EP1402104A1

EP1402104A1 - Method for treating surfaces of textiles and non-textiles, in such a way as to stimulate the detachment of dirt

Info

Publication number: EP1402104A1
Application number: EP02780767A
Authority: EP
Inventors: Christoph Hamers; Dieter Boeckh; Kati Schmidt
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2001-06-15
Filing date: 2002-06-13
Publication date: 2004-03-31
Also published as: WO2002103106A1; DE10128900A1; US20040250354A1

Abstract

The invention relates to a method for treating surfaces of textiles and non-textiles, in such a way as to stimulate the detachment of dirt. Cationically modified hydrophilic nanoparticles based on non-crosslinked polymers consisting of (a) between 60 and 100 wt. % of at least one ethylenically unsaturated monomer containing carboxyl groups, or the salts thereof, (b) between 0 and 40 wt. % of at least one water-insoluble monoethylenically unsaturated monomer, (c) between 0 and 25 wt. % of at least one monomer containing sulfonic acid and/or phosphonic acid groups, or the salts thereof, and (d) between 0 and 30 wt. % of at least one water-insoluble non-ionic monomer from an aqueous dispersion, are applied to the surface of said textiles or non-textiles. The dispersion of the hydrophilic nanoparticles can be stabilised with anionic, non-ionic and/or betainic emulsifiers and/or protective colloids. Said hydrophilic nanoparticles have a particulate size of between 10 nm and 2 mu m and can be cationically modified by coating their surface with at least one cationic polymer, at least one polyvalent metal ion and/or at least one cationic surfactant.

Description

Process for the dirt-removing treatment of surfaces of textile and non-textile materials

The invention relates to a method for the treatment of surfaces of textile and non-textile materials which require dirt removal, using cationically modified hydrophilic nanoparticles, the cationically modified hydrophilic nanoparticles themselves, aqueous dispersions containing them, the use of the hydrophilic nanoparticles and the cationically modified hydrophilic nanoparticles as dirt-removing additive Dishwashing, care, washing and cleaning agents as well as agents for the treatment of surfaces requiring dirt removal.

Dispersions of particles of hydrophobic polymers, in particular aqueous dispersions of synthetic polymers and of waxes, are used in industry to modify the properties of surfaces. For example, aqueous dispersions of finely divided hydrophobic polymers are used as binders in paper coating slips for coating paper or as paints. Each on a substrate using common methods, e.g. dispersions applied by knife coating, brushing, impregnation or impregnation are dried. The dispersed particles film into a coherent film on the respective surface.

Aqueous washing, rinsing, cleaning and care processes, on the other hand, are usually carried out in a highly diluted liquor, the majority of the ingredients of the formulation used not remaining on the substrate, but rather being disposed of with the waste water. The modification of surfaces with dispersed hydrophobic particles is only possible to an entirely unsatisfactory extent in the processes mentioned above. For example, US Pat. No. 3,580,853 discloses a detergent formulation 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.

From US-A-3 993 830 it is known to apply a non-permanent finish for dirt repellency to a textile good by treating the textile good with a dilute aqueous solution comprising a polycarboxylate and a contains water-soluble salt of a polyvalent metal. Suitable polycarboxylates are preferably water-soluble copolymers of ethylenically unsaturated monocarboxylic acids and alkyl acrylates. The blends are used in the household laundry in the washing machine rinse cycle.

From US-A-3 782 898 it is known to apply a non-permanent finish for dirt repellency to a textile good by treating the textile good with an acidic dilute aqueous solution which contains an acrylate polymer in dissolved or emulsified form. The document contains no reference to an advantageous use of particulate polymers and in particular no reference to an advantageous combination of particulate polymers with cationic substances.

The object of the present invention is to provide an improved method for the modification of textile surfaces, leather, hard smooth surfaces and hard porous surfaces which require dirt removal.

The object is achieved according to the invention by a process for the treatment of surfaces of textile and non-textile materials requiring dirt removal, in which cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

(a) 60 to 100% by weight of one or more ethylenically unsaturated monomers containing carboxyl groups or their salts,

(b) 0 to 40% by weight of one or more water-insoluble monoethylenically unsaturated monomers,

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

(d) 0 to 30% by weight of one or more water-soluble non-ionic monomers

can be applied from an aqueous dispersion to the surface of the materials, the dispersion of the hydrophilic nanoparticles being stabilized with anionic, nonionic and / or betaine emulsifiers and / or protective colloids, and the hydrophilic nanoparticles having a particle size of 10 nm to 2 μm and are cationically modified by covering their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants.

The object is further achieved by the use of the hydrophilic nanoparticles and the cationically modified hydrophilic nanoparticles, as well as the aqueous dispersions containing the hydrophilic or cationically modified hydrophilic nanoparticles as a dirt-removing additive to dishwashing, care, washing and cleaning agents.

The invention also relates to the cationically modified hydrophilic nanoparticles themselves and the aqueous dispersions containing them.

Hydrophilic nanoparticles in the sense of the present invention are hydrophilic polymer particles from uncrosslinked polymers or particulate hydrogels from crosslinked polymers, the particle size of which is 10 nm to 2 μm and which can be bound to the surface to be modified by means of cationic components. Particulate hydrogels are polymer particles which are strongly swollen with water, the acidic groups of the polymer particles being partially neutralized with water-soluble bases such as LiOH, NaOH, KOH or ammonium hydroxides. Cationic polymers, polyvalent metal cations or cationic surfactants are suitable as the cationic component. Cationically modified hydrophilic nanoparticles in the sense of the invention have their surface covered with one or more of the cationic components mentioned.

The hydrophilic nanoparticles to be used according to the invention are initially obtained in the form of aqueous dispersions during production and can be used as such, if appropriate after concentration or dilution. The hydrophilic nanoparticles can also be obtained and used as a solid after spray drying. By adding the cationic component, aqueous dispersions of the cationically modified hydrophilic nanoparticles can be obtained from the aqueous dispersions of the hydrophilic nanoparticles and used as such, or the spray-dried, cationically modified hydrophilic nanoparticles can be obtained and used as a solid. The cationically modified hydrophilic nanoparticles can also only be formed under the conditions of use in an aqueous rinsing, care, washing and cleaning liquor. The cationically modified hydrophilic nanoparticles can be obtained, for example, by mixing aqueous dispersions of the hydrophilic nanoparticles with an aqueous solution or dispersion of the cationic polymers, the polyvalent metal cations in the form of their soluble salts or the cationic surfactants. The cationic component is preferably used in the form of aqueous solutions, but it is also possible to use aqueous dispersions of the cationic polymers, the dispersed particles of which have an average diameter of up to 2 μm. The two components are usually mixed at room temperature, but the mixing can take place at temperatures of, for example, 0 ° to 100 ° C., provided that the dispersions do not coagulate when heated.

The hydrophilic nanoparticles to be used according to the invention are insoluble in water at the pH of the application. They are present in aqueous dispersion in the form of particles or particulate hydrogels with an average particle size of 10 nm to 2 μm, preferably from 25 nm to 1 μm, particularly preferably from 40 nm to 800 nm and in particular from 100 to 600 nm the aqueous dispersions can be obtained as powder. The average particle size of the nanoparticles can e.g. can be determined under the electron microscope or with the aid of light scattering experiments.

The pH of the aqueous dispersions of the hydrophilic nanoparticles is generally 1 to 6.5 and is preferably in the range from 1.5 to 5.5, particularly preferably in the range from 2 to 4.5.

The hydrophilic nanoparticles to be used according to the invention usually have a pH-dependent solubility and swelling behavior. The swelling behavior depends on the monomer composition, the average molecular weight of the polymers and the temperature. At pH values below 6.5, preferably below 5.5, particularly preferably below 4.5, the particles are water-insoluble and retain their particulate character or particulate hydrogel character when dispersed in concentrated and in dilute aqueous media. In contrast, the hydrophilic nanoparticles used according to the invention can swell strongly in water under neutral, in particular under alkaline conditions, or partially or completely dissolve.

Nanoparticles used according to the invention contain uncrosslinked polymers (a) 60 to 100% by weight, preferably 70 to 99% by weight, particularly preferably 75 to 95% by weight of one or more carboxyl group-containing ethylenically unsaturated monomers or their salts,

(b) 0 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight, of one or more water-insoluble monoethylenically unsaturated monomers,

(c) 0 to 25% by weight, preferably 0 to 15% by weight, particularly preferably 0.1 to 5% by weight, of one or more monomers containing sulfonic acid and / or phosphonic acid groups or their salts,

(d) 0 to 30% by weight, preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight, of one or more water-soluble nonionic monomers.

Preferred carboxyl group-containing ethylenically unsaturated monomers a) are β-unsaturated C ₃ -C ₆ carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, vinyl acetic acid, itaconic acid, maleic acid, itaconic acid semiesters of Ci-C ₆ alcohols, maleic acid or maleic acid semiesters of C _t -ce alcohols. Particularly preferred are acrylic acid, methacrylic acid, maleic acid or maleic acid half ester of -C _Ö - alcohols. Methacrylic acid is particularly preferred.

Water-insoluble monomers b) are all monomers which are less than 50 g / l soluble in water at room temperature. These are monomers from the group of the alkyl esters of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids and monohydric Ci-C ₂₂ alcohols, hydroxyalkyl esters of monoethylenically unsaturated C ₃ -C ₅ carboxylic acids and dihydric C ₂ -C alcohols, Vinyl esters of saturated Ci-C ^ - carboxylic acids, ethylene, propylene, isobutylene, C -C 2 -alpha-olefins, butadiene, styrene, alpha-methylstyrene, acrylonitrile, methacrylonitrile, tetrafluoroethylene, vinylidene fluoride, fluorethylene, chlorotrifluoroethylene, hexafluoropropene, esters and amides of C ₃ -C ₅ - monoethylenically unsaturated carboxylic acids with alcohols or amines containing perfluoroalkyl groups, allyl and vinyl esters of carboxylic acids containing perfluoroalkyl groups, or mixtures thereof. Higher proportions of water-insoluble monomers b) are preferably present in the polymers when very polar monomers a) such as acrylic acid, itaconic acid and maleic acid or monomers c) or d) in larger amounts, For example, the polymer contains more than 10% by weight, in particular more than 20% by weight.

Preferred water-insoluble monomers b) are acrylonitrile, 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 the perfluoroalkyl-substituted alcohols CF ₃ - (C ₂ F ₄ ) _n - (CH ₂ ) _m -OH or C ₂ F ₅ - (C ₂ F) _n - (CH ₂ ) _m -OH with n = 2-8, m = 1 or 2, vinyl acetate, vinyl propionate, styrene, ethylene, propylene, butylene, isobutene, diisobutene and tetrafluoroethylene, particularly preferred water-insoluble monomers b) are methyl acrylate, methyl methacrylate, ethyl acrylate, n -Butyl acrylate, tert-butyl acrylate and vinyl acetate.

Suitable monomers c) containing sulfonic acid or phosphonic acid groups are, for example, acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid, vinylphosphonic acid and the alkali metal and ammonium salts of these monomers.

Suitable water-soluble monomers d) have a solubility of at least 50 g / 1 water at room temperature. Suitable monomers d) are, for example, acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinyloxazolidone, methylpolyglycol acrylates, methylpolyglycol methacrylates and methylpolyglycol acrylamides. Monomers d) which are preferably used are vinylpyrrolidone, acrylamide and N-vinylformamide.

A characteristic feature of the uncrosslinked polymers contained in the nanoparticles is their particulate, i.e. unresolved character under the conditions of application. This particulate character is present in most compositions at a pH below 6.5, preferably below 5.5, particularly preferably below 4.5. In the case of high proportions of readily water-soluble monomers a), c) or d), it may be necessary to lower the pH further during use, e.g. under 3 or under 2 to ensure the particulate character. In the case of very small particles in the range of 10-100 nm, the particles can sometimes only be detected using special techniques such as electron microscopy.

Uncrosslinked polymers from the monomers a) and optionally b), c) and / or d) can be prepared by the known methods of solution, precipitation, suspension or Emulsion polymerization of the monomers can be prepared using radical polymerization initiators. The hydrophilic nanoparticles are preferably obtained by the process of emulsion polymerization in water. The polymers have, for example, molecular weights from 1,000 to 5,000,000, preferably from 5,000 to 1,000,000, and most of the time the molecular weights of the polymers are in the range from 10,000 to 500,000.

In addition to the polymerization processes mentioned, other processes for producing the hydrophilic nanoparticles can also be used. So you can e.g. Precipitate polymers by lowering the solubility of the polymers in the solvent. Such a method consists, for example, in that a polymer containing acidic groups is dissolved in a suitable water-miscible solvent and metered into an excess of water in such a way that the pH of the initial charge is at least 1 lower than the equivalent pH of the polymers. Equivalence pH is to be understood as the pH at which 50% of the acidic groups of the polymer are neutralized. In this process, it may be necessary to add a dispersing aid, pH regulators and / or salts in order to obtain stable, finely divided dispersions.

The aqueous dispersions of the hydrophilic nanoparticles can be stabilized with anionic, nonionic or betaine emulsifiers and / or protective colloids. The emulsifiers and protective colloids can already be present as dispersing aids in the production of the nanoparticles or can be added subsequently.

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

Nonionic and / or betaine emulsifiers can also be used. A description of suitable emulsifiers can be found e.g. in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

Examples of anionic protective colloids are water-soluble anionic polymers. Very different types of polymer can be used. Preferably come Anionically substituted polysaccharides and / or water-soluble anionic copolymers of acrylic acid, methacrylic acid, maleic acid, maleic acid semi-ester, vinyl sulfonic acid, styrene sulfonic acid or acrylamidopropane sulfonic acid with other vinyl monomers are used. Suitable anionically substituted polysaccharides are, for example, carboxymethyl cellulose, carboxymethyl starch, oxidized starch, oxidized cellulose and other oxidized polysaccharides and the corresponding derivatives of the freely 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.

Non-ionic and / or betaine protective colloids can also be used. An overview of commonly used protective colloids can be found in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 411 to 420.

For the production of dispersions of hydrophilic nanoparticles, polymers containing only monomers a) and optionally b) can be dispersed in water at a pH below 6.5. It is often advantageous to use nonionic emulsifiers or protective colloids. Polymers which contain at least one monomer c) in copolymerized form are preferably used and / or the polymers are emulsified with at least one anionic emulsifier and / or the dispersion is stabilized with at least one anionic protective colloid.

To stabilize hydrophilic nanoparticles to be used according to the invention, which contain anionic groups, additional polymers can be added during the dispersion. Examples of such polymers are polysaccharides, polyvinyl alcohols and polyacrylamides.

Hydrophilic nanoparticles can also be produced by controlled emulsification of a melt of the hydrophilic polymers. For this purpose, for example, the polymer or a mixture of the polymer is melted with further additives and metered into an excess of water under the action of strong shear forces, for example in an Ultra-Turrax, so that the pH of the initial charge is at least 1 lower than the equivalence - pH of the polymer. It may be necessary to add emulsifying agents, pH regulators and / or salts to obtain stable, finely divided dispersions. In this variant, too, the production of finely divided polymer Dispersions can use additional polymers such as polysaccharides, polyvinyl alcohols or polyacrylamides, especially if the hydrophilic polymer contains anionic groups.

Another method for producing hydrophilic nanoparticles which contain anionic groups consists in adding an acid to aqueous, alkaline solutions of the polymers, preferably under the action of strong shear forces.

The cationically modified, hydrophilic nanoparticles to be used according to the invention can be obtained by covering the surface of the hydrophilic nanoparticles with cationic polymers, polyvalent metal ions and / or cationic surfactants.

When anionically adjusted dispersions of the hydrophilic nanoparticles are treated 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. For example, cationically modified dispersions of particulate hydrophilic nanoparticles in 0.1% by weight aqueous dispersion at pH 4 have an interface potential of -5 to +50 mV, preferably from -2 to +25 mV, in particular from 0 to +15 mV , The interface potential is determined by measuring the electrophoretic mobility in dilute aqueous dispersion at the pH of the intended application liquor.

All natural or synthetic cationic polymers which contain amino and / or ammonium groups and are water-soluble can be used as cationic polymers. Examples of such cationic polymers are vinylamine unit-containing polymers, vinylimidazole unit-containing polymers, quaternary vinylimidazole unit-containing polymers, condensates of imidazole and epichlorohydrin, crosslinked polyamidoamines, crosslinked polyamidoamines grafted with ethyleneimine, polyethyleneimines, alkoxylated polyethyleneimines, crosslinked polyethyleneimineimines, amidated polyethyleneimines, amine-linked polyethyleneimines, amine-linked polyethyleneimines, amine-linked polyethyleneimines, amine-containing polyethyleneimines, amine-linked polyethyleneimines, amine Amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylarnins, polydimethyldiallylammonium chlorides, polymers containing basic (meth) acrylamide or ester units, polymers containing basic quaternary (meth) acrylamide or ester units, and or lysine condensates. Cationic polymers are also understood to mean amphoteric polymers which have a net cationic charge, ie the polymers contain both anionic and cationic monomers copolymerized, but the molar proportion of the cationic units contained in the polymer is greater than that of the anionic units.

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

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

Suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are all compounds which can be copolymerized therewith. Examples of these are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as Ci to Cβ alkyl vinyl ether, for example methyl or ethyl vinyl ether. Further suitable comonomers are ethylenically unsaturated C ₃ - to C ₆ -carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl acetic acid, and also their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate and ethyl acrylate ethyl methacrylate. Further suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are carboxylic esters which are derived from glycols or polyalkylene glycols, only one OH group being esterified in each case, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate and hydroxypropyl methacrylate of polyalkylene glycols with a molecular weight of 500 to 10,000. Further suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylate, dimethylaminopropyl methacrylate diethylamethylobylethylethylamethyloblylethyl acrylate diethylamethyloblylethyl acrylate, The basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form. Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.

Other suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as

Acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl residues of 1 to 6 carbon atoms, e.g.

N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide,

N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic

(Meth) acrylamides, e.g. dimethylaminoethyl,

Dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide,

Diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and

Diethylaminopropylmethacrylamide.

Also suitable as comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole, N-vinyl-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline. In addition to the free bases, N-vinylimidazoles and N-vinylimidazolines are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, Methyl chloride or benzyl chloride is made. Diallyldialallmonmonium halides such as diallyldimethylammonium chlorides are also suitable.

In addition, monomers containing sulfo groups such as vinylsulfonic acid, AUylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfo-propyl acrylate are suitable as comonomers, the content of the amphoteric copolymers of cationic units being the content of anionic units Units exceeds, so that the polymers have a total cationic charge.

The copolymers contain, for example

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

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

in polymerized form.

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

- N-vinylformamide with

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

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

The polymers described above are hydrolysed by known processes by the action of acids, bases or enzymes. Here arise from the polymerized monomers of the above formula (I) by splitting off the grouping

C - R

(II)

O

where R ^{2 has} the meaning given for it in formula I, polymers, the vinylamine units of the formula (III)

CH ₂ - CH-

N ( ^m )

/ \ _!

MR

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

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

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

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

Suitable polymers containing amino and / or ammonium groups are also polyamidoamines, which can be obtained, for example, by condensing dicarboxylic acids with polyamines. Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids with 4 to 10 carbon atoms with polyalkylene polyamines which contain 3 to 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. Mixtures of dicarboxylic acids can also be used in the preparation of the polyamidoamines, as can mixtures of several polyalkylene polyamines. Suitable polyalkylene polyamines are for example diethylenetriamine, triethylenetetramine, tettaethylenepentamine,

Dipropylenetriamine, tripropylenetetramine, dimexamethylenetriamine, aminopropylethylenediamine and bis-aminopropylethylenediamine. The dicarboxylic acids and polyalkylene polyamines are heated to higher temperatures to produce the polyamidoamines, e.g. to temperatures in the range of 120 to 220, preferably 130 to 180 ° C. The water generated during the condensation is removed from the system. Lactones or lactams of carboxylic acids having 4 to 8 carbon atoms can optionally also be used in the condensation. For example, 0.8 to 1.4 moles of a polyalkylene polyamine are used per mole of a dicarboxylic acid.

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

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

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

Other suitable cationic polymers are copolymers of, for example, 1 to 99 mol%, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol%, of cationic monomers such as dialkylaminoalkylacrylamide, esters and / or methacrylamide and / or methacrylic ester. The basic acrylamides and methacrylamides are also preferably in neutralized or quaternized form with acids. Examples include N-trimethylammonium ethyl acrylamide chloride,

N-Trimethylanimoniumethylmethacrylamidchlorid, N-trimethylammoniumethyl methacrylic ester chloride, N-triethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl acrylamide methosulfate, trimethylamine methyl methacrylamide ^ ethosulfate, N-ethyl dimethylammonium ethyl acrylamide ethosulfate,

N-ethyldimethylammoniumethyl methacrylamide ethosulfate, trimemylammonium propylacrylamide chloride, trimethylarnmonium propyl methacrylamide chloride, trimethylarnmonium propylacrylamide methosulfate, trimemylarrmionium propyl methacrylamide methosulfate and N-ethyldimemylammonium propyl acrylamide. Trimethylammonium propyl methacrylamide chloride is preferred.

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

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

The cationic polymers have, for example, K values from 8 to 300, preferably 100 to 180 (determined according to H. Fikentscher in 5% by weight aqueous saline 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. Examples of preferred cationic polymers are polydimemyldiallylammonium chloride, polyethyleneimine, polymers containing vinylamine units, copolymers of acrylamide or methacrylamide containing copolymerized basic monomers, polymers containing lysine units or mixtures thereof. Examples of cationic polymers are:

• Copolymers of 50% vinyl pyrrolidone and 50% trimethylammonium ethyl methacrylate methosulfate, M _w 1000 to 500 000;

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

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

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

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

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

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

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

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

Vinylimidazole homopolymers, vinylimidazole copolymers with vinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate with molecular weights from 5,000 to 500,000 and their quaternary derivatives, Polyethyleneimines, crosslinked polyethyleneimines or amidated polyethyleneimines with molecular weights from 500 to 3,000,000,

Amine-epichlorohydrin polycondensates which contain imidazole, piperazine, Ci-Cs-alkylamines, Ci-Cg-dialkylamines and / or dimethylaminopropylamine as amine component and which have a molecular weight of 500 to 250,000,

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

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

In order to cationically modify hydrophilic nanoparticles, they can also be treated with polyvalent metal ions and / or cationic surfactants. A coating of the particles with polyvalent metal ions is achieved, for example, by adding an aqueous solution of at least one water-soluble, polyvalent metal salt to an aqueous dispersion of anionically dispersed hydrophilic nanoparticles or by dissolving a water-soluble, polyvalent metal salt therein, with a modification of the anionically dispersed hydrophilic nanoparticles cationic polymers can 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. Water-soluble heavy metal salts derived, for example, from Cu, Ni, Co and Mn can also be used in principle, but are not desirable in all applications. Examples of water-soluble metal salts are calcium chloride, calcium acetate, magnesium chloride, aluminum sulfate, aluminum chloride, barium chloride, zinc chloride, zinc sulfate, zinc acetate, iron (II) sulfate, iron (III) chloride, chromium (III) sulfate. Copper sulfate, nickel sulfate, cobalt sulfate and manganese sulfate. The water-soluble salts of Ca, Al and Zn are preferably used for the cationic modification.

The transfer of the hydrophilic nanoparticles is also possible with cationic surfactants.

Mer are potentially suitable for cationic surfactants with different structures. An overview of a selection of suitable cationic surfactants is in Ullmanns

Encyclopedia of Industrial Chemistry, Sixth Edition, 1999, Electronic Release, chapter "Surfactants", Chapter 8, Cationic Surfactants.

Particularly suitable cationic surfactants are, for example, C ₇ to C ₂₅ alkylamines, Cη to C ₂₅ - N, N-dimethyl-N- (hydroxyalkyl) ammonium salts, mono- and di- (C ₇ - to C ₂₅ -) quaternized with alkylating agents -alkyldimethylammonium compounds, ester quats such as quaternary esterified mono-, di- or trialkanolamines esterified with C ₈ -C ₂₂ -carboxylic acids, imidazoline quats such as 1-alkylimidazolinium salts of the general formulas

R ³

, / R ² RR ^z

IV V

wherein

R ¹ = Ci-C ₂₅ alkyl or C ₂ -C ₂₅ alkenyl, R ² = Ci-C ₄ alkyl or hydroxyalkyl and R ³ = Ci-C ₄ alkyl, hydroxyalkyl or an Rr (C = O) - X- (CH ₂ ) „- with X = O or NH and n2 or 3

mean and wherein at least one radical R ¹ = C -C ₂₂ - alkyl.

In many commercial and technical applications in everyday domestic life, the dirt-removing modification of textiles, textile surfaces, leather, wood, smooth and structured hard surfaces is important. For example, the surfaces of textile and non-textile materials to be treated according to the invention include microscopic hard surfaces, floor and wall coverings, glass surfaces, ceramic surfaces, stone surfaces, concrete surfaces, metal surfaces, enamelled surfaces, plastic surfaces, wood surfaces, surfaces of coated woods or lacquered surfaces. Microscopic surfaces include, for example, the surfaces of porous bodies such as foams, woods, leather, porous building materials and porous minerals. Other suitable surfaces are floor or wall paints or coatings and cellulose nonwovens. It is not always possible Modification of the surfaces by impregnation and painting processes with concentrated formulations. It is often desirable to carry out the modification by rinsing the material to be treated with a highly diluted liquor containing the active substance, or to achieve the modification by spraying on a highly dilute aqueous formulation. It is often advantageous to combine the modification of the surfaces of the materials to be treated with washing, cleaning and / or care or impregnation of the surface.

All types of fiber fabrics, covers and coverings can be considered as textile materials, it being possible to treat both synthetic fibers and natural fibers and modified natural fibers. In particular, textiles come from cotton fabrics, modified cotton such as Viscose, cotton blend such as Cotton / polyester blended fabrics and cotton / polyamide blended fabrics as well as textiles made from finished fabrics or fibers are considered. Other types of preferably treated textile surfaces are e.g. Carpets, upholstery and decorative fabrics.

All types of smooth and rough leathers are further preferred surfaces to be treated with nanoparticles according to the invention. Of particular interest is the modification of rough leather surfaces (e.g. made of suede) of leather clothing, shoes and furniture to promote dirt release.

Further surfaces to be treated preferably with nanoparticles according to the invention are floor coverings made of plastics, such as Linoleum or PVC.

The modification of the surfaces of the above-mentioned materials consists above all in a dirt-removal-promoting effect by treatment with the cationically modified hydrophilic nanoparticles according to the invention. This means that it is easier to remove dirt during subsequent washing, rinsing or cleaning. In addition, other effects such as a reduction in dirt adhesion, protection against chemical or mechanical influences or damage, an improvement in the structure retention of fibers, an improvement in the shape and structure retention of fabrics, a reduction in static charge and an improvement in grip.

The concentration of the hydrophilic nanoparticles when used in the rinsing or care bath, in the detergent liquor or in the cleaning bath is generally 0.0002 up to 1.0% by weight, preferably 0.0005 to 0.25% by weight, particularly preferably 0.002 to 0.05% by weight.

The respective surfaces are treated with cationically modified hydrohilic nanoparticles according to the invention from aqueous liquors or rinsing or spray formulations which, for example, contain 2.5 to 300 ppm, preferably 5 to 200 ppm and in particular 10 to 100 ppm, one or more cationic polymers and / or 1 to 6 mmol / 1, preferably 1.5 to 4 mmol / 1 one or more water-soluble salts of divalent metals, in particular salts of Ca, Mg or Zn and / or 0.05 to 2 mmol / 1, preferably 0.1 to 0.75 nmol / l contain one or more water-soluble Al salts and / or 1 to 600 ppm, preferably 10 to 300 ppm, of cationic surfactants.

If cationically modified nanoparticles according to the invention are used as additives, the addition of further cationic polymers, polyvalent metal ions or cationic surfactants can be dispensed with in whole or in part.

The rinsing liquor or the formulation to be sprayed on is generally prepared by diluting concentrated formulations with water or predominantly aqueous solvents. If this dilution is carried out with water which contains at least 1.0 mmol of Ca ²⁺ and / or Mg, preferably at least 1.5 mmol / 1, particularly preferably at least 2.0 mmol / 1, treatment with dispersions of the hydrophilic nanoparticles can also be carried out without Cationic polymers, polyvalent metal ions and / or cationic surfactants are added.

Agents according to the invention for treating surfaces which are used in dilution with water can be solid or liquid. Solid agents can be in the form of powder, granules or tablets and are dissolved or dispersed for use in water, the nanoparticles according to the invention being dispersed after dilution.

The cationic modification of the hydrophilic nanoparticles is preferably carried out before use in the aqueous treatment agents. However, it can also take place in the production of the aqueous treatment agents or in the use of non-cationically modified hydrophilic nanoparticles, for example by mixing aqueous dispersions of the hydrophilic nanoparticles with the other constituents of the particular Mixing agent in the presence of cationic polymers, water-soluble salts of polyvalent metals and / or cationic surfactants.

In a special embodiment, the non-cationically modified nanoparticles or formulations containing these particles can also be added directly to the rinsing, washing or cleaning liquor if it is ensured that sufficient amounts of cationic polymers and / or polyvalent metal ions and / or cationic ones are present in the liquor Dissolved surfactants. For example, it is possible to use the non-cationically modified hydrophilic nanoparticles or formulations containing these particles in liquors with a cationic polymer content of 2.5 to 300 ppm, water-soluble salts of Ca, Mg or Zn of more than 0.5 mmol / l, preferably above 1.0 mmol / 1, particularly preferably above 2.0 mmol / 1. If cationic surfactants are used, they are used, for example, in concentrations of 50 to 1000 ppm, preferably 75 to 500 ppm and in particular 100 to 300 ppm in the aqueous liquor.

The hydrophilic, non-cationically modified nanoparticles or formulations containing these nanoparticles can also be metered into the rinsing liquor before, after or at the same time with a formulation comprising cationic polymers, polyvalent metal ions and / or cationic surfactants.

The present invention also relates to an agent for treating surfaces of textile or non-textile materials that require dirt removal:

a) 0.05 to 40% by weight of hydrophilic nanoparticles,

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

c) 0 to 20% by weight of acid,

d) 0 to 80% by weight of conventional additives such as bases, inorganic builders, organic

Cobuilder, other surfactants, polymeric color transfer inhibitors, polymeric

Graying inhibitors, other soil release polymers other than (a), enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, Light stabilizers, dyes, non-aqueous solvents, adjusting agents, hydrotropes, thickeners and / or alkanolamines, and

e) 0 to 99.95 wt .-% water.

In one embodiment, the agents according to the invention contain 0.01 to 10% by weight of acid. In a further embodiment, the agents according to the invention contain 0.01 to 40% by weight of conventional additives. In a further embodiment, the agents according to the invention contain 50 to 95% by weight of water.

Agents according to the invention for the treatment of surfaces which are used in dilution with water can, for example, have the following composition:

(a) 0.1 to 40% by weight of hydrophilic nanoparticles,

(c) 0 to 20% by weight acid, and

(d) 0.01 to 80% by weight of customary additives such as acids, bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, further soil release polymers different from (a),

Enzymes, perfume substances, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines.

Preferred agents according to the invention for the treatment of surfaces which are used in dilution with water have the following composition:

(a) 0.1 to 40% by weight of hydrophilic nanoparticles,

(b) 0.1 to 30% by weight of cationic polymers and / or water-soluble salts of Mg, Ca, Zn or Al and / or cationic surfactants,

(c) 0 to 20% by weight acid, and

(d) 0 to 80% by weight of conventional additives, such as bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, and polymers Graying inhibitors, further soil release polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, different from (a).

Further preferred agents according to the invention for the treatment of surfaces which are used in dilution with water have the following composition:

(a) 0.1 to 40% by weight of hydrophilic nanoparticles,

(b) 0.1 to 10 wt% acid, and

(d) 0 to 80% by weight of customary additives such as bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, further soil release polymers different from (a),

Particularly preferred agents according to the invention for the treatment of surfaces which are used in dilution with water have the following composition:

(a) 0.1 to 40% by weight of hydrophilic nanoparticles,

(b) 0.01 to 30% by weight of cationic polymers, water-soluble salts of Mg, Ca, Zn or Al and / or cationic surfactants,

(c) 0.1 to 10 wt% acid, and

(d) 0.01 to 80% by weight of conventional additives such as bases, inorganic builders, organic cobuilders, further surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, further soil release polymers, enzymes, perfumes, complexing agents which are different from (a) , Corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines. Liquid agents are present as a dispersion, and the dispersion can also be completely transparent if very small nanoparticles according to the invention are used or if their concentration is very low. Liquid agents according to the invention have a pH below 6.5, preferably below 5.5, particularly preferably below 4.5.

Liquid compositions for the dirt-removing treatment of surfaces that are used in dilution with water can also have the following composition:

(a) 0.1 to 40% by weight of hydrophilic nanoparticles,

(c) 0.1 to 10% by weight of acid,

(d) 0.01 to 40% by weight of conventional additives such as bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymers

Graying inhibitors, other soil release polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and, and

(e) 50-95% by weight water,

wherein the pH of the agent is from 1 to 6.5.

Preferred liquid agents for the dirt-removing treatment of surfaces which are used in dilution with water can also have the following composition:

(a) 0.1 to 40% by weight of hydrophilic nanoparticles,

(c) 0.1 to 10% by weight of acid, (d) 0.01 to 40% by weight of conventional additives such as bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, further soil release polymers other than (a), enzymes, perfume substances, complexing agents, Corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, solvents, hydrotropes, thickeners and / or alkanolamines,

(e) 50-95% by weight water,

wherein the pH of the agent is from 1 to 6.5.

In the formulations described above, component (b) can be composed, for example, as follows:

(bl) 0.01 to 10% by weight of cationic polymers and / or

(b2) 0.01 to 30% by weight of water-soluble salts of Mg, Ca, Zn or Al and / or

(b3) 0.01 to 30% by weight of cationic surfactants,

in each case based on the total weight of the agent, the sum of (b1) to (b3) being a maximum of 30% by weight.

Suitable acids (c) are both mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid or organic acids such as carboxylic acids or sulfonic acids, strong mineral acids and sulfonic acids being used either diluted in a small amount below 5% by weight or as partially neutralized acid salts. C ₃ -monocarboxylic acids, C ₂ -C ₁₈ -dicarboxylic acids and Ce-Cis-tricarboxylic acids used - are preferably C _\. In particular, C ₃ -C ₁₄ -Alkenylbemsteinsäuren, maleic acid, adipic acid, malic acid, tartaric acid, butanetetracarboxylic acid and citric acid are formic acid, acetic acid, lactic acid, oxalic acid, succinic acid, C ₃ -C ₁₄ -Alkylbemsteinsäure used.

Laundry detergent and laundry care products that promote dirt detachment, for example, contain

(a) 0.1 to 30% by weight of hydrophilic nanoparticles, (b) 0.1 to 10% by weight of cationic polymers, water-soluble salts of Mg, Ca, Zn or Al and / or cationic surfactants,

(c) 0.05 to 20% by weight of a carboxylic acid such as formic acid, citric acid,

Adipic acid, succinic acid, oxalic acid or mixtures thereof,

(d) 0 to 10% by weight of other customary ingredients such as perfume, silicone oil, light stabilizers, dyes, complexing agents, graying inhibitors, further soil release polymers different from (a), color transfer inhibitors, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and

(e) 30 to 99.65 wt% water.

Preferred laundry detergent and laundry care products that require soil release

(a) 1 to 30% by weight of hydrophilic nanoparticles,

(b) 0.1 to 30% by weight of cationic polymers and / or water-soluble salts of Mg, Ca, Zn and / or Al and / or cationic surfactants,

(c) 1 to 15% by weight of a carboxylic acid such as formic acid, citric acid, adipic acid, succinic acid, oxalic acid or mixtures thereof,

(d) 0 to 10% by weight of at least one other conventional ingredient such as perfume, silicone oil, light stabilizers, dyes, complexing agents, graying inhibitors, soil release polyesters, color transfer inhibitors, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and

(e) 15 to 97.9 wt% water.

Component (b) can, for example, consist of

(bl) 0.1 to 10% by weight of cationic polymers and / or (b2) 0.1 to 30% by weight of water-soluble salts of Mg, Ca, Zn and / or Al, at most 10% by weight, and / or

(b3) 0.1 to 30% by weight of cationic surfactants,

in each case based on the total weight of the laundry aftertreatment or laundry care agent, the sum of components (b1) to (b3) giving 0.1 to 30% by weight.

Component (b2) can consist, for example, of 0.1 to 30% by weight of water-soluble salts of Mg, Ca and / or Zn and / or 0.1 to 10% by weight of water-soluble salts of aluminum, based on the total weight of the Laundry aftercare or laundry care products.

Another application of the cationically modified hydrophilic nanoparticles according to the invention consists in spraying dilute aqueous formulations onto the surface to be treated. This can be done in the home or in commercial use by spraying using a spray bottle or an automatic spraying device. The formulations suitable for this have, for example, the following compositions:

(a) 0.005 to 2% by weight of hydrophilic nanoparticles,

(b) 0.0005 to 1% by weight of cationic polymers and / or water-soluble salts of Mg, Ca, Zn and / or Al and / or cationic surfactants,

(c). 0 to 10% by weight of conventional additives such as bases, inorganic builders, organic

Cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, soil release polymers other than (a), enzymes, perfume substances, complexing agents, corrosion inhibitors, waxes, silicone oils,

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

(d) 87-99.9945 wt% water,

wherein the pH of the agent is from 1 to 6.5. Typical additives used in formulations according to the invention are the additives used in detergents, cleaning agents and textile rinsing agents, for example as described in “Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000, Electronic Version 2.0”.

The following are particularly suitable as surfactants and cobuilders:

Anionic surfactants, especially:

(Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ to Cπ alcohol sulfates, C ₁₂ to C ₁ alcohol sulfates, C _{2 to} C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, Myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;

sulfated alkoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates); Compounds of this type are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product; ethylene oxide is preferably used for the alkoxylation;

linear C ₈ to C ₂ o-alkylbenzenesulfonates (LAS), preferably linear C to C ₁₃ alkylbenzenesulfonates and alkyltoluenesulfonates,

Alkanesulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkanesulfonates;

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

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

alkoxylated C ₈ to C ₂₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These can be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of one of the above-mentioned alkylene oxides added can be used as surfactants. Here, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. The nonionic surfactants generally contain 2 to 50, preferably 3 to 20, per mole of alcohol

Moles of at least one alkylene oxide. These preferably contain ethylene oxide as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;

Alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ - to C _H -alkyl chains and 5 to 30 alkylene oxide units;

Alkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5, glucoside units;

N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

Suitable inorganic builders are in particular:

crystalline or amorphous aluminosilicates with ion-exchanging properties such as, in particular, zeolites. Suitable zeolites are in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium;

crystalline silicates such as, in particular, disilicates or layered silicates, for example δ-Na ₂ Si ₂ θ ₅ or ß-a ₂ Si ₂ O ₅ . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates;

amorphous silicates such as sodium metasilicate or amorphous disilicate; Carbonates and bicarbonates; these can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or bicarbonates are preferred, in particular sodium carbonate and / or sodium bicarbonate;

Polyphosphates such as pentasodium triphosphate;

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

Suitable low molecular weight carboxylic acids are, for example, citric acid, hydrophobically modified citric acid such as. B. agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as e.g. Nitrilotriacetic acid, ß-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic acid;

Suitable oligomeric or polymeric carboxylic acids are, for example, homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid, C ₂ -C ₂₂ olefins such as, for example, isobutene or long-chain α-olefins, vinyl alkyl ethers with CrCg alkyl groups, vinyl acetate, vinyl propionate, (meth) acrylic ester of Ci-C ₈ alcohols and styrene. It is preferred to use the

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

The invention is illustrated by the examples below. Examples

dispersions

Examples of typical anionic dispersions which can be processed by mixing with cationic polymers, water-soluble salts of polyvalent metals and / or cationic surfactants and other components to detergents, cleaning agents or care products are the dispersions 1 to 3 described below, the dispersed particles of which are in each case in dynamic light scattering can be observed as discrete particles with the specified average particle diameter.

With the nanoparticles 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 processes.

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

Dispersion 1

66.8 g of an oxidatively degraded starch with a degree of carboxylate substitution of 0.03 to 0.04 and a K value of 34 are placed in a polymerization vessel which is equipped with a stirrer, reflux condenser, metering devices and facilities for working under a nitrogen atmosphere (determined according to DIN 53726, Amylex 15 from Südstär) and

726 g of water and, with stirring, heated to a temperature of 85 in 25 minutes

° C. Then 0.2 g of a 25% strength by weight aqueous calcium acetate solution and 10 g of a 1% strength by weight commercial enzyme solution (alpha-amylase, Termamyl 120 L of

Novo Nordisk) too. After 15 minutes, the enzymatic starch breakdown is stopped by adding 6 g of glacial acetic acid. 16.8 g of a 1% strength by weight aqueous solution are also added

Iron (II) sulfate solution. The temperature of the reaction mixture is kept at 85 ° C.

At this temperature, a mixture of 55 g of ethyl acrylate, 77.5 g of methacrylic acid and 17 g of acrylic acid is added within 90 minutes. Simultaneously with that

The monomer feed begins, the initiator feed, 42 g become one within 105 minutes 15 wt .-% hydrogen peroxide solution added. After the entire amount of initiator has been metered in, the mixture is cooled to 50.degree. Then 0.3 g of a 70% strength by weight tert-butyl hydroperoxide solution is metered in over the course of 15 minutes and the mixture is subsequently stirred for 30 minutes. It is then cooled to room temperature. A dispersion with a solids content of 21% by weight, an average particle diameter of the dispersed particles of 254 nm and a filtration residue of 0.3 g, based on the total batch, is obtained.

Dispersion 2

In a glass reactor provided with an anchor stirrer, thermometer, gas inlet tube, dropping funnel and reflux condenser, 8 g of a 2.5% strength by weight sodium peroxydisulfate solution as an initiator feed, 4 g of a 15% strength by weight sodium lauryl sulfate solution and 841 g of water are introduced and stirred heated in a heating bath, at the same time displacing the air by introducing nitrogen. When the heating bath has reached the preset temperature of 75 ° C, the introduction of nitrogen is interrupted and an emulsion consisting of 15 g of a 15% by weight sodium lauryl sulfate solution, 266 ml water, 72 g ethyl acrylate, 106 g becomes over 2 hours Methacrylic acid and 22 g of acrylic acid were added dropwise to the template. After the end of the addition, polymerization is continued at 75 ° C. for 1 hour. The mixture is then cooled to room temperature and 0.5 g of a 30% by weight hydrogen peroxide solution are immediately added and a solution consisting of 0.2 g of ascorbic acid, 0.2 g of iron (II) sulfate and 19. 8 g of water added. A dispersion is obtained with a solids content of 15% by weight, a particle diameter of 100 nm, a pH of 3 and a filtration residue of 0.5 g, based on the total batch.

Dispersion 3

In a glass reactor provided with an anchor stirrer, thermometer, gas inlet tube, dropping funnel and reflux condenser, 8 g of a 2.5% strength by weight sodium peroxydisulfate solution as an initiator feed, 4 g of a 15% strength by weight sodium lauryl sulfate solution and 841 g of water are introduced and stirred heated in a heating bath, at the same time displacing the air by introducing nitrogen. If the heating bath has reached the preset temperature of 75 ° C, the introduction of nitrogen is interrupted and an emulsion consisting of 15 g of a 15 wt. -% sodium lauryl sulfate solution, 266 ml of water, 52 g of ethyl acrylate, 126 g of methacrylic acid and 22 g of acrylic acid were added dropwise to the template. After the end of the addition, polymerization is continued at 75 ° C. for 1 hour. The mixture is then cooled to room temperature and 0.5 g of a 30% strength by weight hydrogen peroxide solution are immediately added and a solution consisting of 0.2 g of ascrobic acid, 0.2 g of iron (II) sulfate and 19. 8 g of water added. A dispersion is obtained with a solids content of 15% by weight, a particle diameter of 100 nm, a pH of 3 and a filtration residue of 0.6 g, based on the total batch.

washing tests

The following washing tests were carried out to test the soil-detaching properties of post-rinse formulations with nanoparticles according to the invention in comparison with post-rinse formulations according to the prior art:

example 1

Dispersion 1 was diluted with deionized water of pH 4 to a concentration of 2000 ppm and, with stirring, metered into the same amount of a solution of 200 ppm of high molecular weight polyethylene with a molecular weight of 1 000 000 in deionized water of pH 4. The pH was adjusted with 0.1 N HC1.

The diluted dispersion thus obtained was used as a rinse liquor.

Comparative Example 1

Dispersion 1 was diluted to a concentration of 1000 ppm with deionized water of pH 4, adjusted with 0.1 N HCl, and used as a rinse liquor. Comparative Example 2

The aqueous solution of a copolymer according to Example 1 of US 3,836,496 of methacrylic acid and ethyl acrylate in a weight ratio of 66.6: 33.3 was diluted to a concentration of 1000 ppm and adjusted to a pH of 4 with 1N HCl. This solution was used as a rinse liquor.

Example 2

Dispersion 2 was diluted to a concentration of 1000 ppm with water which contained 3.0 mmol / 1 CaCl ₂ and was adjusted to pH 4 with 0.1 N HCl. The diluted dispersion thus obtained was used as a rinse liquor.

Comparative Example 3

A solution of a copolymer with a polymer content of 1000 ppm according to Example 1 of US 3,993,830 of methacrylic acid and ethyl acrylate in a weight ratio of 66.6: 33.3 was adjusted to pH 4 in water with 0.1 N HCl, the 3.0 mmol / Contained 1 calcium chloride dissolved. This solution was used as a rinse liquor.

Comparative Example 4

Dispersion 2 was diluted with deionized water of pH 4, adjusted with 0.1 N HCl, to a concentration of 1000 ppm and used as a rinse liquor.

Example 3

33.3 g of dispersion 3 were diluted to 50 g with 1.25 M aqueous formic acid. 1.4 g of calcium chloride was diluted to 50 g with 1.25 M aqueous formic acid. The dispersion was mixed with the calcium chloride solution with stirring. The formulation obtained contained 5.0% by weight of hydrophilic nanoparticles and 126 nmol / 1 calcium ions. 16 g of the formulation per liter of water with 0.5 mmol / 1 calcium chloride were used for the rinse liquor. Comparative Example 5

33.3 g of the dispersion from Example 3 were diluted to 100 g with 1.25 M formic acid. The formulation obtained contained 5.0% nanoparticles and no calcium ions. 16 g of the formulation per liter of water with 0.5 mmol / 1 calcium chloride were used for the rinse liquor.

In separate experiments, two 2.5 g cotton fabrics or polyester / cotton (50:50) blended fabrics (test fabrics) together with 5 g ballast fabrics (equal parts cotton and cotton / polyester blended fabrics) with a granular household detergent (Ariel Futur) washed, rinsed with tap water and rinsed with the rinse liquors from Examples 1 to 3. The test fabrics were then dried and soiled.

In a first test series, lipstick mass was used as soiling. The application was done with a brush and a stencil on a circle of 4 cm in diameter.

In a second series of tests, used motor oil was used as soiling. The application was carried out by dropping 0.3 g of the oil onto the horizontal fabric.

The reflectance of the soiled tissue before washing at 460 nm was determined (in% reflectance). The fabrics were then washed again with the heavy-duty detergent (Ariel Futur) with the addition of 15 g of ballast fabric (in equal parts cotton and cotton / polyester blend). In order to evaluate the effect that requires dirt removal, the reflectance of the soiled tissue after washing at 460 nm was measured (in% remission) and the reflectance difference ΔR was determined from the reflectance values before and after washing. The values for both tissues of an experiment were averaged and rounded to whole numerical values.

Washing conditions:

Prewash:

Washing machine: Launder-0-meter Prewash temperature: 20 ° C Prewash time: 15 min liquor ratio: 25

Main wash:

Washing temperature: 40 ° C Detergent: Ariel Futur Detergent dosage: 3.5 g / 1 washing time: 30 min Water hardness: 3 mmol / 1 Ca / Mg ratio: 3: 1 liquor ratio: 12.5

Table 1: Washing tests with lipstick mass as soiling

Table 2: Washing attempts with dirty motor oil as soiling

The comparison of Example 1 with Comparative Examples 1 and 2 shows that when rinsing with nanoparticles in water in the absence of hardness ions, a good dirt-removing effect only occurs if a cationic polymer is present. The dissolved acrylate copolymer according to US 3,836,496 has no effect on the cotton / polyester blend at the same concentration.

The comparison of Example 2 with Comparative Examples 3 and 4 shows that when rinsing with nanoparticles according to the invention in water in the presence of 3 mmol / 1 Ca ions, a very good dirt-removing effect occurs, while this is not observed in the absence of Ca ions , With the dissolved polymer according to US Pat. No. 3,993,830, no satisfactory effect is achieved even in the presence of 3.0 mmol of Ca ions.

The comparison of Example 3 with Comparative Example 5 shows that at low doses of calcium ions, as e.g. occurs in tap water from areas with soft water, only the formulation according to the invention with additional calcium ions produces a good effect.

Claims

claims

1. Process for the dirt-removing treatment of surfaces of textile and non-textile materials, in which cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

(c) 0 to 25% by weight of one or more sulfonic acid and / or

Monomers containing phosphonic acid groups or their salts,

(d) 0 to 30% by weight of one or more water-soluble nonionic monomers

can be applied from an aqueous dispersion to the surface of the materials, the dispersion of the hydrophilic nanoparticles being stabilized with anionic, nonionic and / or betaine emulsifiers and / or protective colloids, and wherein the hydrophilic nanoparticles have a particle size of 10 nm to 2 μm and are cationically modified by covering their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants.

2. The method according spoke 1, characterized in that the aqueous dispersion contains 0.0002 to 1 wt .-% hydrophilic nanoparticles.

3. The method according to claim 1 or 2, characterized in that the pH of the aqueous dispersion is from 1 to 6.5.

4. The method according to any one of claims 1 to 3, characterized in that the cationic polymers are selected from the group consisting of polymers containing vinylamine units, polymers containing vinylimidazole units, polymers containing quaternary vinylimidazole units, imidazole / epichlorohydrin condensates, cross-linked polyamidoamines, with

Crosslinked polyamidoamines, polyethyleneimines, alkoxylated polyemyleneimines, crosslinked polyethyleneimines, amidated polyethyleneimines, alkylated polyethyleneimines, polyamines,

Amine / epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines, polydimethyldiallylammonium chlorides, basic

Polymers containing (meth) acrylamide or (meth) acrylic ester units, basic polymers containing quaternary (meth) acrylamide or (meth) acrylic ester units, and lysine condensates.

5. The method according to any one of claims 1 to 3, characterized in that the polyvalent metal cations are selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Al ³⁺ and Zn ²⁺ .

6. The method according to any one of claims 1 to 4, characterized in that the cationic surfactants are selected from the group consisting of C -C ₂₅ -

Alkylamine, C -C ₂₅ alkylammonium, di (C -C2 ₅ ) alkylammonium, C ₇ -C ₂₅ alkyl ester quat and C ₇ -C ₂₅ alkylimidazolinium compounds.

7. Cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

(c) 0 to 25% by weight of one or more monomers containing sulfonic acid and / or phosphonic acid groups or their salts, (d) 0 to 30% by weight of one or more water-soluble nonionic monomers,

wherein the hydrophilic nanoparticles have a particle size of 10 nm to 2 μm and are cationically modified by coating their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants.

8. Aqueous dispersions of cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

(d) 0 to 30% by weight of one or more water-soluble nonionic monomers,

wherein the dispersion of the hydrophilic nanoparticles can be stabilized with anionic, nonionic and / or betaine emulsifiers and / or protective colloids, and wherein the hydrophilic nanoparticles have a particle size of 10 nm to 2 μm and by covering their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants are cationically modified.

9. Aqueous dispersions according to spoke 8, characterized in that they contain 0.001 to 50 wt .-% hydrophilic nanoparticles.

10. Use of hydrophilic nanoparticles or of cationically modified hydrophilic nanoparticles, as defined in spoke 6, as a dirt-removing additive to dishwashing, care, washing and cleaning agents.

11. Use of aqueous dispersions, as defined in spoke 8 or 9, as a dirt-removing additive to dishwashing, care, washing and cleaning agents.

12. Containing agents for the dirt-removing treatment of surfaces of textile or non-textile materials

a) 0.05 to 40% by weight of hydrophilic nanoparticles according to approach 7,

c) 0 to 20% by weight of acid,

d) 0 to 80% by weight of conventional additives such as bases, inorganic builders, organic cobuilders, other surfactants, polymers

Color transfer inhibitors, polymeric graying inhibitors, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, solvents, adjusting agents, hydrotropes, thickeners and / or alkanolamines,

e) 0 to 99.95 wt .-% water.

13. Containing means according to claim 12

b) 0.1 to 30% by weight of cationic polymers, cationic surfactants and / or water-soluble salts of Mg, Ca, Zn or Al.

14. Containing agents according to claim 12 or 13 c) 0.01 to 10 wt .-% acid.

15. Composition according to one of claims 12 to 14 containing

d) 0.01 to 40% by weight of conventional additives,

e) 50 to 95 wt .-% water.