayness inhibitors, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, Dyes, perfume, solvents, hydrotropes, salts, thickeners and / or alkanolamines.

• (a) 0,1 bis 30 Gew.-% teilchenförmige, hydrophobe Polymere, die mindestens eine Gruppe von anionischen ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, eine Teilchengröße von 10 nm bis 100 µm haben und in Wasser dispergiert sind,
• (b) 0,05 bis 20 Gew.-% einer Säure wie Ameisensäure, Zitronensäure, Adipinsäure, Bernsteinsäure, Oxalsäure oder deren Mischungen,
• (c) 0,1 bis 10 Gew.-% mindestens eines kationischen Polymeren,
• (d) 0 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
• (e) 0 bis 10 Gew.-% mindestens eines anderen üblichen Inhaltsstoffs wie Parfum, weitere Tenside, Silikonöl, Lichtschutzmittel, Farbstoffe, Komplexbildner, Vergrauungsinhibitor, Soil-Release-Polyester, Farbübertragungsinhibitor, nicht-wäßriges Lösungsmittel, Hydrotrop, Verdicker und/oder Alkanolamin und
• (f) Wasser zur Ergänzung auf 100 Gew.-%.

For example, liquid or gel laundry and laundry care compositions include

• (a) from 0.1 to 30% by weight of particulate hydrophobic polymers which contain in copolymerized form at least one group of anionic ethylenically unsaturated monomers, have a particle size of 10 nm to 100 μm and are dispersed in water,
• (b) 0.05 to 20% by weight of an acid such as formic acid, citric acid, adipic acid, succinic acid, oxalic acid or mixtures thereof,
• (c) 0.1 to 10% by weight of at least one cationic polymer,
• (d) 0 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
• (e) 0 to 10% by weight of at least one other conventional ingredient such as perfume, other surfactants, silicone oil, light stabilizers, dyes, complexing agents, grayness inhibitor, soil release polyesters, Color transfer inhibitor, non-aqueous solvent, hydrotrope, thickener and / or alkanolamine and
• (f) water to supplement to 100 wt .-%.

The laundry aftertreatment and conditioning agents described above may also be formulated as solid compositions based on the same ingredients. Examples of possible solid forms are powders, granules and tablets.

For the preparation of solid compositions, it may be necessary to additionally add adjusters, spraying agents, agglomeration aids, coating aids or binders. To ensure the effect and good dissolution behavior, it may additionally be necessary to add dissolution-promoting components such as readily water-soluble salts, polymeric disintegrants or combinations of acids and bicarbonate.

In a preferred embodiment, laundry aftertreatment and laundry care compositions contain, as component (a), from 0.5 to 25% by weight of particulate, hydrophobic polymers which contain from 25 to 60% by weight of an ethylenically unsaturated monomer containing at least one carboxylic acid group 10 nm to 100 microns and are dispersed with an anionic emulsifier and / or an anionic protective colloid in water.

The agents of this preferred embodiment are particularly suitable for achieving soil release promoting properties.
Soils that have been treated in this way will more easily remove soiling that occurs in the use phase during the subsequent wash cycle.

In a further preferred embodiment, laundry aftertreatment and laundry care compositions comprise, as component (a), from 0.5 to 25% by weight of particulate hydrophobic polymers containing from 0.1 to 10% by weight of an ethylenically unsaturated monomer containing at least one carboxylic acid group and at least 80 Wt .-% of a water-insoluble ethylenically unsaturated nonionic monomer in copolymerized form, have a particle size of 10 nm to 100 microns and are dispersed with an anionic emulsifier and / or an anionic protective colloid in water.

The agents of this preferred embodiment are particularly suitable for achieving hydrophobicizing or impregnating properties. From so aftertreated laundry water is absorbed or transmitted to a much lesser extent.

In a further preferred embodiment, laundry aftertreatment and laundry care compositions contain, as component (a), from 0.5 to 25% by weight of particulate, hydrophobic polymers which contain from 10 to 100% by weight of an ethylenically unsaturated monomer containing fluorine substituents, a particle size of 10 nm to 100 microns and are dispersed in water with an anionic emulsifier and / or an anionic protective colloid.

The agents of this preferred embodiment are particularly suitable for achieving dirt-repellent, in particular oil and grease soil repellent properties. So aftertreated tissue absorbs oil and grease dirt to a lesser extent.

Suitable acids are both mineral acids such as sulfuric acid or phosphoric acid or organic acids such as carboxylic acids or sulfonic acids. Strong acids such as sulfuric acid, phosphoric acid, or sulfonic acids are usually used in partially neutralized form.

The cationic modification of the particulate, hydrophobic polymers is preferably carried out before use in the aqueous treatment agents, but it can also in the preparation of aqueous treatment agents or the application of anionically emulsified, particulate, hydrophobic polymers having a particle size of 10 nm to 100 microns done by eg aqueous dispersions of the contemplated particulate hydrophobic polymers with the other constituents of the respective treatment agent in the presence of cationic polymers and optionally water-soluble salts of polyvalent metals and / or cationic surfactants.

In a particular embodiment, it is also possible to add the anionic particles or formulations containing these particles directly to the rinsing, washing or cleaning liquor, if it is ensured that sufficient quantities of cationic polymers and optionally polyvalent metal ions and / or cationic surfactants in dissolved form are present in the liquor available. For example, it is possible to use the anionic hydrophobic particles or formulations containing them in liquors containing from 2.5 to 300 ppm of cationic polymers and optionally in water-soluble salts of Ca, Mg or Zn of more than 0.5 mmol / l, preferably above 1 mmol / l, more preferably above 2 mmol / l. If cationic surfactants are used, they are used, for example, in concentrations of 50 to 100 ppm, preferably 75 to 500 ppm and in particular from 100 to 300 ppm in the aqueous liquor.

The anionic particles or formulations containing these particles can also be added before, after or at the same time as a formulation containing cationic polymers and optionally cationic surfactants.

Examples of the composition of typical anionic dispersions, which can be processed by mixing with cationic polymers and optionally water-soluble salts of polyvalent metals and / or cationic surfactants and other components to rinse, care and detergents are described below dispersions I to V, whose dispersed particles are each to be observed in the electron microscopic examination as discrete particles having the specified average particle diameter:

Dispersion I

40 wt .-% aqueous dispersion of a polymer of 56 wt .-% ethyl acrylate, 33 wt .-% methacrylic acid and 11 wt .-% acrylic acid having an average particle diameter of 288 nm. The dispersion contained 1.25 wt .-% of a Anionic surfactant as an emulsifier and 20 wt .-% of a low molecular weight starch as a protective colloid. It had a pH of 4.

Dispersion II

30% strength by weight aqueous dispersion of a polymer of 66% by weight of ethyl acrylate, 4% by weight of methacrylic acid, 26% by weight of acrylic acid and 4% by weight of acrylamide. The average diameter of the dispersed particles of the dispersion was 176 nm. The dispersion contained 0.8% by weight of an anionic surfactant as an emulsifier and had a pH of 4.

Dispersion III

30 wt .-% aqueous dispersion of a polymer of 50 wt .-% ethyl acrylate and 50 wt .-% methacrylic acid having a mean diameter of the dispersed particles of 123 nm. The dispersion contained 0.8 wt .-% of an anionic surfactant as emulsifier and had a pH of 4.

Dispersion IV

35% by weight dispersion of a polymer of 64% by weight of n-butyl acrylate, 33% by weight of methyl methacrylate and 4% by weight of acrylic acid. The mean diameter of the dispersed particles of the dispersion was 80 nm. The dispersion contained 1.5% by weight of an anionic surfactant as an emulsifier and had a pH of 6.

Dispersion V Anionic fluoropolymer dispersion Nuva® FTA-4 (Clariant)

From the dispersions I to III typical formulations of the invention with soil release effect can be prepared, which are used, for example, in the household washing in the final rinse of the washing machine in a dosage of 0.5 to 5 g / l, preferably 1 to 3 g / l :

Formulation I

50 wt .-% of one of the dispersions I to III described above
1.5% by weight of formic acid
0.5% by weight of polyethyleneimine of molecular weight M _w 25,000
Water to supplement to 100 wt .-%.

Formulation II

50 wt .-% of one of the dispersions I to III described above
4.5% by weight of formic acid
5% by weight calcium chloride
1.0% by weight of polyethyleneimine of molecular weight M _w 5 000
Water to supplement to 100 wt .-%.

Formulation III

50 wt .-% of one of the dispersions I to III described above
2% by weight of 2N sulfuric acid
1.0% by weight crosslinked high molecular weight polyethyleneimine
2.0% by weight of polyvinylpyralidone of molecular weight M _w 50 000
Water to supplement to 100 wt .-%.

Formulation IV

50 wt .-% of one of the dispersions I to III described above
2% by weight of 2N sulfuric acid
0.5% by weight of polyethyleneimine of molecular weight M _w 25,000
5% by weight of an esterquat (methylquat of di-tallow fatty acid ester of triethanolamine)

Water to supplement to 100 wt .-%.

The formulations may optionally contain other ingredients such as common soil release polymers for polyesters, grayness inhibitors, perfume, dyes, enzymes, hydrotropes, solvents, nonionic surfactants, silicone oil, a fabric softener and / or a thickener.

Dispersions IV and V can be used to prepare typical formulations according to the invention having impregnating effects which are used, for example, in household washing in the rinse cycle of the washing machine in a dosage of 0.5 to 5 g / l, preferably 1 to 3 g / l.

Formulation V for water-repellent impregnation

50% by weight of dispersion IV described above
1 wt .-% polyethyleneimine in the molecular weight M _w 25 000
5 wt .-% polyvinylpyrrolidone of molecular weight M _w 50 000
Water to supplement to 100% by weight

Formulation VI for oil-repellent impregnation

50% by weight of dispersion V described above
0.2% by weight of polyethyleneimine of molecular weight M _w 25,000
5% by weight calcium acetate
Water to supplement to 100% by weight

The formulations may optionally contain other ingredients such as common soil release polymers for polyesters, grayness inhibitors, perfume, dyes, enzymes, hydrotropes, solvents, nonionic surfactants, silicone oil, a fabric softener and / or a thickener.

• Copolymerisate aus Butylacrylat und Styrol,
• Copolymerisate aus Butylacrylat und Vinylacetat und
• Tetrafluorethylen-Polymere.

Suitable hydrophobizing, soil-repellent or fiber-reinforcing additives for rinsing or care compositions and detergents are, for example, the following aqueous dispersions of copolymers whose dispersed particles have an average diameter of 10 nm to 100 μm and which are each dispersed with an anionic dispersant:

• Copolymers of butyl acrylate and styrene,
• Copolymers of butyl acrylate and vinyl acetate and
• Tetrafluoroethylene polymers.

The anionic character of the abovementioned dispersions can optionally additionally be adjusted by polymerizing the polymers in the presence of small amounts (up to 10% by weight) of anionic monomers such as acrylic acid, styrenesulfonic acid, vinylphosphonic acid or acrylamido-2-methylpropanesulfonic acid , These dispersions are preferably cationically modified by treatment with water-soluble cationic polymers, or the cationic modification of the dispersions is carried out during the preparation of the rinsing or care agents. The cationically modified, particulate, hydrophobic polymers to be used according to the invention which are thus obtainable have a hydrophobing, fiber-reinforcing and dirt-repellent action on the textiles treated with them in the rinse cycle of the household washing machine.

• (a) 0,05 bis 20 Gew.-% kationisch modifizierte, teilchenförmige, hydrophobe Polymere, deren Oberfläche durch Belegung mit kationischen Polymeren und gegebenenfalls zusätzlich mit mehrwertigen Metallionen und/oder kationischen Tensiden kationisch modifiziert ist und deren Teilchengröße 10 nm bis 100 µm beträgt,
• (b) 0,1 bis 40 Gew.-% mindestens eines nichtionischen, kationischen und/oder anionischen Tensids,
• (c) 0 bis 50 Gew.-% eines anorganischen Builders,
• (d) 0 bis 20 Gew.-% eines organischen Cobuilders und
• (e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe wie Stellmittel, Enzyme, Parfum, weitere Tenside, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Farbstoffe, Auflösungsverbesserer und/oder Sprengmittel

enthält, sowie eine flüssige oder gelförmige Waschmittelformulierung, die

• (a) 0,05 bis 20 Gew.-% kationisch modifizierte, teilchenförmige, hydrophobe Polymere, deren Oberfläche durch Belegung mit mindestens einem kationischen Polymer und gegebenenfalls zusätzlich mit mehrwertigen Metallionen und/oder kationischen Tenside kationisch modifiziert ist und deren Teilchengröße 10 nm bis 100 µm beträgt,
• (b) 0,1 bis 40 Gew.-% mindestens eines nichtionischen, kationischen und/oder anionischen Tensids,
• (c) 0 bis 20 Gew.-% eines anorganischen Builders,
• (d) 0 bis 10 Gew.-% eines organischen Cobuilders,
• (e) 0 bis 20 Gew.-% anderer üblicher Inhaltsstoffe wie Soda, Enzyme, Parfum, weitere Tenside, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Farbstoffe, nicht-wäßrige Lösemittel Hydrotrope, Verdicker und/oder Alkanolamine und
• (f) 0 bis 90 Gew.-% Wasser

enthält.The invention also provides a solid detergent formulation which

• (A) 0.05 to 20 wt .-% cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by occupancy with cationic polymers and optionally additionally with polyvalent metal ions and / or cationic surfactants and whose particle size is 10 nm to 100 microns .
• (b) 0.1 to 40% by weight of at least one nonionic, cationic and / or anionic surfactant,
• (c) 0 to 50% by weight of an inorganic builder,
• (d) 0 to 20% by weight of an organic cobuilder and
• (e) 0 to 60% by weight of other conventional ingredients such as sizing agents, enzymes, perfume, other surfactants, chelants, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibitors, grayness inhibitors, soil release polyesters, dyes, dissolution enhancers, and / or disintegrants

contains, as well as a liquid or gel detergent formulation, the

• (A) 0.05 to 20 wt .-% cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by occupancy with at least one cationic polymer and optionally additionally with polyvalent metal ions and / or cationic surfactants and whose particle size 10 nm to 100 μm,
• (b) 0.1 to 40% by weight of at least one nonionic, cationic and / or anionic surfactant,
• (c) 0 to 20% by weight of an inorganic builder,
• (d) 0 to 10% by weight of an organic cobuilder,
• (e) 0 to 20% by weight of other conventional ingredients such as soda, enzymes, perfume, other surfactants, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibitors, grayness inhibitors, soil release polyesters, dyes, non-aqueous solvents hydrotrope , Thickeners and / or alkanolamines and
• (f) 0 to 90% by weight of water

contains.

The surfactants, builders, co-builders, complexing agents, solvents, color transfer inhibitors, soil release polyesters, bleaches, bleach activators, grayness inhibitors, enzymes, perfumes, solvents, thickeners, oils, waxes, hydrotropes, foam inhibitors, silicones, brighteners and Dyes can be combined within the usual customary in rinsing, care, washing and cleaning formulations starting materials. For typical ingredients, see the chapter Detergents (Part 3, Detergent Ingredients, Part 4, Household Detergents and Part 5, Institutional Detergents) in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Version 2.0.

Preferred nonionic surfactants are, for example, alkoxylated C ₈ -C ₂₂ -alcohols, such as fatty alcohol ethoxylates and oxo alcohol alkoxylates alkoxylated with from 3 to 15 mol of ethylene oxide and optionally additionally with from 1 to 4 mol of propylene oxide and / or butylene oxide, and block polymers of ethylene oxide and propylene oxide with one molecular weight from 900 to 12,000 and a weight ratio of ethylene oxide to propylene oxide of 1 to 20.

Particularly preferred nonionic surfactants are C ₁₃ / C ₁₅ oxo alcohol ethoxylates and C ₁₂ / C ₁₄ fatty alcohol ethoxylates which are reacted with 3 to 11 moles of ethylene oxide per mole of alcohol or first with 3 to 10 moles of ethylene oxide and then with 1 to 3 moles of propylene oxide per mole of alcohol are alkoxylated.

Preferred anionic surfactants are, for example, alkylbenzenesulfonates having linear or branched C ₆ -C ₂₅ -alkyl groups, fatty alcohol and oxoalcohol sulfates having C ₈ -C ₂₂ -alkyl groups and fatty alcohol or oxoalcohol ether sulfates of C ₈ -C ₂₂ -alcohols containing from 1 to 5 mol Ethylene oxide per mole of alcohol are ethoxylated and sulfated at the OH end group of the ethoxylate.

Preferably, formulations according to the invention are formulated with low content of anionic surfactants, particularly preferably without anionic surfactants. When anionic surfactants are used in the formulations, ether sulfates are preferably used.

Preferred solvents are alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and butanediol.

Preferably, only small amounts, more preferably no solvents, are added to the formulations.

Preferred builders are alkali metal carbonates, phosphates, polyphosphates, zeolites and silicates. Particularly preferred builders are zeolite A, zeolite P, phyllosilicates, soda and trisodium polyphosphate.

Preferred complexing agents are nitrilotriacetic acid, methylglycinediacetic acid and ethylenediaminetetraacetate.

Preferred co-builders are acrylic acid homopolymers, acrylic acid / maleic acid copolymers, polyaspartic acid and citric acid. Particularly preferred cobuilders are acrylic acid homopolymers of molecular weight 1,500 to 30,000 and acrylic acid / maleic acid copolymers having a molar ratio of the monomers of 10: 1 to 1: 2 and molecular weights of 4,000 to 100,000.

Preferred soil-release polyesters are polyesters of terephthalic acid, ethylene glycol and polyethylene glycol, wherein polyethylene glycols having molecular weights of from 1 000 to 5 000 are condensed in, and those in which terephthalic acid is replaced by up to 50 mol% by sulfocarboxylic acids or sulfodicarboxylic acids.

Preferred dye transfer inhibitors are polyvinylpyrrolidone of molecular weights 8,000 to 70,000, vinylimidazole / vinylpyrrolidone copolymers having a molar ratio of the monomers of 1:10 to 2: 1 and molecular weights of 8,000 to 70,000 and poly-4-vinylpyridine N-oxides having molecular weights from 8,000 to 70,000.

Preferred enzymes are proteases, lipases, cellulases and amylases.

Formulations according to the invention may optionally additionally contain further protective colloids for stabilizing the disperse state. This is especially true for liquid formulations of of particular importance to prevent coagulation. However, the protective colloids can also advantageously be added to solid formulations in order to prevent coagulation during use.

As protective colloids it is possible to use water-soluble polymers, in particular water-soluble nonionic polymers. Preferably, suitable protective colloids have molecular weights of from 8,000 to 200,000, more preferably from 5,000 to 75,000, especially from 10,000 to 50,000.

Suitable protective colloids are e.g. Polyvinylpyrrolidone, polyethylene glycol, block polymers of ethylene oxide and propylene oxide, enzymatically degraded starches, and polyacrylamides.

With the cationically modified dispersions to be used according to the invention, a much higher soil release effect is achieved, in particular on cotton and cellulose fibers, than with known water-soluble soil release polymers.

The percentages in the examples are by weight.

Examples

For the examples and comparative examples, the dispersion I was used.

Dispersion I

40 wt .-% aqueous dispersion of a polymer of 56 wt .-% ethyl acrylate, 33 wt .-% methacrylic acid and 11 wt .-% acrylic acid having an average particle diameter of 288 nm. The dispersion contained 1.25 wt .-% of a Anionic surfactant as an emulsifier and 20 wt .-% of a low molecular weight starch as a protective colloid. It had a pH of 4.

Comparative Example 1

The anionic dispersion I was brought to a content of 0.040% with deionized water of pH 4. A white cotton fabric was hung in the magnetically stirred liquor for 30 minutes. The extinction of the liquor was measured by means of a Vis spectrometer at 520 nm. Within 30 minutes, no change in absorbance was observed. Electron micrographs showed almost no coverage of the cotton fibers with dispersion particles.

example 1

Dispersion I was made with deionized water of pH 4 to a content of particles of 10 wt .-%. This dispersion was metered in with stirring by means of a magnetic stirrer to the same volume of a 1% strength solution of high molecular weight crosslinked polyethyleneimine (molecular weight 2,000,000) adjusted to pH 4 over a period of 30 minutes. The dispersion was stable for hours.

This dispersion was diluted with deionized water of pH 4 to a level of 0.040%. A white cotton fabric was hung in the magnetically stirred liquor for a period of 30 minutes. Over 30 minutes, the extinction of the liquor was measured by means of a Vis spectrometer at 520 nm. A large decrease in absorbance was observed.

Example 2

Example 1 was repeated with the exception that the cationic polymer used was a copolymer of vinylimidazole and vinylpyrrolidone (monomer ratio 1: 1) of molecular weight 10,000 for coating the dispersion particles.

Example 3

Example 1 was repeated with the exception that the cationic polymer used was a polycondensate of imidazole and epichlorohydrin (molar ratio of the components 1: 1) of molar mass 12,000 for coating the dispersion particles. Table 1: Extinction of the dispersions measured at 520 nm in a 1 cm cuvette. The values reflect the extinction of the diluted dispersion before dipping the cotton fabric and after 30 minutes. measuring time Comparative Example 1 example 1 Example 2 Example 3 t = 0 min 1.0 0.99 0.99 1.00 t = 30 min 1.0 0.65 0.77 0.69

The comparison of Examples 1 to 3 with Comparative Example 1 shows that significantly higher levels of hydrophobic particles are adsorbed onto the surface of the cotton fabric when the particles are coated with the cationic polymers than in the absence of the cationic polymers. This finding is confirmed by electron micrographs.

Examples 4 to 6 and Comparative Examples 2 to 4

To test the soil release properties of Nachspülformulierungen with particles of the invention the following washing tests were carried out:

Cotton fabric was prewashed with Dispersion I. In Comparative Experiment 3, the dispersion was used in the absence of cationic polymer. In Examples 4 to 6, the dispersion particles were initially coated with 10% by weight of the cationic polymers as described in Examples 1 to 3. The prewashed fabrics were soiled with lipstick and then washed with a heavy duty detergent (Ariel Futur). To evaluate the soil release effect, the remission of the soiled fabrics before and after the wash was measured and the soil release in% oil release was determined in a known manner together with the remission value of the white cotton fabric.

wash conditions: Prewash:

• Washing device: Launder-O-meter
• Pre-wash temperature: 20 ° C
• Prewash time: 15 min

Main wash:

• Washing temperature: 40 ° C
• Wash time: 30 min
• Water hardness: 3 mmol / l
• Ca / Mg ratio: 3: 1

Table 2: Wash results Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 4 Example 5 Example 6 Concentration of particles from dispersion I in the prewash 0 400 mg / l 0 400 mg / l 400 mg / l 400 mg / l Cationic polymer no no PEI PEI PVI / VP Imidazole / epi Dirt-removing effect in subsequent wash in% Soil-Release 32 33 30 52 49 50

• PEI: Polyethylenimin
• PVI/VP: Copolymerisat aus Vinylimidazol und N-Vinylpyrrolidon
• Imidazol/Epi: Kondensat aus Imidazol und Epichlorhydrin

The abbreviations in the table have the following meaning:

• PEI: polyethyleneimine
• PVI / VP: Copolymer of vinylimidazole and N-vinylpyrrolidone
• Imidazole / Epi: condensate of imidazole and epichlorohydrin

The results of the washing experiments show that neither the anionic polymer dispersion alone nor the cationic polymer alone has a soil release effect on the soil. By contrast, the anionic polymer dispersions coated with cationic polymers according to the invention show a marked improvement in the soil release of cotton.

Example 7

The dispersion IV was brought with deionized water of pH 6 to a content of 0.4% by weight of particles. This dispersion was added with stirring in 30 min to the same volume of a adjusted to pH 6 0.02 wt .-% solution of polyethyleneimine in the molecular weight M _w 25 000 metered. A stable dispersion was obtained.

Example 8

To test the water-repellent properties of cotton fabrics obtained with rinse-in formulations according to the invention, washing tests were carried out in Launder-O-meter. Cotton fabric was washed with commercial detergent and rinsed in the final rinse with the cationically modified dispersion of Example 7. In comparative experiment 5, no dispersion was added in the final rinse bath. In Comparative Experiment 6, the non-cationic modified dispersion IV was added. The rinsed fabrics were spun, dried and ironed. To test the water repellency, the fabrics were laid flat over the opening of a 5 cm diameter beaker. Then a drop of water was applied centrally. The time was determined until the drop had completely penetrated the tissue.

Washing conditions: Main wash:

• Detergent: Ariel Futur
• Detergent dosage: 3.5 g / l
• Wash time: 30 min
• Washing temperature: 40 ° C
• Water hardness: 3 mmol / l
• Ca / Mg ratio: 3: 1

rinsing:

• Rinsing temperature: 20 ° C
• Rinsing time: 15 min
• pH value: 6
• Fleet ratio: 12.5

Table 3: Wash results Comparative Example 5 Comparative Example 5 Example 8 Dosing of the dispersion from Example 7 in the final rinse - - 400 ppm Dosing of the dispersion IV in the final rinse - 400 ppm - Penetration time for the water drop 3 sec 12 sec 350 sec

Claims (17)

1. The use of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with cationic polymers, and the particle size of which is 10 nm to 100 µm, as additive to rinse or care compositions for textiles and as additive to detergents.
2. The use according to claim 1, wherein the cationically modified, particulate, hydrophobic polymers are obtainable by treatment of aqueous dispersions of particulate, hydrophobic polymers having a particle size of from 10 nm to 100 µm with an aqueous solution or dispersion of cationic polymers.
3. The use according to claim 1 or 2, wherein the dispersions of the particulate, hydrophobic polymers have been stabilized using an anionic emulsifier and/or anionic protective colloid.
4. The use according to any of claims 1 to 3, wherein the hydrophobic polymers comprise at least one anionic monomer in copolymerized form.
5. The use according to any of claims 1 to 4, wherein the cationically modified dispersions of particulate, hydrophobic polymers have, in 0.1% strength by weight aqueous dispersion, an interface potential of from -5 to +50 mV.
6. The use according to any of claims 1 to 5, wherein the pH of the aqueous dispersions of the cationically modified, particulate, hydrophobic polymers is 2 to 12.
7. The use according to any of claims 1 to 6, wherein the concentration of the cationically modified, particulate, hydrophobic polymers, in the case of use in a rinse or care bath or in the detergent liquor, is 0.0002 to 1.0% by weight.
8. The use according to any of claims 1 to 7, wherein the concentration of the cationically modified, particulate, hydrophobic polymers, in the case of use in a rinse or care bath or in the detergent liquor, is 0.002 to 0.05% by weight.
9. The use according to any of claims 1 to 8, wherein the cationic polymers used are polymers comprising vinylamine units, polymers comprising vinylimidazole units, polymers comprising quaternary vinylimidazole units, condensates of imidazole and epichlorohydrin, crosslinked polyamido amines, crosslinked polyamidoamines grafted with ethylenimine, polyethylenimines, alkoxylated polyethylenimines, crosslinked polyethylenimines, amidated polyethylenimines, alkylated polyethylenimines, polyamines, amine/epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines, polydimethyldiallylammonium chlorides, polymers comprising basic (meth)acrylamide or (meth)acrylic esters, polymers comprising basic quaternary (meth)acrylamide or (meth)acrylic ester units, and/or lysine condensates.
10. The use according to any of claims 1 to 9, wherein the cationically modified, particulate, hydrophobic polymers have additionally been cationically modified by coating with polyvalent metal ions and/or cationic surfactants.
11. A composition for the treatment of laundry and textile surfaces, which comprises

    (a) 0.05 to 40% by weight of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with cationic polymers, and the particle size of which is 10 nm to 100 µm,

    (b) 0.01 to 10% by weight of at least one cationic polymer, and

    (c) 0 to 80% by weight of at least one customary additive, such as acids or bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric antiredeposition agents, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, light protection agents, dyes, perfume, solvents, hydrotropic agents, salts, thickeners and/or alkanolamines.
12. A laundry aftertreatment and laundry care composition in liquid or gel form, which comprises

    (a) 0.1 to 30% by weight of particulate, hydrophobic polymers which comprise at least one group of anionic ethylenically unsaturated monomers in copolymerized form, have a particle size of from 10 nm to 100 µm and have been dispersed in water,

    (b) 0.05 to 20% by weight of an acid,

    (c) 0.1 to 10% by weight of at least one cationic polymer,

    (d) 0 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or A1 and/or of a cationic surfactant,

    (e) 0 to 10% by weight of at least one other customary ingredient, such as perfume, other surfactants, silicone oil, light protection agent, dyes, complexing agent, antiredeposition agent, soil release polyester, color transfer inhibitor, nonaqueous solvent, hydrotropic agent, thickener and/or alkanolamine and

    (f) water to make up to 100% by weight.
13. The laundry aftertreatment and laundry care composition according to claim 12, which comprises, as component (a), 0.5 to 25% by weight of particulate, hydrophobic polymers which comprise, in copolymerized form, 25 to 60% by weight of an ethylenically unsaturated monomer which comprises at least one carboxylic acid group, have a particle size of from 10 nm to 100 µm and have been dispersed using an anionic emulsifier and/or an anionic protective colloid in water.
14. The laundry aftertreatment and laundry care composition according to claim 12, which comprises, as component (a), 0.5 to 25% by weight of particulate, hydrophobic polymers which comprise, in copolymerized form, 0.1 to 10% by weight of an ethylenically unsaturated monomer which comprises at least one carboxylic acid group and at least 80% by weight of a water-insoluble ethylenically unsaturated nonionic monomer, have a particle size of from 10 nm to 100 µm and have been dispersed using an anionic emulsifier and/or an anionic protective colloid in water.
15. The laundry aftertreatment and laundry care composition according to claim 12, which comprises, as component (a), 0.5 to 25% by weight of particulate, hydrophobic polymers which comprise, in copolymerized form, 10 to 100% by weight of an ethylenically unsaturated monomer comprising fluorine substituents, have a particle size of from 10 nm to 100 µm and have been dispersed using an anionic emulsifier and/or an anionic protective colloid in water.
16. A solid detergent formulation which comprises

    (a) 0.05 to 20% by weight of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with cationic polymers and optionally additionally with polyvalent metal ions and/or cationic surfactants, and the particle size of which is 10 nm to 100 µm,

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

    (c) 0 to 50% by weight of an inorganic builder,

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

    (e) 0 to 60% by weight of other customary ingredients, such as extenders, enzymes, perfume, other surfactants, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, color transfer inhibitors, antiredeposition agents, soil release polyesters, dyes, dissolution improvers and/or disintegrants.
17. A detergent formulation in liquid or gel form which comprises

    (a) 0.05 to 20% by weight of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with at least one cationic polymer and optionally additionally with polyvalent metal ions and/or cationic surfactants, and the particle size of which is 10 nm to 100 µm,

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

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

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

    (e) 0 to 10% by weight of other customary ingredients, such as soda, enzymes, perfume, other surfactants, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, color transfer inhibitors, antiredeposition agents, soil release polyesters, dyes, nonaqueous solvents, hydrotropic agents, thickeners and/or alkanolamines and

    (f) 0 to 90% by weight of water.