EP1287102B1 - Use of cationically modified, particle-shaped, hydrophobic polymers as addition agents in rinsing, care, detergent and cleaning products - Google Patents

Abstract

Use of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with polyvalent metal ions and/or cationic surfactants, the particle size of which is 10 nm to 100 mum, as additive to rinse compositions, care compositions, detergents and cleaners, and also rinse compositions, care compositions, detergents and cleaners which comprise the cationically modified, particulate, hydrophobic polymers.

Description

The invention relates to the use of cationically modified, particulate, hydrophobic polymers as an additive to rinsing, care, washing and cleaning agents and rinsing, care, washing and cleaning agents 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 means of doctoring, 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.

From US Pat. No. 4,746,455 it is known to add polymer latices with cationic or tertiary amino groups to detergents in order to prevent the shrinkage of felting materials.

The present invention has for its object to provide a further method for modifying surfaces available.

The object is achieved according to the invention with the use of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by coating with polyvalent metal ions and / or cationic surfactants and whose particle size is 10 nm to 100 μm, as an additive to rinsing, care, , Detergents and cleaners.

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 of polyvalent metal salts, an aqueous solution of a cationic surfactant or mixtures thereof. This is most easily accomplished by combining an aqueous dispersion of particulate hydrophobic polymers having a particle size of 10 nm to 100 μm with an aqueous solution of a water-soluble metal salt or a surfactant. Most of the time, the two components are mixed at room temperature, but can be mixed at temperatures of, for example, 0 ° to 100 ° C, provided that the dispersions do not coagulate on heating. 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 polyvalent metal salt and / or a cationic surfactant, 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.

A preferred embodiment of particles of the hydrophobic polymers to be used according to the invention exhibits 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 when dispersed in concentrated as well as 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) report the behavior of particles of 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 and amides of C ₃ -C ₅ monoethylenically unsaturated carboxylic acids with perfluoroalkyl-containing alcohols or amines, allyl 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.

1. (a) 40 bis 100 Gew.-%, vorzugsweise 50 bis 90 Gew.-%, besonders bevorzugt 60 bis 75 Gew.-%, mindestens eines wasserunlöslichen nichtionischen Monomeren,
2. (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,
3. (c) 0 bis 25 Gew.-%, vorzugsweise 0 bis 15 Gew.-%, eines Sulfonsäure- und/oder Phosphonsäuregruppen enthaltenden Monomeren oder dessen Salze,
4. (d) 0 bis 55 Gew.-%, vorzugsweise 0 bis 40 Gew.-%, mindestens eines wasserlöslichen nichtionischen Monomeren und
5. (e) 0 bis 10 Gew.-%, vorzugsweise 0 bis 5 Gew.-%, mindestens eines mehrfach ethylenisch ungesättigten Monomers

in einpolymerisierter Form.Hydrophobic polymers include, for example

1. (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,
2. (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,
3. (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,
4. (D) 0 to 55 wt .-%, preferably 0 to 40 wt .-%, of at least one water-soluble nonionic monomer and
5. (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% by weight of anionic monomers are most commonly used together 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 (in the index) 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 multiply ethylenically 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 template copolymers. By equivalence pH is meant 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 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 e.g. 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. Preferably, 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. Suitable anionically substituted polysaccharides are, for example, 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 polyvalent metal ions and / or cationic surfactants. An occupancy of the particles with polyvalent metal ions is achieved by, for example, adding 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. Alternatively, it is also possible to provide an aqueous solution of at least one water-soluble polyvalent metal salt and to add an aqueous dispersion of an anionically dispersed hydrophobic polymer. 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 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.

Particularly suitable cationic surfactants are e.g.

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.

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, which are esterified with C ₈ -C ₂₂ carboxylic acids, Imidazolinquats such as 1-alkyl-imidazolinium salts of the general formulas I or II

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 smooth or textured surfaces with dispersions is important. It is not always possible to modify the surfaces by impregnating, spraying and brushing with concentrated dispersions. Often it is desirable to modify by means of rinsing the material to be treated with a highly diluted, active substance-containing liquor or by spraying a highly diluted one to carry out aqueous formulation. It is often desirable to combine the modification of the surface of materials in the context of a laundry, cleaning and / or care or impregnation of the surface. In practice, surfaces of different materials are considered, eg hard macroscopic surfaces such as floor and wall coverings, exposed concrete, stone facades, plastered facades, glass surfaces, ceramic surfaces, metal surfaces, enamelled surfaces, plastic surfaces, wood surfaces, surfaces of coated wood or painted surfaces, microscopic Surfaces such as porous bodies (eg foams, woods, leather, porous building materials, porous minerals), fiber structures such as fiber surfaces in textiles and textile tiles, floor and wall coverings, floor and wall coatings or coatings, furniture coverings and cellulose fleeces. Preferably treated surfaces are floor and wall coverings made of plastics or ceramics, furniture surfaces and objects made of glass and metal. Of the microscopic surfaces, textiles, in particular cotton fabric and cotton blended fabrics, carpets and upholstery covers are preferably required for treatment.

The modification of the surfaces can consist, for example, in a hydrophobing, soil release finish, 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 rinse, conditioner, impregnating, washing and cleaning products. They can be used, for example, as the sole active component in aqueous rinsing and care compositions and, depending on the composition of the polymer, for example, facilitate soil removal in a subsequent wash, lower soil adhesion during use, an improvement in the structural integrity of fibers, an improvement in the molding process. and structure preservation 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 .-%.

1. (a) 0,05 bis 40 Gew.-% kationisch modifizierte, teilchenförmige, hydrophobe Polymere, deren Oberfläche durch Belegung mit mehrwertigen Metallionen und/oder kationischen Tensiden kationisch modifiziert ist und deren Teilchengröße 10 nm bis 100 µm beträgt,
2. (b) 0,01 bis 20 Gew.-% mindestens eines wasserlöslichen Salzes von Ca, Mg, Al, Zn und/oder 0,01 bis 30 Gew.-% mindestens eines kationischen Tensids,
3. (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 und
4. (d) Wasser zur Ergänzung auf 100 Gew.-%.

Agents for the treatment of laundry, textile surfaces, leather, wood and hard surfaces which contain the cationically modified, particulate, hydrophobic polymers may have, for example, the following composition:

1. (a) 0.05 to 40% by weight of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by coating with polyvalent metal ions and / or cationic surfactants and whose particle size is 10 nm to 100 μm,
2. (b) 0.01 to 20% by weight of at least one water-soluble salt of Ca, Mg, Al, Zn and / or 0.01 to 30% by weight of at least one cationic surfactant,
3. (c) 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 and
4. (d) water to supplement to 100 wt .-%.

The treatment of laundry, textile surfaces, leather, wood and hard surfaces is preferably carried out with aqueous liquors containing at least 0.5 mmol / l of water-soluble Ca, Mg or Zn salts and / or at least 0.05 mmol of water-soluble Al Salts and / or contain at least 50 ppm of at least one cationic surfactant.

Laundry aftertreatment and laundry care products may be liquid, gel or solid.

1. (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,
2. (b) 0,05 bis 20 Gew.-% einer Säure,
3. (c) 0,1 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 10 Gew.-% mindestens eines anderen üblichen Inhaltsstoffs wie Parfum, weitere Tenside, Silikonöl, Lichtschutzmittel, Farbstoff, Komplexbildner, Vergrauungsinhibitor, Soil-Release-Polyester, Farbübertragungsinhibitor, nicht-wäßriges Lösemittel, Hydrotrop, Verdicker und/oder Alkanolamin und
5. (e) Wasser zur Ergänzung auf 100 Gew.-%.

Liquid or gel-like agents may have, for example, the following composition:

1. (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,
2. (b) 0.05 to 20% by weight of an acid,
3. (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (d) 0 to 10% by weight of at least one other conventional ingredient such as perfume, other surfactants, silicone oil, light stabilizer, dye, complexing agent, grayness inhibitor, Soil-release polyester, color transfer inhibitor, non-aqueous solvent, hydrotrope, thickener and / or alkanolamine and
5. (e) water to supplement to 100 wt .-%.

1. (a) 0,5 bis 25 Gew.-% teilchenförmige, hydrophobe Polymere, die 25 bis 60 Gew.-% eines mindestens eine Carbonsäuregruppe enthaltenden ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, eine Teilchengröße von 10 nm bis 100 µm haben und mit einem anionischen Emulgator und/oder einem anionischen Schutzkolloid in Wasser dispergiert sind,
2. (b) 0,05 bis 10 Gew.-% mindestens einer Säure,
3. (c) 0,1 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 10 Gew.-% mindestens eines anderen üblichen Inhaltsstoffs wie Parfum, weitere Tenside, Silikonöl, Lichtschutzmittel, Farbstoff, Komplexbildner, Vergrauungsinhibitor, Soil-Release-Polyester, Farbübertragungsinhibitor, nicht-wäßriges Lösemittel, Hydrotrop, Verdicker und/oder Alkanolamin und
5. (e) Wasser zur Ergänzung auf 100 Gew.-%.

The liquid or gel wash and aftertreatment agents contain in a preferred embodiment

1. (A) 0.5 to 25 wt .-% of particulate, hydrophobic polymers containing from 25 to 60 wt .-% of at least one carboxylic acid group-containing ethylenically unsaturated monomer copolymerized, have a particle size of 10 nm to 100 microns and with an anionic emulsifier and / or an anionic protective colloid dispersed in water,
2. (b) 0.05 to 10% by weight of at least one acid,
3. (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (D) 0 to 10 wt .-% of at least one other conventional ingredient such as perfume, other surfactants, silicone oil, light stabilizer, dye, complexing agent, grayness inhibitor, soil release polyester, dye transfer inhibitor, non-aqueous solvent, hydrotrope, thickener and / or Alkanolamine and
5. (e) water to supplement to 100 wt .-%.

The agents of this preferred embodiment are particularly suitable for achieving soil release promoting properties. From so aftertreated laundry soiling that occur in the use phase, easily removed in the subsequent wash.

1. (a) 0,5 bis 25 Gew.-% teilchenförmige, hydrophobe Polymere, die 75 bis 100 Gew.-% mindestens eines wasserunlöslichen ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, eine Teilchengröße von 10 nm bis 100 µm haben und mit einem anionischen Emulgator und/oder einem anionischen Schutzkolloid in Wasser dispergiert sind,
2. (b) 0 bis 10 Gew.-% mindestens einer Säure,
3. (c) 0,1 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 10 Gew.-% mindestens eines anderen üblichen Inhaltsstoffs wie Parfum, weitere Tenside, Silikonöl, Lichtschutzmittel, Farbstoff, Komplexbildner, Vergrauungsinhibitor, Soil-Release-Polyester, Farbübertragungsinhibitor, nicht-wäßriges Lösemittel, Hydrotrop, Verdicker und/oder Alkanolamin und
5. (e) Wasser zur Ergänzung auf 100 Gew.-%.

The liquid or gelled laundry aftertreatment and laundry care compositions comprise in a further preferred embodiment

1. (a) from 0.5 to 25% by weight of particulate, hydrophobic polymers containing from 75 to 100% by weight of at least one water-insoluble ethylenically unsaturated monomer in copolymerized form, having a particle size of from 10 nm to 100 μm and containing an anionic emulsifier and / or or an anionic protective colloid dispersed in water,
2. (b) 0 to 10% by weight of at least one acid,
3. (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (d) 0 to 10% by weight of at least one other conventional ingredient such as perfume, other surfactants, silicone oil, light stabilizer, dye, complexing agent, grayness inhibitor, Soil-release polyester, color transfer inhibitor, non-aqueous solvent, hydrotrope, thickener and / or alkanolamine and
5. (e) water to supplement to 100 wt .-%.

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.

1. (a) 0,5 bis 25 Gew.-% teilchenförmige, hydrophobe Polymere, die 10 bis 100 Gew.-% mindestens eines Fluorsubstituenten enthaltenden ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, eine Teilchengröße von 10 nm bis 100 µm haben und mit einem anionischen Emulgator und/oder einem anionischen Schutzkolloid in Wasser dispergiert sind,
2. (b) 0 bis 10 Gew.-% mindestens einer Säure,
3. (c) 0,1 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 10 Gew.-% mindestens eines anderen üblichen Inhaltsstoffs wie Parfum, weitere Tenside, Silikonöl, Lichtschutzmittel, Farbstoff, Komplexbildner, Vergrauungsinhibitor, Soil-Release-Polyester, Farbübertragungsinhibitor, nicht-wäßriges Lösemittel, Hydrotrop, Verdicker und/oder Alkanolamin und
5. (e) Wasser zur Ergänzung auf 100 Gew.-%.

The liquid or gelled laundry aftertreatment and laundry care compositions comprise in a further preferred embodiment

1. (A) 0.5 to 25 wt .-% of particulate hydrophobic polymers containing 10 to 100 wt .-% of at least one fluorine substituent containing ethylenically unsaturated monomers in copolymerized, have a particle size of 10 nm to 100 microns and with an anionic emulsifier and / or an anionic protective colloid dispersed in water,
2. (b) 0 to 10% by weight of at least one acid,
3. (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (D) 0 to 10 wt .-% of at least one other conventional ingredient such as perfume, other surfactants, silicone oil, light stabilizer, dye, complexing agent, grayness inhibitor, soil release polyester, dye transfer inhibitor, non-aqueous solvent, hydrotrope, thickener and / or Alkanolamine and
5. (e) water to supplement to 100 wt .-%.

The agents of this preferred embodiment are particularly suitable for achieving dirt-repellent properties, in particular oil and grease-soiling. 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 generally 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 with a particle size of 10 nm to 100 microns, for example, by mixing aqueous dispersions of eligible particulate polymers with the other constituents of the respective treatment agent in the presence of 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 amounts of polyvalent metal ions and / or cationic surfactants are present in dissolved form in the liquor. For example, it is possible to use the formulations containing anionic particles or these particles in liquors containing water-soluble salts of Ca, Mg or Zn of more than 0.5 mmol / l, preferably more than 1 mmol / l, particularly preferably more than 2 mmol / l use. For example, it is possible to use the formulations containing anionic particles or these particles in liquors having a water-soluble salt content of Al of more than 0.05 mmol / l, preferably more than 0.1 mmol / l, particularly preferably more than 0.2 mmol / l use. Cationic surfactants 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 surfactants.

Examples of the composition of typical anionic dispersions, which can be processed by mixing with water-soluble salts of polyvalent metals and / or cationic surfactants and other components to rinse, care, impregnating, washing and cleaning agents, are the dispersions I to V described below whose dispersed particles are each to be observed in the electron microscopic examination as discrete particles with the indicated 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

Anionic fluoropolymer dispersion Nuva ^® FTA-4 (Clariant)

Dispersion V

35% by weight aqueous dispersion of a polymer of 64% by weight of n-butyl acrylate, 32% 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.

From the dispersions I to III, typical formulations according to the invention with soil release action can be prepared, which are used, for example, in household washing in the final rinse of the washing machine in a dosage of 2 to 5 g / l, preferably 3 g / l:

Formulation I

50% by weight of one of the dispersions I to III described above 1.5% by weight of formic acid
12% by weight calcium chloride
Water to supplement to 100 wt .-%.

The formulation 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.

Formulation II

50 wt .-% of one of the dispersions I to III described above
1.5% by weight of formic acid 12% by weight of calcium chloride
10% by weight of an esterquat (methylquat of di-tallow fatty acid ester of triethanolamine)
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
1.5% by weight of aluminum sulfate
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
1.5% by weight of aluminum sulfate
5% by weight of an esterquat (methylquat of di-tallow fatty acid ester of triethanolamine)
Water to supplement to 100 wt .-%.

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

• Anionisches Dispergiermittel enthaltende Copolymerisate aus Butylacrylat und Styrol
• Anionisches Dispergiermittel enthaltende Copolymerisate aus Butylacrylat und Vinylacetat
• Anionisches Dispergiermittel enthaltende Tetrafluorethylen-Polymere.

Suitable hydrophobicizing, dirt-repellent or fiber-reinforcing additives for rinsing, care, washing and cleaning agents are, for example, the following aqueous dispersions whose dispersed particles have an average diameter of 10 nm to 100 μm:

• Anionic dispersant containing copolymers of butyl acrylate and styrene
• Anionic dispersant containing copolymers of butyl acrylate and vinyl acetate
• Anionic dispersant containing 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 first cationically modified by treatment with water-soluble polyvalent metal salts or with cationic surfactants, or the cationic modification of the dispersions is carried out during the preparation of the rinse or conditioner as described above under Formulations I to IV. 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.

Example of a suitable formulation for stain-resistant modification of textiles, textile floor coverings and other materials and surfaces

Formulation V

50% by weight of dispersion IV described above
5% by weight of formic acid
12% by weight calcium acetate
Water to supplement to 100 wt .-%.

The formulation can be used, for example, in a dilution with water in a weight ratio of 1:50 to 1: 1000 for rinsing or aftertreatment of the abovementioned materials.

Example of a suitable formulation for the hydrophobization of textiles, wood, leather and other materials and surfaces

Formulation VI

20% by weight of dispersion V described above
8% by weight calcium acetate
5 wt .-% polyvinylpyrrolidone of molecular weight M _w 30 000
Water to supplement to 100 wt .-%.

The formulation can be used, for example, in a dilution with water in a weight ratio of 1:20 to 1: 5000 for rinsing or aftertreatment of the abovementioned materials.

The dispersions I to V can also be used, for example, directly or as a formulation with further constituents in water containing at least 0.5 mol / l of Ca ²⁺ , Mg ²⁺ or Zn ²⁺ or at least 0.05 mol / l of Al ^{3 +} contains.

1. (a) 0,05 bis 30 Gew.-% kationisch modifizierte, teilchenförmige, hydrophobe Polymere, deren Oberfläche durch Belegung mit mehrwertigen Metallionen und/oder kationischen Tensiden kationisch modifiziert ist und deren Teilchengröße 10 nm bis 100 µm beträgt,
2. (b) 0,1 bis 40 Gew.-% mindestens eines nichtionischen oder anionischen Tensids,
3. (c) 0,01 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 10 Gew.-% mindestens eines Komplexbildners,
5. (e) 0 bis 20 Gew.-% anderer üblicher Inhaltsstoffe wie pH-Regulatoren, Stellmittel, weitere Tenside, Verdicker, Lösemittel, Hydrotrope, Polycarbonsäuren, Silikone, Glanzbildner, Parfum und Farbstoffe
6. (f) 0 bis 90 Gew.-% Wasser.

The invention also provides a liquid or gel cleansing and care formulation having the following composition:

1. (a) 0.05 to 30% by weight of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by coating with polyvalent metal ions and / or cationic surfactants and whose particle size is 10 nm to 100 μm,
2. (b) 0.1 to 40% by weight of at least one nonionic or anionic surfactant,
3. (c) from 0.01 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (d) 0 to 10% by weight of at least one complexing agent,
5. (E) 0 to 20 wt .-% of other conventional ingredients such as pH regulators, stabilizers, other surfactants, thickeners, solvents, hydrotropes, polycarboxylic acids, silicones, brighteners, perfume and dyes
6. (f) 0 to 90% by weight of water.

• (a) 0,1 bis 30 Gew.-% teilchenförmige, hydrophobe Polymere, die mindestens eine Gruppe von anionischen ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, die eine Teilchengröße von 10 nm bis 100 µm haben und in Wasser dispergiert sind,
• (b) 0,05 bis 20 Gew.-% einer Säure,
• (c) 0,1 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 Komplexbildners,
• (f) 0 bis 20 Gew.-% anderer üblicher Inhaltsstoffe wie pH-Regulatoren, Stellmittel, weitere Tenside, Verdicker, Lösemittel, Hydrotrope, Polycarbonsäuren, Silikone, Glanzbildner, Parfum und/oder Farbstoffe und
• (g) 0 bis 90 Gew.-% Wasser.

Another object of the invention is a liquid or gel acidic cleaning formulation having the following composition:

• (a) from 0.1 to 30% by weight of particulate hydrophobic polymers containing in copolymerized form at least one group of anionic ethylenically unsaturated monomers having a particle size of 10 nm to 100 μm and being dispersed in water,
• (b) 0.05 to 20% by weight of an acid,
• (c) 0.1 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 complexing agent,
• (f) 0 to 20 wt .-% of other conventional ingredients such as pH regulators, stabilizers, other surfactants, thickeners, solvents, hydrotropes, polycarboxylic acids, silicones, brighteners, perfume and / or dyes and
• (g) 0 to 90% by weight of water.

1. (a) 0,5 bis 25 Gew.-% teilchenförmige, hydrophobe Polymere, die 25 bis 60 Gew.-% eines mindestens eine anionische Gruppe, vorzugsweise eine Carbonsäuregruppe enthaltenden ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, eine Teilchengröße von 10 nm bis 100 µm haben und mit einem anionischen Emulgator und/oder einem anionischen Schutzkolloid in Wasser dispergiert sind,
2. (b) 0,1 bis 40 Gew.-% mindestens eines nichtionischen oder anionischen Tensids,
3. (c) 0,1 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0,1 bis 20 Gew.-% mindestens einer Säure,
5. (e) 0 bis 10 Gew.-% mindestens eines Komplexbildners,
6. (f) 0 bis 20 Gew.-% anderer üblicher Inhaltsstoffe wie pH-Regulatoren, Stellmittel, weitere Tenside, Verdicker, Lösemittel, Hydrotrope, Polycarbonsäuren, Silikone, Glanzbildner, Parfum und/oder Farbstoffe und
7. (g) 0 bis 90 Gew.-% Wasser.

Such liquid or gel acidic cleaning formulations contain in a preferred embodiment

1. (A) 0.5 to 25 wt .-% of particulate, hydrophobic polymers containing from 25 to 60 wt .-% of at least one anionic group, preferably a carboxylic acid group-containing ethylenically unsaturated monomers in copolymerized, have a particle size of 10 nm to 100 microns and are dispersed in water with an anionic emulsifier and / or an anionic protective colloid,
2. (b) 0.1 to 40% by weight of at least one nonionic or anionic surfactant,
3. (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (d) 0.1 to 20% by weight of at least one acid,
5. (e) 0 to 10% by weight of at least one complexing agent,
6. (f) 0 to 20 wt .-% of other conventional ingredients such as pH regulators, stabilizers, other surfactants, thickeners, solvents, hydrotropes, polycarboxylic acids, silicones, brighteners, perfume and / or dyes and
7. (g) 0 to 90% by weight of water.

The formulations of this preferred embodiment are particularly suitable for imparting improved soil release to the surfaces so treated in the subsequent cleaning. The better soil removal is achieved in particular if the subsequent cleaning is carried out with a neutral or alkaline cleaning liquor.

1. (a) 0,5 bis 25 Gew.-% teilchenförmige, hydrophobe Polymere, die 75 bis 100 Gew.-% mindestens eines wasserlöslichen ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, eine Teilchengröße von 10 nm bis 100 µm haben und mit einem anionischen Emulgator und/oder einem anionischen Schutzkolloid in Wasser dispergiert sind,
2. (b) 0,1 bis 40 Gew.-% mindestens eines nichtionischen oder anionischen Tensids,
3. (c) 0,1 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 20 Gew.-% mindestens einer Säure,
5. (e) 0 bis 10 Gew.-% mindestens eines Komplexbildners,
6. (f) 0 bis 20 Gew.-% anderer üblicher Inhaltsstoffe wie pH-Regulatoren, Stellmittel, weitere Tenside, Verdicker, Lösemittel, Hydrotrope, Polycarbonsäuren, Silikone, Glanzbildner, Parfum und/oder Farbstoffe und
7. (g) 0 bis 90 Gew.-% Wasser.

Liquid or gel cleaning formulations contain in a further preferred embodiment

1. (a) from 0.5 to 25% by weight of particulate, hydrophobic polymers containing from 75 to 100% by weight of at least one water-soluble ethylenically unsaturated monomer in copolymerized form having a particle size of from 10 nm to 100 μm and containing an anionic emulsifier and / or or an anionic protective colloid dispersed in water,
2. (b) 0.1 to 40% by weight of at least one nonionic or anionic surfactant,
3. (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (d) 0 to 20% by weight of at least one acid,
5. (e) 0 to 10% by weight of at least one complexing agent,
6. (f) 0 to 20 wt .-% of other conventional ingredients such as pH regulators, stabilizers, other surfactants, thickeners, solvents, hydrotropes, polycarboxylic acids, silicones, brighteners, perfume and / or dyes and
7. (g) 0 to 90% by weight of water.

The formulations of this preferred embodiment are particularly suitable for imparting water-repellent or impregnating properties to the cleaned surfaces. Water is absorbed to a lesser extent from surfaces treated in this way, and water is less able to penetrate the surface.

1. (a) 0,5 bis 25 Gew.-% teilchenförmige, hydrophobe Polymere, die 10 bis 100 Gew.-% mindestens eines Fluorsubstituenten enthaltenden ethylenisch ungesättigten Monomeren einpolymerisiert enthalten, eine Teilchengröße von 10 nm bis 100 µm haben und mit einem anionischen Emulgator und/oder einem anionischen Schutzkolloid in Wasser dispergiert sind,
2. (b) 0,1 bis 40 Gew.-% mindestens eines nichtionischen oder anionischen Tensids,
3. (c) 0,1 bis 30 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 20 Gew.-% mindestens einer Säure,
5. (e) 0 bis 10 Gew.-% mindestens eines Komplexbildners,
6. (f) 0 bis 20 Gew.-% anderer üblicher Inhaltsstoffe wie pH-Regulatoren, Stellmittel, weitere Tenside, Verdicker, Lösemittel, Hydrotrope, Polycarbonsäuren, Silikone, Glanzbildner, Parfum und/oder Farbstoffe und
7. (g) 0 bis 90 Gew.-% Wasser.

Liquid or gel cleaning formulations contain in a further preferred embodiment

1. (A) 0.5 to 25 wt .-% of particulate hydrophobic polymers containing 10 to 100 wt .-% of at least one fluorine substituent containing ethylenically unsaturated monomers in copolymerized, have a particle size of 10 nm to 100 microns and with an anionic emulsifier and / or an anionic protective colloid dispersed in water,
2. (b) 0.1 to 40% by weight of at least one nonionic or anionic surfactant,
3. (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (d) 0 to 20% by weight of at least one acid,
5. (e) 0 to 10% by weight of at least one complexing agent,
6. (f) 0 to 20 wt .-% of other conventional ingredients such as pH regulators, stabilizers, other surfactants, thickeners, solvents, hydrotropes, polycarboxylic acids, silicones, brighteners, perfume and / or dyes and
7. (g) 0 to 90% by weight of water.

The formulations of this preferred embodiment are particularly suitable for imparting dirt-repellent, in particular oil and greasy soil-repelling properties to the surface thus cleaned.

The laundry aftertreatment and conditioning agents and detergents 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, spray aids, agglomerating 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.

The surfaces of fabrics, fibers, glass, plastics, metals, wood and ceramics treated with the cationically modified dispersions of hydrophobic polymers to be used according to the invention are easier to remove from soiling after a soiling in a subsequent aqueous washing or cleaning process than the untreated surfaces , 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.

1. (a) 0,05 bis 15 Gew.-% kationisch modifizierte, teilchenförmige, hydrophobe Polymere, deren Oberfläche durch Belegung mit mehrwertigen Metallionen und/oder kationischen Tensiden kationisch modifiziert ist und deren Teilchengröße 10 nm bis 100 µm beträgt,
2. (b) 0 bis 20 Gew.-% mindestens eines nichtionischen oder anionischen Tensids,
3. (c) 0 bis 15 Gew.-% mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn oder Al und/oder eines kationischen Tensids,
4. (d) 0 bis 5 Gew.-% mindestens eines Komplexbildners,
5. (e) 0 bis 10 Gew.-% anderer üblicher Inhaltsstoffe wie pH-Regulatoren, Stellmittel, weitere Tenside, Verdicker, Lösemittel, Hydrotrope, Polycarbonsäuren, Silikone, Glanzbildner, Parfum und/oder Farbstoffe und
6. (f) 0 bis 99,5 Gew.-% Wasser.

Another object of the invention are liquid or gel care and after-treatment agents which are sprayed as a highly diluted aqueous formulation on the surfaces and materials to be treated. Such formulations applied by spraying

1. (a) 0.05 to 15% by weight of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by coating with polyvalent metal ions and / or cationic surfactants and whose particle size is 10 nm to 100 μm,
2. (b) 0 to 20% by weight of at least one nonionic or anionic surfactant,
3. (c) 0 to 15% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and / or a cationic surfactant,
4. (d) 0 to 5% by weight of at least one complexing agent,
5. (E) 0 to 10 wt .-% of other conventional ingredients such as pH regulators, regulators, other surfactants, thickeners, solvents, hydrotropes, polycarboxylic acids, silicones, brighteners, perfume and / or dyes and
6. (f) 0 to 99.5% by weight of water.

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

enthält.Another object of the invention is a solid detergent formulation, the

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

contains.

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

enthält.The invention also provides a liquid or gel detergent formulation which

1. (a) from 0.05 to 20% by weight of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by coating with polyvalent metal ions and / or cationic surfactants and whose particle size is from 10 nm to 100 μm,
2. (b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,
3. (c) 0 to 20% by weight of an inorganic builder,
4. (d) 0 to 10% by weight of an organic cobuilder,
5. (e) 0 to 10% by weight of other common ingredients such as soda, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibitors, grayness inhibitors, soil release polyesters, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines and
6. (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, hydroptropes, 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, which are reacted with from 3 to 15 mol of ethylene oxide and optionally additionally with 1 to 4 mol of propylene oxide and / or butylene oxide are alkoxylated, and block polymers of ethylene oxide and propylene oxide having a molecular weight of 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 -alcohols 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, 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 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 with 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, with polyethylene glycols having molecular weights of from 1 000 to 5 000 condensed in, and those polyesters 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 particularly important in liquid formulations 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 800 to 200,000, more preferably from 5,000 to 70,000, 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.

The percentages in the examples are by weight.

Examples

For the examples and comparative examples, the anionic dispersions I and IV were used.

Anionic 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 surfactants as emulsifier and 20 wt .-% of a low molecular weight starch as a protective colloid. It had a pH of 4.

Anionic dispersion IV

Anionic fluoropolymer dispersion Nuva FTA-4 (Clariant)

Comparative Example 1

The anionic dispersion I was brought to a level 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

The anionic dispersion I was brought to a content of particles of 10% with deionized water of pH 4. At pH 4, the dispersion was metered in with stirring with a magnetic stirrer over the course of 30 minutes to the same volume of a 50 mmol solution of CaCl ₂ , pH 4. The dispersion was stable for hours. This dispersion was diluted with 1 mmol of Ca ^{2+ -containing} water of pH 4 to a content 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.

The anionic dispersion I was brought to a content of 0.040% with 3 mmol of Ca ^{2+ -containing} 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, a large decrease in absorbance was observed.

Example 3

The anionic dispersion I was brought to a content of 0.040% with 3 mmol of Zn ^{2+ -containing} 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 measured at 520 nm. Within 30 minutes, a large decrease in absorbance was observed.

Example 4

The anionic dispersion I was brought to a content of 0.040% with 3 mmol of Al ³⁺ -containing 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, a large decrease in absorbance was observed.

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 Example 4 t = 0 min 1.0 0.99 0.99 1.00 1.04 t = 30 min 1.0 0.84 0.74 0.75 0.72

The comparison of Examples 1 to 4 with Comparative Example 1 shows that when using a polyvalent metal cation as a retention aid significantly higher levels of hydrophobic particles are adsorbed on the surface than in the absence of the retention aid.

Examples 5 and 6 and Comparative Examples 2 to 4

To test the soil release properties of rinse-off formulations with particles to be used according to the invention, washing tests were carried out:

Cotton fabric was prewashed with the anionic dispersion I. In Comparative Experiment 3, the dispersion was used in the absence of polyvalent metal salt and cationic surfactant. In Example 5, Ca acetate was added to the dispersion before washing. In Example 6, esterquat (methyl quat of di-tallow fatty acid ester of triethanolamine) was added as a cationic surfactant to the dispersion prior to washing. 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 was measured before and after the wash and combined in a known manner with the remission value of the white cotton fabric determines the soil release in% oil release.

Washing 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 5 Example 6 Concentration of particles from dispersion I in the prewash 0 400 mg / l 0 400 mg / l 400 mg / l Concentration of Ca-acetate in the prewash 0 0 0 3.0 mmol / l 0 Concentration of cationic surfactant in the prewash 0 0 400 mg / l 0 400 mg / l Dirt-removing effect in subsequent wash in% Soil-Release 35% 32% 36% 58% 49% The results of the washing experiments show that neither the anionic polymer dispersion alone nor the cationic surfactant alone have a soil release effect on the soil. The inventive combination of Ca salt or cationic surfactant with the anionic polymer dispersion, however, shows a significant improvement in the soil release of cotton. Example 7 and Comparative Examples 5 and 6

To test the soil-repellent properties of cotton fabrics obtained with rinse-in formulations according to the invention, laundering tests were carried out in Launder-O-meter.

Cotton fabric was washed with commercial detergent and rinsed in the rinse with hard water containing the fluoropolymer dispersion IV. In comparative experiment 5, no dispersion was added in the final rinse bath. In comparative experiment 6, demineralized water containing the fluoropolymer disperse IV was used in the final rinse.

The rinsed fabrics were spun, dried and ironed. To test for stain resistance, each fabric was placed flat over the opening of a 5 cm diameter beaker. Then a drop of dirty engine oil was applied centrally. It was checked after every 10 seconds, 180 minutes and 1 day, whether the oil drop had penetrated into 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
• ca / Mg ratio: 3: 1
• Fleet ratio: 12.5

rinsing

• Rinsing temperature: 20 ° C
• Rinsing time: 15 min
• pH value: 4
• Fleet ratio: 25

Table 3: Wash results Comparative Example 5 Comparative Example 6 Example 7 Concentration of particles from dispersion IV in the final rinse 0 400 ppm 400 ppm Concentration of Ca acetate in the final rinse 3.0 mmol / l 0 3.0 mmol / l Dwell time of oil drop on the cotton fabric << 10 sec <10 sec > 1 d

The results of the washing experiments show that neither in the absence of the dispersion IV with the addition of polyvalent metal ions, nor in the presence of the dispersion IV in demineralized water, a rejection of the oil contamination is observed. When using the dispersion IV in the presence of 3.0 mmol Ca ²⁺ ions, however, an excellent repellency of the oil contamination is observed.

Claims (21)

1. The use of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with polyvalent metal ions and/or cationic surfactants, and the particle size of which is 10 nm to 100 µm, as additive to rinse compositions, care compositions, detergents and cleaners.
2. The use according to claim 1, wherein the cationically modified, particulate, hydrophobic polymers are obtainable by treating aqueous dispersions of particulate, hydrophobic polymers having a particle size of from 10 nm to 100 µm with an aqueous solution of polyvalent metal salts, an aqueous solution of a cationic surfactant or mixtures thereof.
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 metal salts are chosen from the group of the water-soluble salts of Ca, Mg, Al, Zn or mixtures thereof.
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 the rinse or care bath, in the detergent liquor or the cleaning bath, is 0.0002 to 1.0% by weight.
9. The use according to any of claims 1 to 8, wherein the concentration of the cationically modified, particulate, hydrophobic polymers in the case of use in the rinse or care bath, in the detergent liquor or the cleaning bath, is 0.002 to 0.05% by weight.
10. A composition for the treatment of laundry, textile surfaces, leather, wood and hard 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 polyvalent metal ions and/or cationic surfactants, and the particle size of which is 10 mm to 100 µm,

    (b) 0.01 to 20% by weight of at least one water-soluble salt of Ca, Mg, Al, Zn and/or 0.01 to 30% by weight of at least one cationic surfactant,

    (c) 0 to 80% by weight of at least one customary additive, such as acids or bases, inorganic builders, organic cobuilders, further surfactants, polymeric color transfer inhibitors, polymeric antiredeposition agents, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, light protection agents, dyes, solvents, hydrotropic agents, thickeners and/or alkanolamines and

    (d) water to make up to 100% by weight.
11. A composition according to claim 10, wherein the aqueous liquors comprise at least 0.5 mmol/l of water-soluble Ca, Mg, or Zn salts and/or at least 0.05 mmol of water-soluble Al salts and/or at least 50 ppm of at least one cationic surfactant.
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, in copolymerized form, at least one group of anionic ethylenically unsaturated monomers, which 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 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and/or a cationic surfactant,

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

    (e) water to make up to 100% by weight.
13. The laundry aftertreatment and laundry care composition in liquid or gel form according to claim 12 which comprises

    (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 comprising at least one carboxylic acid group, have a particle size of from 10 nm to 100 µm and which have been dispersed in water using an anionic emulsifier and/or an anionic protective colloid,

    (b) 0.05 to 10% by weight of at least one acid,

    (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and/or a cationic surfactant,

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

    (e) water to make up to 100% by weight.
14. A laundry aftertreatment and laundry care composition in liquid or gel form which comprises

    (a) 0.5 to 25% by weight of particulate, hydrophobic polymers which comprise, in copolymerized form, 75 to 100% by weight of at least one water-soluble ethylenically unsaturated monomer or 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 which have been dispersed in water using an anionic emulsifier and/or an anionic protective colloid,

    (b) 0 to 10% by weight of at least one acid,

    (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and/or a cationic surfactant,

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

    (e) water to make up to 100% by weight.
15. A cleaning and care formulation in liquid or gel form which comprises

    (a) 0.05 to 30% by weight of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with polyvalent metal ions and/or cationic surfactants, and the particle size of which is 10 nm to 100 µm,

    (b) 0.01 to 40% by weight of at least one nonionic or anionic surfactant,

    (c) 0.01 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and/or a cationic surfactant,

    (d) 0 to 10% by weight of at least one complexing agent,

    (e) 0 to 20% by weight of other customary ingredients, such as pH regulators, extenders, further surfactants, thickeners, solvents, hydrotropic agents, polycarboxylic acids, silicones, brighteners, perfume and/or dyes and

    (f) 0 to 90% by weight of water.
16. An acidic cleaning formulation in liquid or gel form which comprises

    (a) 0.1 to 30% by weight of particulate, hydrophobic polymers which comprise, in copolymerized form, at least one group of anionic ethylenically unsaturated monomers, which 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 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 complexing agent,

    (f) 0 to 20% by weight of other customary ingredients, such as pH regulators, extenders, further surfactants, thickeners, solvents, hydrotropic agents, polycarboxylic acids, silicones, brighteners, perfume and/or dyes and

    (g) 0 to 90% by weight of water.
17. An acidic cleaning formulation in a liquid or gel form which comprises

    (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 comprising at least one carboxylic acid group, have a particle size of from 10 nm to 100 µm and which have been dispersed in water using an anionic emulsifier and/or an anionic protective colloid,

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

    (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and/or a cationic surfactant,

    (d) 0.1 - 20% by weight of at least one acid

    (e) 0 to 10% by weight of at least one complexing agent,

    (f) 0 to 20% by weight of other customary ingredients, such as pH regulators, extenders, further surfactants, thickeners, solvents, hydrotropic agents, polycarboxylic acids, silicones, brighteners, perfume and/or dyes and

    (g) 0 to 90% by weight of water.
18. A cleaning formulation in a liquid or gel form which comprises

    (a) 0.5 to 25% by weight of particulate, hydrophobic polymers which comprise, in copolymerized form, 75 to 100% by weight of at least one water-soluble ethylenically unsaturated monomer or 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 which have been dispersed in water using an anionic emulsifier and/or an anionic protective colloid,

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

    (c) 0.1 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn or Al and/or a cationic surfactant,

    (d) 0.1 - 20% by weight of at least one acid

    (e) 0 to 10% by weight of at least one complexing agent,

    (f) 0 to 20% by weight of other customary ingredients, such as pH regulators, extenders, further surfactants, thickeners, solvents, hydrotropic agents, polycarboxylic acids, silicones, brighteners, perfume and/or dyes and

    (g) 0 to 90% by weight of water.
19. A care and aftertreatment composition in liquid or gel form which comprises

    (a) 0.05 to 15% by weight of cationically modified, particulate, hydrophobic polymers, the surface of which has been cationically modified by coating with polyvalent metal ions and/or cationic surfactants, and the particle size of which is 10 nm to 100 µm,

    (b) 0 to 20% by weight of at least one nonionic, cationic and/or anionic surfactant,

    (c) 0 to 15% by weight of at least one water-soluble salt of Mg, Ca, Zn or A1 and/or a cationic surfactant,

    (d) 0 to 5% by weight of at least one complexing agent,

    (e) 0 to 10% by weight of other customary ingredients, such as pH regulators, extenders, further surfactants, thickeners, solvents, hydrotropic agents, polycarboxylic acids, silicones, brighteners, perfume and/or dyes and

    (f) 0 to 99.5% by weight of water.
20. 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 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,

    (e) 0 to 60% by weight of other customary ingredients, such as extenders, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, color transfer inhibitors, antiredeposition agents, soil release polyesters, dyes, dissolution improvers and/or disintegrants.
21. 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 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, complexing agent, 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.