DE10141006A1 - Use of amphoteric polymers as a dirt-removing additive for the treatment of surfaces - Google Patents

Abstract

The invention relates to the use of amphoteric polymers based on ethylenically unsaturated monomers, as additives for promoting dirt separation in products for surface conditioning. Said polymers contain (a) 20 to 95 wt. % of at least one monoethylenically unsaturated carboxylic acid, (b) 5 to 80 wt. % of at least one monoethylenically unsaturated cationic monomer, (c) 0 to 75 wt. % of other monoethylenically unsaturated non-ionic or amphoteric monomers, (d) 0 to 20 wt. % of other monoethylenically unsaturated monomers containing acid groups and (e) 0 to 15 wt. % of multi-ethylenically unsaturated monomers, said compounds being incorporated by statistic or block polymerisation. Said polymers have an isoelectric point from 2.5 to 11 and a mean molar weight MW from 5,000 to 5,000,000.

Description

• a) 20 bis 95 Gew.-% mindestens einer monoethylenisch ungesättigten Carbonsäure,
• b) 5 bis 80 Gew.-% mindestens eines kationischen, monoethylenisch ungesättigten Monomeren,
• c) 0 bis 75 Gew.-% weitere nichtionische oder amphotere, monoethylenisch ungesättigte Monomere,
• d) 0 bis 20 Gew.-% weitere saure Gruppen enthaltende, monoethylenisch ungesättigte Monomere und
• e) 0 bis 15 Gew.-% mehrfach ethylenisch ungesättigte Monomere

statistisch oder blockweise einpolymerisiert enthalten, einen isoelektrischen Punkt von 2,5 bis 11 und eine mittlere Molmasse M_W von 5 000 bis 5 000 000 aufweisen, als schmutzablösungsfördernder Zusatz zu Mitteln für die Behandlung von Oberflächen. The present invention relates to the use of amphoteric polymers based on ethylenically unsaturated monomers

• a) 20 to 95% by weight of at least one monoethylenically unsaturated carboxylic acid,
• b) 5 to 80% by weight of at least one cationic, monoethylenically unsaturated monomer,
• c) 0 to 75% by weight of further nonionic or amphoteric, monoethylenically unsaturated monomers,
• d) 0 to 20% by weight of further acidic groups containing monoethylenically unsaturated monomers and
• e) 0 to 15 wt .-% polyethylenically unsaturated monomers

Contained in copolymerized form in random or block form, have an isoelectric point of 2.5 to 11 and an average molecular weight M _W of 5,000 to 5,000,000, as a dirt-removing additive to agents for the treatment of surfaces.

Furthermore, the invention relates to agents that amphoteric Contain polymers, as well as new amphoteric polymers.

As is well known, detergents and detergents contain Surfactants and builder materials with other ingredients Functions, e.g. B. dirt-removing substances that the surface to be treated (e.g. hard or textile surfaces) Change so that it is dirt-repellent or the dirt the next cleaning or washing is easier to remove.

From DE-A-196 49 288 nitrogenous polymers are considered dirt-promoting additives to detergents known. This Polymers are usually cationic, but others can Structural elements of non-ionic and / or anionic kind contain. Among other things, a copolymer is made here Methacrylamidopropyltrimethylammonium chloride, acrylic acid and Isobutylacrylat described in a molar ratio of 1: 1: 2, which differs from the Polymers used according to the invention by a stronger im alkaline range isoelectric point different.

DE-A-195 45 630 describes cationic polymers as soil Release connections for detergents for hard surfaces described, which are also anionic or nonionic Structural units, but only to a minor extent, can contain.

DE-A-195 32 542 describes cationic polymers as soil Release connections for rinse aid for dishwashers known. It is mentioned that these polymers are also non-ionic or may have anionic structural units, this will however not explained in more detail.

EP-A-995 791 describes polymers with anionic, described nonionic and cationic structural elements that differ from the polymers used according to the invention in the quantitative composition and the location of the isoelectric point differentiate in the more acidic range.

The polymers known from the above publications promote the Soil removal, however, is not satisfactory.

The invention was therefore based on the object of using polymers To provide those that are better at promoting dirt removal Modification of textile surfaces, leather, hard smooth and hard porous surfaces are suitable.

• a) 20 bis 95 Gew.-% mindestens einer monoethylenisch ungesättigten Carbonsäure,
• b) 5 bis 80 Gew.-% mindestens eines kationischen, ethylenisch ungesättigten Monomeren,
• c) 0 bis 75 Gew.-% weitere nichtionische oder amphotere, monoethylenisch ungesättigte Monomere,
• d) 0 bis 20 Gew.-% weitere saure Gruppen enthaltende, monoethylenisch ungesättigte Monomere und
• e) 0 bis 15 Gew.-% mehrfach ethylenisch ungesättigte Monomere

statistisch oder blockweise einpolymerisiert enthalten, einen isoelektrischen Punkt von 2,5 bis 11 und eine mittlere Molmasse M_W von 5 000 bis 5 000 000 aufweisen, als schmutzablösungsfördernder Zusatz zu Mitteln für die Behandlung von Oberflächen gefunden. Accordingly, the use of amphoteric polymers based on ethylenically unsaturated monomers, which

• a) 20 to 95% by weight of at least one monoethylenically unsaturated carboxylic acid,
• b) 5 to 80% by weight of at least one cationic, ethylenically unsaturated monomer,
• c) 0 to 75% by weight of further nonionic or amphoteric, monoethylenically unsaturated monomers,
• d) 0 to 20% by weight of further acidic groups containing monoethylenically unsaturated monomers and
• e) 0 to 15 wt .-% polyethylenically unsaturated monomers

Contained in copolymerized form, randomly or in blocks, having an isoelectric point of 2.5 to 11 and an average molecular weight M _W of 5,000 to 5,000,000, found as a dirt-removing additive to agents for treating surfaces.

Agents for treating surfaces have also been found, that contain these polymers.

• a) 30 bis 90 Gew.-% mindestens einer monoethylenisch ungesättigten Carbonsäure,
• b) als kationisches, ethylenisch ungesättigtes Monomer
• c) (b') 10 bis 50 Gew.-% mindestens eines quaternären Monomeren aus der Gruppe der N-Alkyl-N'-vinylimidazoliumsalze, N,N,N-Trialkylammoniumalkyl(meth)acrylamidsalze und N,N- Dialkyl-N,N-diallylammoniumsalze oder
• d) (b") 10 bis 70 Gew.-% mindestens eines quaternären Monomeren aus der Gruppe der N,N,N-Trialkylammoniumalkyl(meth)acrylestersalze oder
• e) (b''') 20 bis 70 Gew.-% mindestens eines Monomeren aus der Gruppe der N,N-Dialkylaminoalkyl(meth)acrylester, N,N- Dialkylaminoalkyl(meth)acrylamide, N-Alkyl-N,N-diallylamine und N-Vinylimidazole,
• f) 0 bis 50 Gew.-% weitere nichtionische oder amphotere, monoethylenisch ungesättigte Monomere,
• g) 0 bis 20 Gew.-% weitere saure Gruppen enthaltende, monoethylenisch ungesättigte Monomere und
• h) 0 bis 10 Gew.-% mehrfach ethylenisch ungesättigte Monomere

einpolymerisiert enthalten, einen isoelektrischen Punkt von 3 bis 11 und eine mittlere Molmasse M_W von 5 000 bis 5 000 000 aufweisen. Finally, new amphoteric statistical polymers were found that

• a) 30 to 90% by weight of at least one monoethylenically unsaturated carboxylic acid,
• b) as a cationic, ethylenically unsaturated monomer
• c) (b ') 10 to 50% by weight of at least one quaternary monomer from the group of the N-alkyl-N'-vinylimidazolium salts, N, N, N-trialkylammoniumalkyl (meth) acrylamide salts and N, N-dialkyl-N, N-diallylammonium salts or
• d) (b ") 10 to 70% by weight of at least one quaternary monomer from the group of the N, N, N-trialkylammoniumalkyl (meth) acrylic ester salts or
• e) (b ''') 20 to 70% by weight of at least one monomer from the group consisting of the N, N-dialkylaminoalkyl (meth) acrylic esters, N, N-dialkylaminoalkyl (meth) acrylamides, N-alkyl-N, N- diallylamines and N-vinylimidazoles,
• f) 0 to 50% by weight of further nonionic or amphoteric, monoethylenically unsaturated monomers,
• g) 0 to 20% by weight of further acidic groups containing monoethylenically unsaturated monomers and
• h) 0 to 10% by weight of polyethylenically unsaturated monomers

contain in copolymerized form, have an isoelectric point of 3 to 11 and an average molecular weight M _W of 5,000 to 5,000,000.

The term amphoteric means according to the invention that the Polymers both cationic or basic as well as acidic or contain anionic groups. Preferred cationic groups are protonated and quaternized amino groups or Imidazole groups, preferred acidic or anionic groups are above all Carboxylic acid groups but also phosphonic acid groups and Sulfonic acid groups or those formed therefrom by deprotonation Carboxylate, phosphonate and sulfonate groups.

• 1. α,β-ungesättigte Monocarbonsäuren, die vorzugsweise 3 bis 6 Kohlenstoffatome aufweisen, wie Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure und Vinylessigsäure,
• 2. ungesättigte Dicarbonsäuren, die vorzugsweise 4 bis 6 Kohlenstoffatome aufweisen, wie Itaconsäure und Maleinsäure, und
• 3. Halbester von ungesättigten Dicarbonsäuren mit C₁-C₆ -Alkoholen, wie Itacon- und Maleinsäurehalbester.

The amphoteric polymers contain, as copolymerized component (a), monoethylenically unsaturated carboxylic acids. For example, the following are suitable:

• 1. α, β-unsaturated monocarboxylic acids, which preferably have 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and vinyl acetic acid,
• 2. unsaturated dicarboxylic acids, which preferably have 4 to 6 carbon atoms, such as itaconic acid and maleic acid, and
• 3. Half esters of unsaturated dicarboxylic acids with C ₁ -C ₆ alcohols, such as itacon and maleic acid half esters.

Preferred components (a) are acrylic acid, methacrylic acid, Maleic acid and maleic acid semiesters.

Particularly preferred components (a) are acrylic acid and Methacrylic acid.

The proportion of the monomers (a) in the according to the invention polymers used is 20 to 95 wt .-%, preferably 30 to 90 % By weight, particularly preferably 50 to 85% by weight and very particularly preferably 60 to 80% by weight.

• 1. basische Ester von ethylenisch ungesättigten Carbonsäuren, insbesondere die Ester von α,β-ungesättigten C₃-C₆ -Monocarbonsäuren, vor allem Acrylsäure und Methacrylsäure, mit Aminoalkoholen, vor allem N,N-Di-C₁-C₄-alkylamino-C₂-C₆-alkoholen, und deren Quaternisierungsprodukte, wie Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Dimethylaminopropylacrylat, Dimethylaminopropylmethacrylat, Diethylaminoethylacrylat, Diethylaminopropylacrylat, Dimethylaminobutylacrylat und Diethylaminobutylacrylat,
• 2. basische Amide von ethylenisch ungesättigten Carbonsäuren, insbesondere die N,N-di-C₁-C₄-alkylamino-C₂-C₆-alkylamide von α,β-ungesättigten C₃-C₆-Monocarbonsäuren, vor allem Acrylsäure und Methacrylsäure, und deren Quaternisierungsprodukte, wie Dimethylaminoethylacrylamid, Dimethylaminoethylmethacrylamid, Diethylaminoethylacrylamid, Diethylaminoethylmethacrylamid, Dimethylaminopropylacrylamid, Dimethylaminopropylmethacrylamid, Diethylaminopropylacrylamid und Diethylaminopropylmethacrylamid,
• 3. Vinylimidazol- und Vinylimidazolineinheiten enthaltende Monomere und deren Alkylderivate, insbesondere C₁-C₅ -Alkylderivate, sowie deren Quaternisierungsprodukte, wie N-Vinylimidazol, N-Vinyl-2-methylimidazol, N-Vinyl-4-methylimidazol, N-Vinyl-5-methylimidazol, N-Vinyl-2-ethylimidazol, N-Vinylimidazolin, N-Vinyl-2-methylimidazolin und N-Vinyl-2-ethylimidazolin,
• 4. basische Diallylalkylamine, insbesondere die Diallyl-C₁-C₄- alkylamine, und deren Quaternisierungsprodukte, wie Diallylmethylamin und Diallyldimethylammoniumchlorid,
• 5. Vinylpyridine und deren Quaternisierungsprodukte, wie 4-Vinylpyridin, 2-Vinylpyridin, N-Methyl-4-vinylpyridin und N-Methyl-2-vinylpyridin und
• 6. nach der Polymerisation verseifte N-Vinylcarbonsäureamide und N-Vinyl-N-alkylcarbonsäureamide, insbesondere verseifte N-Vinyl-C₁-C₄-carbonsäureamide und N-Vinyl-N-C₁-C₄-alkyl-C₁-C₄- carbonsäureaimide, wie N-Vinylformamid, N-Vinylacetamid, N- Vinylpropionamid, N-Vinyl-N-methylformamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid und N-Vinyl-N-methylpropionamid, deren freie Aminogruppen durch Hydrolyse mit Säuren, Basen oder Enzymen erhalten werden.

The amphoteric polymers contain cationic, ethylenically unsaturated monomers as polymerized component (b). Suitable components (b) are, for example:

• 1. Basic esters of ethylenically unsaturated carboxylic acids, especially the esters of α, β-unsaturated C ₃ -C ₆ monocarboxylic acids, especially acrylic acid and methacrylic acid, with amino alcohols, especially N, N-di-C ₁ -C ₄ alkylamino -C ₂ -C ₆ alcohols, and their quaternization products, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminoethyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate,
• 2. Basic amides of ethylenically unsaturated carboxylic acids, in particular the N, N-di-C ₁ -C ₄ alkylamino-C ₂ -C ₆ alkylamides of α, β-unsaturated C ₃ -C ₆ monocarboxylic acids, especially acrylic acid and Methacrylic acid, and their quaternization products, such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, dimethylaminopropyl methacrylamide, diethylaminopropylacrylamide and diethylaminopropyl methacrylamide,
• 3. Monomers containing vinylimidazole and vinylimidazoline units and their alkyl derivatives, in particular C ₁ -C ₅ -alkyl derivatives, and their quaternization products, such as N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl 5-methylimidazole, N-vinyl-2-ethylimidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline,
• 4. basic diallylalkylamines, in particular the diallyl-C ₁ -C ₄ -alkylamines, and their quaternization products, such as diallylmethylamine and diallyldimethylammonium chloride,
• 5. vinyl pyridines and their quaternization products, such as 4-vinyl pyridine, 2-vinyl pyridine, N-methyl-4-vinyl pyridine and N-methyl-2-vinyl pyridine and
• 6. after the polymerization, saponified N-vinylcarboxamides and N-vinyl-N-alkylcarboxamides, in particular saponified N-vinyl-C ₁ -C ₄ -carboxamides and N-vinyl-NC ₁ -C ₄ -alkyl-C ₁ -C ₄ - carboximides, such as N-vinylformamide, N-vinyl acetamide, N-vinyl propionamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide and N-vinyl-N-methylpropionamide, their free amino groups can be obtained by hydrolysis with acids, bases or enzymes.

The monomers (b1) to (b5) can be in the form of the free bases or salts with inorganic acids, such as hydrochloric acid, sulfuric acid, Phosphoric acid and nitric acid, or organic acids such as Formic acid, acetic acid and propionic acid, or in quaternized form can be used. Suitable quaternizing agents are in particular alkylating agents, such as dimethyl sulfate, Diethyl sulfate, methyl chloride, ethyl chloride and benzyl chloride.

Preferred components (b) are N, N-dimethylamino-C ₂ -C ₃ alkyl acrylates, N, N-dimethylamino-C ₂ -C ₃ alkyl methacrylates, N, N-dimethylamino-C ₂ -C ₃ alkyl acrylamides, N, N-Dimethylamiho-C ₂ -C ₃ -alkyl methacrylamides, N-vinylimidazole and their quaternary NC ₁ -C ₁₂ -alkylated derivatives and polymerized vinylamine obtained by hydrolysis of polymerized N-vinylformamide.

Particularly preferred components (b) are with methyl chloride or Dimethyl sulfate quaternized dimethylaminoethyl acrylate, Dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate and Dimethylaminopropyl.

The proportion of the monomers (b) in the according to the invention polymers used is 5 to 80 wt .-%, preferably 10 to 60 % By weight, particularly preferably 15 to 50% by weight and very particularly preferably 20 to 40% by weight.

The amphoteric polymers can also be polymerized Component (c) nonionic or amphoteric, monoethylenic contain unsaturated monomers.

• 1. Ester von monoethylenisch ungesättigten C₃-C₆-Carbonsäuren, vor allem Acrylsäure und Methacrylsäure, mit einwertigen C₁-C₂₂-Alkoholen oder mit C₁-C₄-Alkylpolyalkylenglykolen mit 2 bis 40 C₂-C₄-Alkylenglykoleinheiten sowie Hydroxyalkylester von monoethylenisch ungesättigten C₃-C₆-Carbonsäuren, vor allem Acrylsäure und Methacrylsäure, mit zweiwertigen C₂-C₄ -Alkoholen, wie Methyl(meth)acrlyat, Ethyl(meth)acrylat, n- Butyl(meth)acrylat, sec.-Butyl(meth)acrylat, tert.-Butyl (meth)acrylat, Ethylhexyl(meth)acrylat, Ester von (Meth)Acrylsäure mit C₁-C₄-Alkylpolyalkylenglykolen mit 2 bis 40 C₂-C₄-Alkylenglykoleinheiten, Hydroxyethyl(meth)acrylat und Hydroxypropyl(meth)acrylat,
• 2. Amide von monoethylenisch ungesättigten C₃-C₆-Carbonsäuren, vor allem Acrylsäure und Methacrylsäure, mit primären und sekundären C₁-C₁₂-Aminen und endgruppenaminierten C₁-C₄ -Alkylpolyalkylenglykolen mit 2 bis 40 C₂-C₄-Alkylenglykoleinheiten, wie (Meth)Acrylamid, N-Methyl(meth)acrylamid und N-Butyl(meth)acrylamid und Amide von (Meth)Acrylsäure mit endgruppenaminierten Methylpolyalkylenglykolen mit 2 bis 40 C₂-C₄-Alkylenglykoleinheiten,
• 3. Vinylester von gesättigten C₁-C₁₈-Carbonsäuren, wie Vinylacetat und Vinylpropionat,
• 4. N-Vinylamide von gesättigten C₁-C₁₈-Carbonsäuren und N-Vinyllactame von Lactamen mit 5- bis 7-gliedrigen Ringen, wie N- Vinylformamid, N-Vinylacetamid, N-Vinylpyrrolidon, N-Vinylcaprolactam und N-Vinyloxazolidon,
• 5. aliphatische und aromatische Olefine, wie Ethylen, Propylen, C₄-C₂₄-α-Olefine, z. B. Butylen, Isobutylen, Diisobuten, Styrol und α-Methylstyrol, sowie auch Diolefine mit einer aktiven Doppelbindung, z. B. Butadien,
• 6. ungesättigte Nitrile, wie Acrylnitril und Methacrylnitril, und
• 7. fluorhaltige Monomere, wie Fluorethylen, Tetrafluorethylen, Chlortrifluorethylen, Vinylidenfluorid, Hexafluorpropen, Ester und Amide von C₃-C₆-monoethylenisch ungesättigten Carbonsäuren, vor allem Acrylsäure und Methacrylsäure, mit Perfluoralkylgruppen enthaltenden Alkoholen, vor allem CF₃-(C₂F₄)_n-(CH₂)_m-OH oder C₂F₅-(C₂F₄)_n-(CH₂)_m-OH (n = 1-10, m = 0-10), bzw. Aminen, und Allyl- und Vinylester von Perfluoralkylgruppen enthaltenden Carbonsäuren.

Suitable nonionic monomers (c) are, for example:

• 1. esters of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids, especially acrylic acid and methacrylic acid, with monohydric C ₁ -C ₂₂ alcohols or with C ₁ -C ₄ alkyl polyalkylene glycols with 2 to 40 C ₂ -C ₄ alkylene glycol units and Hydroxyalkyl esters of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids, especially acrylic acid and methacrylic acid, with dihydric C ₂ -C ₄ alcohols, such as methyl (meth) acrylic, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec .-Butyl (meth) acrylate, tert-butyl (meth) acrylate, ethylhexyl (meth) acrylate, esters of (meth) acrylic acid with C ₁ -C ₄ alkyl polyalkylene glycols with 2 to 40 C ₂ -C ₄ alkylene glycol units, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate,
• 2. Amides of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids, especially acrylic acid and methacrylic acid, with primary and secondary C ₁ -C ₁₂ amines and end group-aminated C ₁ -C ₄ alkyl polyalkylene glycols with 2 to 40 C ₂ -C ₄ - Alkylene glycol units, such as (meth) acrylamide, N-methyl (meth) acrylamide and N-butyl (meth) acrylamide and amides of (meth) acrylic acid with end group-aminated methyl polyalkylene glycols with 2 to 40 C ₂ -C ₄ alkylene glycol units,
• 3. vinyl esters of saturated C ₁ -C ₁₈ carboxylic acids, such as vinyl acetate and vinyl propionate,
• 4. N-vinyl amides of saturated C ₁ -C ₁₈ carboxylic acids and N-vinyl lactams of lactams with 5- to 7-membered rings, such as N-vinyl formamide, N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl caprolactam and N-vinyl oxazolidone,
• 5. aliphatic and aromatic olefins, such as ethylene, propylene, C ₄ -C ₂₄ -α-olefins, e.g. B. butylene, isobutylene, diisobutene, styrene and α-methylstyrene, and also diolefins with an active double bond, for. B. butadiene,
• 6. unsaturated nitriles, such as acrylonitrile and methacrylonitrile, and
• 7. fluorine-containing monomers, such as fluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropene, esters and amides of C ₃ -C ₆ -monoethylenically unsaturated carboxylic acids, especially acrylic acid and methacrylic acid, with alcohols containing perfluoroalkyl groups, especially 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), or amines, and allyl and vinyl esters of perfluoroalkyl group-containing carboxylic acids.

Particularly preferred nonionic components (c) are Methyl (meth) acrylate, ethyl acrylate, hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, esters of (meth) acrylic acid with Methyl polyethylene glycols with 2 to 25 ethylene glycol units, Amides of (meth) acrylic acid with end group aminated Methyl polyethylene glycols with 2 to 25 ethylene glycol units, vinyl acetate, N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam.

Suitable amphoteric components (c) are, for example, N'- Carboxymethyl-N-vinylimidazole, N-carboxymethyl-4-vinylpyridine and N-carboxymethylhydroxyethyl N, N-dimethylammoniumehtyl (meth) acrylate.

Are monomers (c) in those to be used according to the invention Containing polymers, their proportion can be up to 75% by weight, preferably 2 to 50% by weight, particularly preferably 5 to 40% by weight and most preferably 10 to 30% by weight.

In addition, the amphoteric polymers can be polymerized Component (d) containing acidic groups, monoethylenic contain unsaturated monomers. Suitable monomers (d) are unsaturated sulfonic acids and phosphonic acids, such as vinyl sulfonic acid, Acrylamidopropanoic acid and vinylphosphonic acid, where Vinyl sulfonic acid is preferred.

Are monomers (d) in those to be used according to the invention Contain polymers, their proportion can be up to 20 wt .-%, preferably 0.25 to 10% by weight, particularly preferably 0.5 to 5 % By weight and very particularly preferably 0.5 to 2.5% by weight.

Finally, the amphoteric polymers can be polymerized Component (s) polyethylenically unsaturated monomers contain. They are usually suitable as crosslinkers used connections, e.g. B. acrylic esters, methacrylic esters, allyl ethers and vinyl ethers of at least dihydric alcohols in which the OH groups of the alcohols are completely or partially esterified or can be etherified and the at least two ethylenic contain unsaturated groups, such as glycol diacrylate, Glycol dimethacrylate, butanediol diacrylate, hexanediol diacrylate, Trimethylolpropane triacrylate and tripropylene glycol diacrylate, allyl esters unsaturated carboxylic acids, such as (meth) acrylic acid allyl esters, Divinylbenzene, methylenebisacrylamide and divinylurea.

Are monomers (s) in those to be used according to the invention Contain polymers, their proportion can be up to 15 wt .-%, preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5 % By weight and very particularly preferably 0.2 to 2.5% by weight.

In suitable amphoteric polymers to be used according to the invention is the molar ratio of the monomers (a), (b) and optionally (d) generally chosen so that the polymer has a isoelectric point in the pH range from 2.5 to 11, preferably 3 to 10, particularly preferably 3.5 to 8 and very particularly preferably 4 to 7.

In the case of quaternary hydrolysis-stable monomers (b) is therefore the Number of cationic charge equivalents at pH 11 in the Usually lower than the number of anionic charge equivalents, d. H. the molar proportion of such monomers (b) is a maximum of 75% the molar proportion of monomers (a) and optionally (d) together when the monomers (a), (b) and (d) each have only one loaded group included.

In the case of quaternary hydrolysis-unstable or non-quaternary Monomers (b) can significantly increase the molar fraction of these monomers are higher because the charge state of these monomers (b) with increasing pH - depending on other parameters such as temperature, Medium and time - decreases. Quaternary hydrolysis-labile monomers (b) in this context are in particular the quaternized ones basic esters of unsaturated carboxylic acids. The molar fraction such monomers (b) can therefore be up to 3 times preferred here up to 1.5 times the molar proportion of the monomers (a) and if necessary, make up (d), particularly preferably corresponds to proportion on (b) the proportion of (a) and optionally (d).

The polymers to be used according to the invention have an average molecular weight M _W of 5,000 to 5,000,000, preferably 15,000 to 2,000,000, particularly preferably 25,000 to 1,000,000 and very particularly preferably 50,000 to 750,000.

• a) 30 bis 90 Gew.-% mindestens einer monoethylenisch ungesättigten Carbonsäure,
• b) als kationisches, ethylenisch ungesättigtes Monomer
• c) (b') 10 bis 50 Gew.-% mindestens eines quaternären Monomeren aus der Gruppe der N-Alkyl-N'-vinylimidazoliumsalze, N,N,N-Trialkylammoniumalkyl(meth)acrylamidsalze und N,N- Dialkyl-N,N-diallylammoniumsalze oder
• d) (b") 10 bis 70 Gew.-% mindestens eines quaternären Monomeren aus der Gruppe der N,N,N-Trialkylammoniumalkyl(meth)acrylestersalze oder
• e) (b''') 20 bis 70 Gew.-% mindestens eines Monomeren aus der Gruppe der N,N-Dialkylaminoalkyl(meth)acrylester, N,N- Dialkylaminoalkyl(meth)acrylamide, N-Alkyl-N,N-diallylamine und N-Vinylimidazole,
• f) 0 bis 50 Gew.-% weitere nichtionische oder amphotere monoethylenisch ungesättigte Monomere,
• g) 0 bis 20 Gew.-% weitere saure Gruppen enthaltende monoethylenisch ungesättigte Monomere und
• h) 0 bis 10 Gew.-% mehrfach ethylenisch ungesättigte Monomere

einpolymerisiert enthalten, einen isoelektrischen Punkt von 3 bis 11 und eine mittlere Molmasse M_W von 5 000 bis 5 000 000 aufweisen. The novel amphoteric polymers, which are likewise according to the invention, are preferably used

• a) 30 to 90% by weight of at least one monoethylenically unsaturated carboxylic acid,
• b) as a cationic, ethylenically unsaturated monomer
• c) (b ') 10 to 50% by weight of at least one quaternary monomer from the group of the N-alkyl-N'-vinylimidazolium salts, N, N, N-trialkylammoniumalkyl (meth) acrylamide salts and N, N-dialkyl-N, N-diallylammonium salts or
• d) (b ") 10 to 70% by weight of at least one quaternary monomer from the group of the N, N, N-trialkylammoniumalkyl (meth) acrylic ester salts or
• e) (b ''') 20 to 70% by weight of at least one monomer from the group consisting of the N, N-dialkylaminoalkyl (meth) acrylic esters, N, N-dialkylaminoalkyl (meth) acrylamides, N-alkyl-N, N- diallylamines and N-vinylimidazoles,
• f) 0 to 50% by weight of further nonionic or amphoteric monoethylenically unsaturated monomers,
• g) 0 to 20% by weight of further acidic monoethylenically unsaturated monomers and
• h) 0 to 10% by weight of polyethylenically unsaturated monomers

contain in copolymerized form, have an isoelectric point of 3 to 11 and an average molecular weight M _W of 5,000 to 5,000,000.

The amphoteric polymers to be used according to the invention can produced by radical polymerization of the monomers become. It can be done according to all known radicals Polymerization processes are worked, the process of Solution polymerization and emulsion polymerization are preferred.

Polymerization initiators are suitable both thermally and also photochemically (photoinitiators) decaying and thereby Radical compounds.

Among the thermally activated polymerization initiators are Initiators with a decay temperature in the range of 20 to 180 ° C, in particular from 50 to 90 ° C, preferred. examples for particularly preferred thermal initiators are organic Peroxides, such as dibenzoyl peroxide and di-tert-butyl peroxide, peresters, Perketals, hydroperoxides, inorganic peroxides, such as Hydrogen peroxide, percarbonates, peroxosulfates, peroxodisulfates, Azo compounds, boralkyl compounds and homolytically disintegrating Hydrocarbons.

Examples of suitable photoinitiators are benzophenone, Acetophenone, benzoin ethers, benzyl dialkyl ketones and their derivatives.

The thermal initiators and / or photoinitiators are each according to the requirements of the material to be polymerized usually in amounts of 0.01 to 15 wt .-%, based on the monomers to be polymerized, and can be used individually or, to take advantage of beneficial synergistic effects, in Combination with each other.

To limit the molecular weights of the amphoteric polymers, the usual polymerization regulator, e.g. B. mercapto compounds, such as Mercaptoethanol and thioglycolic acid can be added. suitable Regulator quantities are generally between 0.01 and 3% by weight on the components to be polymerized.

The amphoteric polymers used according to the invention are suitable excellent for the modification of Surfaces of all kinds. These can be structured or porous surfaces, but also smooth, slightly structured Treat surfaces of flexible or hard materials.

Structured and porous surfaces can fiber-based materials (fibers, yarns, fabrics, nonwovens, etc.) or formed by porous macroscopic materials.

Examples of fiber-based materials are textiles and textile surfaces, d. H. all types of fiber-based fabrics, in particular clothing and decorative fabrics, covers, such as Furniture covers, and coverings, such as carpets, made of synthetic fibers, such as Polyester, polypropylene and polyamide, natural fibers such as cotton, Wool and silk, and / or modified natural fibers, such as modified cotton, e.g. B. viscose, and from blended fabrics aforementioned fibers, such as cotton blends, e.g. B. Cotton / polyester and cotton / polyamide blended fabrics.

Examples of porous materials are leather, preferably not or only slightly surface-treated leather, such as suede, and Leather items, e.g. B. leather clothing, leather shoes and Leather furniture.

Other examples of porous materials are woods, preferably not or only slightly surface-tempered woods, and Wooden objects, e.g. B. unpainted furniture, open-pore wooden Wall and floor coverings and construction wood under construction, and porous Building materials, such as exposed concrete, gas concrete, plasters, unglazed Ceramics, bricks and porous minerals, e.g. B. sandstone.

Examples of smooth, slightly structured surfaces are surfaces made of:
Plastics and plastic or resin coatings, e.g. B. furniture, cladding, vehicles, dishes made of polypropylene, polyvinyl chloride or polymethyl methacrylate and floor coverings made of polyvinyl chloride, polypropylene or linoleum;
Glass, e.g. B. glass, glazed ceramics, bottles and glassware;
Stone, e.g. B. stoneware tiles and stone cladding;
Metal, e.g. B. unpainted cladding, pig iron and aluminum structures and galvanized or chrome-plated surfaces;
Porcelain, e.g. B. dishes and sanitary ware;
closed-pore treated woods and leather, e.g. B. surface-treated wooden furniture and parquet floors as well as furniture covers, shoes and clothing made of surface-treated leather;
Paintings and varnishes on various documents, e.g. B. painted vehicles, wall paintings and painted or painted furniture.

The treatment of the surfaces mentioned can be done by washing, Cleaning, rinsing, impregnation or care treatment as well targeted treatment with the dirt-removing agents Polymers, e.g. B. by spraying, watering or painting.

The modification of the surfaces with the inventive Polymers that promote dirt detachment are expressed in one Facilitation of dirt removal during subsequent washing, Rinsing or cleaning. In addition, other effects, e.g. B. Reduction of dirt adhesion, protection against chemical and mechanical influences or damage, improvement of Structure retention of fibers, improvement of shape and structure retention of tissues, reduction of static electricity and Grip improvement, occur.

The concentration of the amphoteric polymers in the underlying aqueous liquors, rinsing or spray formulations (e.g. in the detergent fleet, the cleaning, rinsing or care bath) is usually 0.0002 to 1 wt .-%, preferably 0.0005 to 0.25% by weight and particularly preferably 0.002 to 0.05% by weight.

The liquors or rinsing or spray formulations can amphoteric polymers as the sole component or in combination included with additional ingredients.

For example, amphoteric polymers can be used together with cationic polymers, e.g. B. polyethyleneimines, amine-epichlorohydrin polymers, polyvinylamines, polymers of basic acrylates and their quaternization products, water-soluble salts of polyvalent metals, in particular calcium, magnesium, zinc and / or aluminum salts, for. B. calcium chloride, calcium acetate, magnesium chloride, zinc chloride, zinc sulfate, aluminum sulfate and aluminum chloride, and / or cationic surfactants, e.g. B. NC ₇ -C ₂₅ alkyl-N, N-dimethyl-N- (hydroxy-C ₂ -C ₃ alkyl) ammonium salts, mono- and di- (NC ₇ -C ₂₅ alkyl) -N, N- dimethylammonium compounds, imidazoline quats and esterquats can be used.

Suitable amounts of cationic polymers or cationic Surfactants are usually up to 20% by weight or up to 200 % By weight, based in each case on the amphoteric polymers.

The concentration of the water-soluble Ca, Mg or Zn salts in The liquors or rinsing or spray formulations can usually are up to 10 mmol / l, preferably up to 4 mmol / l, water-soluble Al salts can be used in concentrations of up to 2 mmol / l, preferably up to 0.75 mmol / l, are used.

The liquors or rinsing or spray formulations can also be used up to 0.2 mol / l, preferably up to 0.05 mol / l, particularly preferably up to 0.02 mol / l, acids, bases or buffering Combinations of acids and bases contain, creating a pH generally from 2 to 11, preferably from 2.5 to 10, particularly preferably from 3 to 8 and very particularly preferably from 3.5 to 6.5 is set.

Using the amphoteric polymers as formulations that promote soil release can be produced by diluted with water while being dissolved or be dispersed. The formulations can be liquid, gel or be firm. Solid formulations can be powders, granules or shaped bodies, e.g. B. tablets or bullets. The Formulations can include detergents (rinse aid, fabric softener or rinse aid), Care products, waterproofing agents, detergents or cleaning agents his.

• A) 0,05 bis 40 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, besonders bevorzugt, 0,5 bis 15 Gew.-%, mindestens eines erfindungsgemäßen amphoteren Polymeren,
• B) 0,1 bis 30 Gew.-%, bevorzugt 0,2 bis 15 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-%, mindestens einer Säure oder einer puffernden Kombination aus einer Säure und einer Base,
• C) 0 bis 10 Gew.-%, bevorzugt 0,05 bis 5 Gew.-%, besonders bevorzugt 0,1 bis 2 Gew.-%, mindestens eines kationischen Polymeren, 0 bis 30 Gew.-%, bevorzugt 0,05 bis 15 Gew.-%, besonders bevorzugt 0,1 bis 7,5 Gew.-%, mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn und/oder Al und/oder 0 bis 30 Gew.-%, bevorzugt 0,05 bis 15 Gew.-%, besonders bevorzugt 0,1 bis 7,5 Gew.-%, eines kationischen Tensids, wobei der Anteil der kationischen Komponenten (C) zusammen nicht mehr als 30 Gew.-%, bevorzugt nicht mehr als 15 Gew.-%, besonders bevorzugt nicht mehr als 7,5 Gew.-%, ausmacht, und
• D) 0 bis 80 Gew.-% mindestens eines üblichen Zusatzstoffs, wie anorganische Builder, organische Cobuilder, weitere Tenside, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, weitere schmutzablösungsfördernde Polymere, Enzyme, Parfums, Komplexbildner, Korrosionsinhibitoren, Wachse, Silikonöle, Lichtschutzmittel, Farbstoffe, Lösungsmittel, Hydrotrope, Verdicker und/oder Alkanolamine.

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

• A) 0.05 to 40% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, of at least one amphoteric polymer according to the invention,
• B) 0.1 to 30% by weight, preferably 0.2 to 15% by weight, particularly preferably 0.5 to 10% by weight, of at least one acid or a buffering combination of an acid and a base,
• C) 0 to 10% by weight, preferably 0.05 to 5% by weight, particularly preferably 0.1 to 2% by weight, of at least one cationic polymer, 0 to 30% by weight, preferably 0.05 up to 15% by weight, particularly preferably 0.1 to 7.5% by weight, of at least one water-soluble salt of Mg, Ca, Zn and / or Al and / or 0 to 30% by weight, preferably 0.05 up to 15% by weight, particularly preferably 0.1 to 7.5% by weight, of a cationic surfactant, the proportion of the cationic components (C) together not more than 30% by weight, preferably not more than 15% by weight .-%, particularly preferably not more than 7.5 wt .-%, and
• D) 0 to 80% by weight of at least one customary additive, such as inorganic builders, organic cobuilders, further surfactants, color transfer inhibitors, graying inhibitors, further dirt-promoting polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, solvents, Hydrotropes, thickeners and / or alkanolamines.

• A) 0,05 bis 40 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines erfindungsgemäßen amphoteren Polymeren,
• B) 0,1 bis 40 Gew.-%, bevorzugt 0,2 bis 25 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines nichtionischen, kationischen, amphoteren und/oder anionischen Tensids,
• C) 0 bis 20 Gew.-%, bevorzugt 0,2 bis 25 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-%, mindestens einer Säure oder einer puffernden Kombination aus einer Säure und einer Base,
• D) 0 bis 10 Gew.-%, bevorzugt 0,05 bis 5 Gew.-%, besonders bevorzugt 0,1 bis 2 Gew.-%, mindestens eines kationischen Polymeren und/oder 0 bis 30 Gew.-%, bevorzugt 0,05 bis 15 Gew.-%, besonders bevorzugt 0,1 bis 7,5 Gew.-%, mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn und/oder Al, wobei der Anteil der kationischen Komponenten (D) zusammen nicht mehr als 30 Gew.-%, bevorzugt nicht mehr als 15 Gew.-%, besonders bevorzugt nicht mehr als 7,5 Gew.-%, ausmacht, und
• E) 0 bis 80 Gew.-% mindestens eines üblichen Zusatzstoffs, wie anorganische Builder, organische Cobuilder, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, weitere schmutzablösungsfördernde Polymere, Enzyme, Parfums, Komplexbildner, Korrosionsinhibitoren, Wachse, Silikonöle, Lichtschutzmittel, Farbstoffe, Lösungsmittel, Hydrotrope, Verdicker und/oder Alkanolamine.

Agents according to the invention for treating surfaces that are used in dilution with water can also have the following composition, for example:

• A) 0.05 to 40% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, of at least one amphoteric polymer according to the invention,
• B) 0.1 to 40% by weight, preferably 0.2 to 25% by weight, particularly preferably 0.5 to 15% by weight, of at least one nonionic, cationic, amphoteric and / or anionic surfactant,
• C) 0 to 20% by weight, preferably 0.2 to 25% by weight, particularly preferably 0.5 to 10% by weight, of at least one acid or a buffering combination of an acid and a base,
• D) 0 to 10% by weight, preferably 0.05 to 5% by weight, particularly preferably 0.1 to 2% by weight, of at least one cationic polymer and / or 0 to 30% by weight, preferably 0 , 05 to 15% by weight, particularly preferably 0.1 to 7.5% by weight, of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D) no longer together than 30% by weight, preferably not more than 15% by weight, particularly preferably not more than 7.5% by weight, and
• E) 0 to 80% by weight of at least one customary additive, such as inorganic builders, organic cobuilders, color transfer inhibitors, graying inhibitors, other dirt-promoting polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, solvents, hydrotropes, thickeners and / or alkanolamines.

If anionic surfactants (B) are used, they come preferably used together with other surfactants. Prefers are formulations in which the proportion of anionic surfactants, based on the total amount of surfactants used, at most 70% by weight, in particular at most 50% by weight, especially at most 30% by weight. Particularly preferred formulations do not contain anionic surfactants.

• A) 0,05 bis 30 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines erfindungsgemäßen amphoteren Polymeren,
• B) 0,05 bis 20 Gew.-%, bevorzugt 0,2 bis 15 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-%, mindestens einer Säure oder einer puffernden Kombination aus einer Säure und einer Base,
• C) 0 bis 30 Gew.-%, bevorzugt 0,05 bis 15 Gew.-%, besonders bevorzugt 0,1 bis 7,5 Gew.-%, eines kationischen Tensids,
• D) 0 bis 10 Gew.-%, bevorzugt 0 bis 5 Gew.-%, besonders bevorzugt 0 bis 2 Gew.-%, mindestens eines kationischen Polymeren und/oder 0 bis 30 Gew.-%, bevorzugt 0,05 bis 15 Gew.-%, besonders bevorzugt 0,1 bis 7,5 Gew.-%, mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn und/oder Al, wobei der Anteil der kationischen Komponenten (D) zusammen nicht mehr als 30 Gew.-%, bevorzugt nicht mehr als 15 Gew.-%, besonders bevorzugt nicht mehr als 7,5 Gew.-%, ausmacht,
• E) 0 bis 10 Gew.-% mindestens eines üblichen Zusatzstoffs, wie weitere Tenside, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, weitere schmutzablösungsfördernde Polymere, Enzyme, Parfums, Komplexbildner, Korrosionsinhibitoren, Wachse, Silikonöle, Lichtschutzmittel, Farbstoffe, nichtwäßrige Lösungsmittel, Hydrotrope, Verdicker und/oder Alkanolamine, und
• F) Wasser zur Ergänzung auf 100 Gew.-%.

Liquid or gel-like laundry aftertreatment or care agents according to the invention can, for example, have the following composition:

• A) 0.05 to 30% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, of at least one amphoteric polymer according to the invention,
• B) 0.05 to 20% by weight, preferably 0.2 to 15% by weight, particularly preferably 0.5 to 10% by weight, of at least one acid or a buffering combination of an acid and a base,
• C) 0 to 30% by weight, preferably 0.05 to 15% by weight, particularly preferably 0.1 to 7.5% by weight, of a cationic surfactant,
• D) 0 to 10% by weight, preferably 0 to 5% by weight, particularly preferably 0 to 2% by weight, of at least one cationic polymer and / or 0 to 30% by weight, preferably 0.05 to 15 % By weight, particularly preferably 0.1 to 7.5% by weight, of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D) together not exceeding 30% by weight. -%, preferably not more than 15% by weight, particularly preferably not more than 7.5% by weight,
• E) 0 to 10% by weight of at least one customary additive, such as further surfactants, color transfer inhibitors, graying inhibitors, further dirt-releasing polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / / or alkanolamines, and
• F) water to make up to 100% by weight.

• A) 0,05 bis 30 Gew.-%, bevorzugt 0,1 bis 20 Gew.-, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines erfindungsgemäßen amphoteren Polymeren,
• B) 0,1 bis 40 Gew.-%, bevorzugt 0,2 bis 25 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines nichtionischen, kationischen, amphoteren und/oder anionischen Tensids,
• C) 0 bis 20 Gew.-%, bevorzugt 0 bis 10 Gew.-%, besonders bevorzugt 0 bis 5 Gew.-%, eines anorganischen Builders,
• D) 0 bis 10 Gew.-%, bevorzugt 1 bis 7,5 Gew.-%, besonders bevorzugt 2 bis 5 Gew.-%, eines organischen Cobuilders,
• E) 0 bis 3 Gew.-%, bevorzugt 0,05 bis 1,5 Gew.-%, besonders bevorzugt 0,1 bis 1 Gew.-%, mindestens eines kationischen Polymeren und/oder 0 bis 5 Gew.-%, bevorzugt 0 bis 2,5 Gew.-%, besonders bevorzugt 0 bis 1,5 Gew.-%, mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn und/oder Al, wobei der Anteil der kationischen Komponenten (E) zusammen nicht mehr als 5 Gew.-%, bevorzugt nicht mehr als 2,5 Gew.-%, besonders bevorzugt nicht mehr als 1,5 Gew.-%, ausmacht,
• F) 0 bis 10 Gew.-% mindestens eines üblichen Zusatzstoffes, wie Soda, Natriumsulfat, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, weitere schmutzablösungsfördernde Polymere, Enzyme, Parfums, Komplexbildner, Korrosionsinhibitoren, Wachse, Silikonöle, Lichtschutzmittel, Farbstoffe, nichtwäßrige Lösungsmittel, Hydrotrope, Verdicker und/oder Alkanolamine, und
• G) Wasser zur Ergänzung auf 100 Gew.-%.

Liquid or gel detergents according to the invention can, for example, have the following composition:

• A) 0.05 to 30% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, of at least one amphoteric polymer according to the invention,
• B) 0.1 to 40% by weight, preferably 0.2 to 25% by weight, particularly preferably 0.5 to 15% by weight, of at least one nonionic, cationic, amphoteric and / or anionic surfactant,
• C) 0 to 20% by weight, preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight, of an inorganic builder,
• D) 0 to 10% by weight, preferably 1 to 7.5% by weight, particularly preferably 2 to 5% by weight, of an organic cobuilder,
• E) 0 to 3% by weight, preferably 0.05 to 1.5% by weight, particularly preferably 0.1 to 1% by weight, of at least one cationic polymer and / or 0 to 5% by weight, preferably 0 to 2.5% by weight, particularly preferably 0 to 1.5% by weight, of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (E) no longer together than 5% by weight, preferably not more than 2.5% by weight, particularly preferably not more than 1.5% by weight,
• F) 0 to 10% by weight of at least one customary additive, such as sodium carbonate, sodium sulfate, color transfer inhibitors, graying inhibitors, further dirt-releasing polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, colorants, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and
• G) water to make up to 100% by weight.

• A) 0,05 bis 30 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines erfindungsgemäßen amphoteren Polymeren,
• B) 0,1 bis 40 Gew.-%, bevorzugt 0,2 bis 25 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines nichtionischen, kationischen, amphoteren und/oder anionischen Tensids,
• C) 0 bis 50 Gew.-%, bevorzugt 5 bis 40 Gew.-%, besonders bevorzugt 10 bis 30 Gew.-%, eines anorganischen Builders,
• D) 0 bis 15 Gew.-%, bevorzugt 0,5 bis 10 Gew.-%, besonders bevorzugt 1,5 bis 7,5 Gew.-%, eines organischen Cobuilders,
• E) 0 bis 3 Gew.-%, bevorzugt 0,05 bis 1,5 Gew.-%, besonders bevorzugt 0,1 bis 1 Gew.-%, mindestens eines kationischen Polymeren und/oder 0 bis 5 Gew.-%, bevorzugt 0 bis 2,5 Gew.-%, besonders bevorzugt 0 bis 1,5 Gew.-%, mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn und/oder Al, wobei der Anteil der kationischen Komponenten (E) zusammen nicht mehr als 5 Gew.-%, bevorzugt nicht mehr als 2,5 Gew.-%, besonders bevorzugt nicht mehr als 1,5 Gew.-%, ausmacht,
• F) 0 bis 60 Gew.-% mindestens eines üblichen Zusatzstoffs, wie Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Stellmittel, Soda, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, weitere schmutzablösungsfördernde Polymere, Sprengmittel, Auflöseverbesserer, Enzyme, Parfums, Komplexbildner, Korrosionsinhibitoren, Silikonöle, Lichtschutzmittel und/oder Farbstoffe.

Solid detergents according to the invention can have the following composition:

• A) 0.05 to 30% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, of at least one amphoteric polymer according to the invention,
• B) 0.1 to 40% by weight, preferably 0.2 to 25% by weight, particularly preferably 0.5 to 15% by weight, of at least one nonionic, cationic, amphoteric and / or anionic surfactant,
• C) 0 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, of an inorganic builder,
• D) 0 to 15% by weight, preferably 0.5 to 10% by weight, particularly preferably 1.5 to 7.5% by weight, of an organic cobuilder,
• E) 0 to 3% by weight, preferably 0.05 to 1.5% by weight, particularly preferably 0.1 to 1% by weight, of at least one cationic polymer and / or 0 to 5% by weight, preferably 0 to 2.5% by weight, particularly preferably 0 to 1.5% by weight, of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (E) no longer together than 5% by weight, preferably not more than 2.5% by weight, particularly preferably not more than 1.5% by weight,
• F) 0 to 60% by weight of at least one customary additive, such as bleaching agents, bleach activators, bleaching catalysts, adjusting agents, soda, color transfer inhibitors, graying inhibitors, other dirt-promoting polymers, disintegrants, dissolving improvers, enzymes, perfumes, complexing agents, corrosion inhibitors, silicone oils and light oils. or dyes.

• A) 0,05 bis 30 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines erfindungsgemäßen amphoteren Polymeren,
• B) 0,1 bis 40 Gew.-%, bevorzugt 0,2 bis 25 Gew.-%, besonders bevorzugt 0,5 bis 15 Gew.-%, mindestens eines nichtionischen, kationischen, amphoteren und/oder anionischen Tensids,
• C) 0 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, bsonders bevorzugt 1 bis 3 Gew.-%, mindestens eines Komplexbildners,
• D) 0 bis 3 Gew.-%, bevorzugt 0,05 bis 1,5 Gew.-%, besonders bevorzugt 0,1 bis 1 Gew.-%, mindestens eines kationischen Polymeren und/oder 0 bis 15 Gew.-%, bevorzugt 0 bis 5 Gew.-%, besonders bevorzugt 0 bis 0 bis 2,5 Gew.-% Gew.-%, mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn und/oder Al, wobei der Anteil der kationischen Komponenten (D) zusammen nicht mehr als 15 Gew.-%, bevorzugt nicht mehr als 5 Gew.-%, besonders bevorzugt nicht mehr als 2,5 Gew.-%, ausmacht,
• E) 0 bis 10 Gew.-% mindestens eines üblichen Zusatzstoffs, wie pH-Regulatoren, Stellmittel, Enzyme, Polycarbonsäuren, Parfums, Korrosionsinhibitoren, Wachse, Silikonöle, Glanzbildner, Lichtschutzmittel, Farbstoffe, nichtwäßrige Lösungsmittel, Hydrotrope, Verdicker und/oder Alkanolamine, und
• F) Wasser zur Ergänzung auf 100 Gew.-%.

Liquid or gel detergents according to the invention for textile surfaces, leather and hard surfaces can have, for example, the following composition:

• A) 0.05 to 30% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, of at least one amphoteric polymer according to the invention,
• B) 0.1 to 40% by weight, preferably 0.2 to 25% by weight, particularly preferably 0.5 to 15% by weight, of at least one nonionic, cationic, amphoteric and / or anionic surfactant,
• C) 0 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 1 to 3% by weight, of at least one complexing agent,
• D) 0 to 3% by weight, preferably 0.05 to 1.5% by weight, particularly preferably 0.1 to 1% by weight, of at least one cationic polymer and / or 0 to 15% by weight, preferably 0 to 5% by weight, particularly preferably 0 to 0 to 2.5% by weight% by weight, of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D. ) together does not make up more than 15% by weight, preferably not more than 5% by weight, particularly preferably not more than 2.5% by weight,
• E) 0 to 10% by weight of at least one customary additive, such as pH regulators, adjusting agents, enzymes, polycarboxylic acids, perfumes, corrosion inhibitors, waxes, silicone oils, brighteners, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and
• F) water to make up to 100% by weight.

• A) 0,05 bis 15 Gew.-%, bevorzugt 0,1 bis 7,5 Gew.-%, besonders bevorzugt 0,2 bis 5 Gew.-%, mindestens eines erfindungsgemäßen amphoteren Polymeren,
• B) 0 bis 20 Gew.-%, bevorzugt 0,1 bis 15 Gew.-%, besonders bevorzugt 0,2 bis 10 Gew.-%, mindestens eines nichtionischen, kationischen, amphoteren und/oder anionischen Tensids,
• C) 0 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, besonders bevorzugt 1 bis 3 Gew.-%, mindestens eines Komplexbildners,
• D) 0 bis 1,5 Gew.-%, bevorzugt 0,01 bis 1 Gew.-%, besonders bevorzugt 0,02 bis 1 Gew.-%, mindestens eines kationischen Polymeren und/oder 0 bis 5 Gew.-%, bevorzugt 0 bis 2,5 Gew.-%, besonders bevorzugt 0 bis 1,5 Gew.-%, mindestens eines wasserlöslichen Salzes von Mg, Ca, Zn und/oder Al, wobei der Anteil der kationischen Komponenten (D) zusammen nicht mehr als 5 Gew.-%, bevorzugt nicht mehr als 2,5 Gew.-%, besonders bevorzugt nicht mehr als 1,5 Gew.-%, ausmacht,
• E) 0 bis 10 Gew.-% mindestens eines üblichen Zusatzstoffs, wie pH-Regulatoren, Stellmittel, Enzyme, Polycarbonsäuren, Parfums, Korrosionsinhibitoren, Wachse, Silikonöle, Glanzbildner, Lichtschutzmittel, Farbstoffe, nichtwäßrige Lösungsmittel, Hydrotrope, Verdicker und/oder Alkanolamine, und
• F) Wasser zur Ergänzung auf 100 Gew.-%.

Liquid dirt-releasing impregnating agents according to the invention for textile surfaces, leather, hard surfaces and porous surfaces, which are sprayed onto the surfaces and materials to be treated as a highly dilute aqueous formulation, can have the following composition, for example:

• A) 0.05 to 15% by weight, preferably 0.1 to 7.5% by weight, particularly preferably 0.2 to 5% by weight, of at least one amphoteric polymer according to the invention,
• B) 0 to 20% by weight, preferably 0.1 to 15% by weight, particularly preferably 0.2 to 10% by weight, of at least one nonionic, cationic, amphoteric and / or anionic surfactant,
• C) 0 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 1 to 3% by weight, of at least one complexing agent,
• D) 0 to 1.5% by weight, preferably 0.01 to 1% by weight, particularly preferably 0.02 to 1% by weight, of at least one cationic polymer and / or 0 to 5% by weight, preferably 0 to 2.5% by weight, particularly preferably 0 to 1.5% by weight, of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D) no longer together than 5% by weight, preferably not more than 2.5% by weight, particularly preferably not more than 1.5% by weight,
• E) 0 to 10% by weight of at least one customary additive, such as pH regulators, adjusting agents, enzymes, polycarboxylic acids, perfumes, corrosion inhibitors, waxes, silicone oils, brighteners, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and
• F) water to make up to 100% by weight.

The surfactants mentioned in the different formulations, Builder, cobuilder, complexing agent, solvent, acid, base, Color transfer inhibitors, soil release polymers, bleaches, Bleach activators, graying inhibitors, enzymes, perfumes, Thickeners, oils, waxes, hydrotropes, foam dampers, silicones, pH regulators, adjusting agents, corrosion inhibitors, light stabilizers, Disintegrants, dissolving improvers, brighteners and dyes can be used in the usual in dishwashing, care, washing and Combined cleaning formulations common ingredients become. For typical ingredients, please refer to 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.

Cationic polymers are all in aqueous Solvents soluble or finely dispersible cationic synthetic polymers containing amino and / or ammonium groups, suitable. Examples of such cationic polymers are Polymers containing vinylamine units, vinylimidazole units containing polymers containing quaternary vinylimidazole units Polymers, condensates from imidazole and epichlorohydrin, cross-linked Polyamidoamines, crosslinked grafted with ethyleneimine Polyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines, cross-linked Polyethyleneiminde, amidated polyethyleneimines, alkylated Polyethyleneimines, polyamines, amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines, Polydimethyldiallylammoniumchloride, basic (meth) acrylamide or ester units containing polymers, basic quaternary (meth) acrylamide or polymers and / or lysine condensates containing ester units.

The following are listed as particularly suitable examples of cationic polymers:
Copolymers of 50 mol% vinylpyrrolidone and 50 mol% trimethylammoniumethyl methacrylate methosulfate, M _W 1,000 to 500,000;
Copolymers of 30 mol% of acrylamide and 70 mol% of trimethylammonium ethyl methacrylate method sulfate, M _W 1,000 to 1,000,000;
Copolymers of 70 mol% acrylamide and 30 mol% dimethylaminoethyl methacrylamide, M _W 1,000 to 1,000,000;
Copolymers of 50 mol% hydroxyethyl methacrylate and 50 mol% 2-dimethylaminoethyl methacrylamide, M _W 1,000 to 500,000.

Cationic polymers are also suitable minor (usually <10% by weight) anionic comonomers, z. As acrylic acid, methacrylic acid, vinyl sulfonic acid or their Polymerized alkali salts included.

The following may be mentioned as examples of these cationic polymers:
Copolymers of 70 mol% hydroxyethyl methacrylate and 30 mol% 2-dimethylaminoethyl methacrylamide; Copolymers of 30 mol% vinylimidazole methochloride, 50 mol% dimethylaminoethyl acrylate, 15 mol% acrylamide and 5 mol% acrylic acid;
Polylysines with molar masses M _W of 250 to 250,000, preferably 500 to 100,000, and lysine cocondensates with molar masses M _W of 250 to 250,000, the z. B. amines, polyamines, ketene dimers, lactams, alcohols, alkoxylated amines, alkoxylated alcohols and / or non-proteinogenic amino acids;
Vinylamine homopolymers, 1 to 99 mol% hydrolyzed polyvinylformamides, copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or acrylamide with molecular weights M _W of 3,000 to 500,000;
Vinylimidazole homopolymers, copolymers of vinylimidazole and vinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate with molecular weights M _W of 5,000 to 500,000 and their quaternary derivatives;
Polyethyleneimines, crosslinked polyethyleneimines or amidated polyethyleneimines with molecular weights M _W of 500 to 3,000,000;
Amine-epichlorohydrin polycondensates which contain imidazole, piperazine, C ₁ -C ₈ -alkylamines, di- (C ₁ -C ₈ -alkyl) amines and / or dimethylaminopropylamine as the amine component and have molar masses M _W of 500 to 250,000; polymers containing basic (meth) acrylamide or ester units, basic polymers containing quaternary (meth) acrylamide or ester units with molecular weights M _W of 10,000 to 2,000,000.

Preferred cationic surfactants are C ₇ -C ₂₅ -alkylamines, NC ₇ -C ₂₅ -alkyl-N, N-dimethyl-N- (hydroxy-C ₂ -C ₃ -alkyl) ammonium salts, mono- (NC ₇ - C ₂₅ -alkyl) -N, N-dimethylammonium compounds, di- (NC ₇ -C ₂₅ -alkyl) -N, N-dimethylammonium compounds, ester quats, such as quaternary esterified mono-, di- and trialkanolamines, which are mixed with C ₅ -C ₂₂ -Carboxylic acids are esterified, imidazoline quats, such as 2-alkylimidazolinium salts of the formulas


in which R ^{1 is} C ₁ -C ₂₅ -alkyl or C ₂ -C ₂₅ -alkenyl, R ² C ₁ -C ₄ -alkyl or hydroxy-C ₁ -C ₄ -alkyl, R ³ C ₁ -C ₄ -alkyl, Hydroxy-C ₁ -C ₄ alkyl or a radical R ¹ -CO-X- (CH ₂ ) _n - with X = 0 or NH and n = 2 or 3, where at least one radical R ¹ = C ₇ -C ₂₂ alkyl or C ₇ -C ₂₂ alkenyl.

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

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

Preferred anionic surfactants are e.g. B. alkylbenzenesulfonates with linear or branched C ₆ -C ₂₅ alkyl groups, fatty alcohol and oxo alcohol sulfates with C ₈ -C ₂₂ alcohols and fatty alcohol or oxo alcohol ether sulfates from C ₈ -C ₂₂ alcohols containing 1 to 5 moles of ethylene oxide per mole Alcohol are ethoxylated and are sulfated at the OH end group of the ethoxylate.

Formulations according to the invention are preferred Low in anionic surfactants, particularly preferably formulated free of anionic surfactants. If Anionic surfactants are used in the formulations preferably ether sulfates 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 are added to the formulations, particularly preferably no solvents are added.

Preferred acids are inorganic acids, such as sulfuric acid and Phosphoric acid, and organic acids such as carboxylic acids and Sulfonic acids. Strong acids such as sulfuric acid, phosphoric acid and Sulphonic acids are usually partially neutralized Form used.

Preferred builders are alkali carbonates, phosphates, Polyphosphates, zeolites and silicates. Particularly preferred builder are zeolite A, zeolite P, layered silicates, soda and Trisodium polyphosphate.

Preferred cobuilders are acrylic acid homopolymers, acrylic acid / maleic acid copolymers, polyaspartic acid and citric acid. Particularly preferred cobuilders are acrylic acid homopolymers with a molecular weight of M _W 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 M _W of 4,000 to 100,000.

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

Preferred soil release polymers are polyesters of terephthalic acid, ethylene glycol and polyethylene glycol, polyethylene glycols having molecular weights M _n of 1,000 to 5,000 being condensed in, and polyesters in which up to 50 mol% of terephthalic acid has been replaced by sulfocarboxylic acids or sulfodicarboxylic.

Preferred color transfer inhibitors are polyvinylpyrrolidones of molecular weights M _W 8,000 to 70,000, vinylimidazole / vinylpyrrolidone copolymers with a molar ratio of the monomers of 1:10 to 2: 1 and molecular weights M _W of 8,000 to 70,000 and poly-4-vinylpyridine-N -oxides with molecular weights M _W of 8,000 to 70,000.

Preferred enzymes are proteases, lipases, cellulase and Amylases.

Examples A) Preparation and characterization of amphoteric polymers

To characterize the polymers obtained, their isoelectric point was determined by turbidity titration as follows:
In each case 0.2% by weight aqueous solutions of the polymers were prepared and adjusted to pH 2 by adding 10% by weight hydrochloric acid. Using an optical turbidity sensor (Metrohm), the transmission of the solutions was determined as a function of the pH in a 50 ml measuring cell. For this purpose, 1 m sodium hydroxide solution was added in 10 μl units at 15 s intervals using an automatic metering device, and the pH value was measured with a pH electrode after each metering step. The pH value at which the maximum turbidity, ie the lowest transmission, was registered was assumed to be the isoelectric point.

example 1

In a 2 l polymerization vessel with stirrer, reflux condenser, The internal thermometer and 3 dropping funnels were followed by 688.5 g of water Purge with nitrogen heated to 75 ° C. Then 154 g Acrylic acid (feed 1), 57.5 g of an 80% by weight aqueous solution of [2- (acryloxy) ethyl] trimethylammonium chloride, adjusted to pH 3.5 with 50 wt .-% aqueous citric acid (feed 2), and one Initiator mixture from 0.5 g 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride and 50 g of water (feed 3) in 3 h in parallel dripped continuously.

After stirring for another hour at 75 ° C, was again Initiator mixture of 1.0 g 2,2'-Azobis (2-methylpropionic acid amidine) dihydrochloride and 50 g of water were added in one portion.

After stirring for another two hours at 75 ° C, the Cooled reaction mixture to room temperature.

The isoelectric point of the. Determined by turbidity titration The polymer obtained was at pH 3.0.

Example 2

The procedure was analogous to Example 1, but 673.2 g Water, 92.9 g acrylic acid (feed 1) and 133.8 g of feed 2 used.

The isoelectric point of the. Determined by turbidity titration The polymer obtained was at pH 4.55.

Example 3

The procedure was analogous to Example 1, but 663.5 g Water, 54.2 g of acrylic acid (feed 1), 182.3 g of feed 2 and an initiator mixture of 0.2 g 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride and 50 g of water (feed 3) are used.

The isoelectric point of the. Determined by turbidity titration The polymer obtained was pH 5.5.

Example 4

In a 2 l polymerization vessel with stirrer, reflux condenser, Internal thermometer, pH electrode and 4 dropping funnels were 613.3 g Water heated to 75 ° C after flushing with nitrogen. Then were 113.3 g of acrylic acid (feed 1), 173.4 g of a 50% by weight aqueous solution of [3- (methacryloylamino) propyl] trimethylammonium chloride (feed 2) and an initiator mixture of 0.2 g 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride and 50 g Water (feed 3) was continuously added dropwise in parallel in 3 h. As Feed 4, 25% by weight sodium hydroxide solution was added so that the pH Value of the mixture was kept at 3.5.

After stirring for another hour at 75 ° C, was again Initiator mixture from 1.0 g of 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride and 50 g of water added in one portion.

After stirring for another two hours at 75 ° C, the Cooled reaction mixture to room temperature.

Example 5

The procedure was analogous to Example 4, but 700.0 g Water, 44 g acrylic acid (feed 1) and feed 156 156 g Methacrylic acid [(3-dimethylamino) propylamide] used. 25% by weight Sodium hydroxide solution (feed 4) was added so that the pH at 8.0 was held.

The isoelectric point of the. Determined by turbidity titration The polymer obtained was at pH 9.6.

Example 6

The procedure was analogous to Example 4, but 700.0 g Water, 50.3 g acrylic acid (feed 1) and 2 149.7 g as feed 2 Acrylic acid [(2-dimethylamino) ethyl ester] used. 25% by weight Sodium hydroxide solution (feed 4) was added so that the pH at 6.0 was held.

Example 7

The procedure was analogous to Example 1, but 681.5 g Water, as feed 1, a mixture of 68.8 g of acrylic acid and 57.3 g of methyl methacrylate and 92.4 g of feed 2 are used. The The reaction mixture was finally passed through a Perlon filter filtered.

The isoelectric point of the. Determined by turbidity titration The polymer obtained was at pH 4.6.

Example 8

The procedure was analogous to Example 1, but 700.0 g Water, as feed 1, a mixture of 39.7 g of acrylic acid and 55.2 g methyl methacrylate and 2 105.2 g acrylic acid [(2- dimethylamino) ethyl ester] used.

The isoelectric point of the. Determined by turbidity titration The polymer obtained was at pH 4.8.

B) Use of amphoteric polymers

To test their dirt-removing effects, the amphoteric polymers obtained in those described below Trials of washing as a rinse formulation for impregnation used.

For this purpose, the solutions of amphoteric polymers by adding 1.25 N formic acid to a Concentration of 12.5 wt .-% diluted and then with stirring 1 N sodium hydroxide solution adjusted to a pH of 2.5. Then was added by adding deionized water Polymer concentration of 5 wt .-% diluted. The 5 wt .-% acidic formulations were added to the wash used for the rinse liquor (1.6 g polymer / l rinse liquor).

In separate experiments, two 5 g polyester / cotton (50:50) blended fabrics (test fabric) together with 10 g ballast fabric (equal parts cotton and cotton / polyester blended fabrics) were washed with a household detergent (Ariel Futur) and rinsed with tap water and rinsed with the rinse liquors containing the amphoteric polymers. Washing conditions prewash:
Washing machine: Launder-O-Meter
Prewash temperature: 20 ° C
Prewash time: 15 min
Water hardness: 3.0 mmol / l
Ca / Mg ratio: 3: 1
Fleet ratio: 12.5
Main wash:
Washing temperature: 40 ° C
Detergent: Ariel Futur
Detergent dosage: 3.5 g / l
Washing time: 30 min
Water hardness: 3.0 mmol / l
Ca / Mg ratio: 3: 1
Fleet ratio: 12.5

After drying, the test fabrics were then used Motor oil dirty. For this purpose, 0.3 g of the oil was applied to the horizontal fabric applied. Then the Remission of the soiled tissue determined at 460 nm (in% Remission).

Then the fabrics were again with the heavy duty detergent washed. After washing, the remission was again at 460 nm measured (in% remission).

To evaluate the dirt-removing effect, the Remission difference ΔR from before and after washing measured remission values determined. The two were for in each case a polymer determined certain values and on the in the Whole numerical values given in table are rounded. The bigger the ΔR value is, the stronger the dirt-removing promoting Effect of the polymer used.

• 1. V1: Nachspülflotte ohne Polymerzusatz
• 2. V2: Nachspülflotte, enthaltend 1,6 g/l des in der DE-A-196 49 288 als Polymer 3 beschriebenen Copolymers aus [3-(Methacryloylamino)propyl]trimethylammoniumchlorid/Isobutylacrylat/Acrylsäure (Molverhältnis 1 : 2 : 1)
• 3. V3: Nachspülflotte, enthaltend 1,6 g/l des in Beispiel 6 der EP-A-995 791 beschriebenen Copolymers aus (Polyethylenglykol-400-monomethylether)methacrylat/Acrylsäure (Gewichtsverhältnis 7 : 1)
  
  
  

For comparison, the ΔR values are listed that were obtained using the following rinse liquors:

• 1. V1: rinse liquor without addition of polymer
• 2. V2: rinse liquor, containing 1.6 g / l of the copolymer of [3- (methacryloylamino) propyl] trimethylammonium chloride / isobutyl acrylate / acrylic acid described as polymer 3 in DE-A-196 49 288 (molar ratio 1: 2: 1)
• 3. V3: rinse liquor containing 1.6 g / l of the copolymer of (polyethylene glycol 400 monomethyl ether) methacrylate / acrylic acid (weight ratio 7: 1) described in Example 6 of EP-A-995 791
  
  
  

The washing tests with the polymers from Examples 1 to 8 prove in comparison to this Comparative Example V1 without the addition of polymer, the high dirt-removing effect of the inventive amphoteric polymers under the test conditions. The comparison with the comparative examples V2 and V3 shows that the amphoteric polymers according to the invention have a significantly higher soil release promoting effect Have an effect as polymers according to the prior art.

Claims (11)

1. Use of amphoteric polymers based on ethylenically unsaturated monomers a) 20 to 95% by weight of at least one monoethylenically unsaturated carboxylic acid, b) 5 to 80% by weight of at least one cationic, monoethylenically unsaturated monomer, c) 0 to 75% by weight of further nonionic or amphoteric, monoethylenically unsaturated monomers, d) 0 to 20% by weight of further acidic groups containing monoethylenically unsaturated monomers and e) 0 to 15 wt .-% polyethylenically unsaturated monomers Contained in copolymerized form, randomly or in blocks, have an isoelectric point of 2, 5 to 11 and an average molecular weight M _W of 5,000 to 5,000,000, as a dirt-removing additive to agents for treating surfaces. 2. Use according to claim 1, characterized in that the amphoteric polymers as a dirt-removing additive in Dishwashing, care, impregnation, washing and cleaning agents be used. 3. Use according to claim 1 or 2, characterized in that that the amphoteric polymers together with cationic Polymers, water-soluble salts of polyvalent metals and / or cationic surfactants are used. 4. Water-thinnable agent for treating surfaces that A) 0.05 to 40% by weight of at least one amphoteric polymer according to claim 1, B) 0.1 to 30% by weight of at least one acid or a buffering combination of an acid and a base, C) 0 to 20% by weight of at least one cationic polymer, 0 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn and / or Al and / or 0 to 30% by weight of a cationic surfactant, where the proportion of the cationic components (C) together is not more than 30% by weight, and D) 0 to 80% by weight of at least one customary additive, such as inorganic builders, organic cobuilders, further surfactants, color transfer inhibitors, graying inhibitors, further dirt-promoting polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, solvents, Hydrotropes, thickeners and / or alkanolamines, contain. 5. Water-thinnable agent for treating surfaces that A) 0.05 to 40% by weight of at least one amphoteric polymer according to claim 1, B) 0.1 to 40% by weight of at least one nonionic, cationic, amphoteric and / or anionic surfactant, C) 0 to 20% by weight of at least one acid or a buffering combination of an acid and a base, D) 0 to 10% by weight of at least one cationic polymer and / or 0 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D) together not exceeding 30% by weight, and E) 0 to 80% by weight of at least one customary additive, such as inorganic builders, organic cobuilders, color transfer inhibitors, graying inhibitors, other dirt-promoting polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, solvents, hydrotropes, thickeners and / or alkanolamines, contain. 6. Liquid or gel-like laundry aftertreatment or care products that A) 0.05 to 30% by weight of at least one amphoteric polymer according to claim 1, B) 0.05 to 20% by weight of at least one acid or a buffering combination of an acid and a base, C) 0 to 30% by weight of a cationic surfactant, D) 0 to 10% by weight of at least one cationic polymer and / or 0 to 30% by weight of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D) no longer together than 30% by weight, E) 0 to 10% by weight of at least one customary additive, such as further surfactants, color transfer inhibitors, graying inhibitors, further dirt-releasing polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / / or alkanolamines, and F) water to make up to 100% by weight contain. 7. Liquid or gel detergents that A) 0.05 to 30% by weight of at least one amphoteric polymer according to claim 1, B) 0.1 to 40% by weight of at least one nonionic, cationic, amphoteric 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 3% by weight of at least one cationic polymer and / or 0 to 5% by weight of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (E) no longer together than 5% by weight, F) 0 to 10% by weight of at least one customary additive, such as sodium carbonate, sodium sulfate, color transfer inhibitors, graying inhibitors, further dirt-releasing polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, colorants, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and G) water to make up to 100% by weight contain. 8. Solid detergents that A) 0.05 to 30% by weight of at least one amphoteric polymer according to claim 1, B) 0.1 to 40% by weight of at least one nonionic, cationic, amphoteric and / or anionic surfactant, C) 0 to 50% by weight of an inorganic builder, D) 0 to 15% by weight of an organic cobuilder, E) 0 to 3% by weight of at least one cationic polymer and / or 0 to 5% by weight of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (E) no longer together than 5% by weight, F) 0 to 60% by weight of at least one customary additive, such as bleaching agents, bleach activators, bleaching catalysts, adjusting agents, soda, color transfer inhibitors, graying inhibitors, other dirt-promoting polymers, disintegrants, dissolving improvers, enzymes, perfumes, complexing agents, corrosion inhibitors, silicone oils and light oils. or dyes, contain. 9. Liquid or gel detergents for textile surfaces, leather and hard surfaces A) 0.05 to 30% by weight of at least one amphoteric polymer according to claim 1, B) 0.1 to 40% by weight of at least one nonionic, cationic, amphoteric and / or anionic surfactant, C) 0 to 10% by weight of at least one complexing agent, D) 0 to 3% by weight of at least one cationic polymer and / or 0 to 15% by weight of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D) no longer together than 15% by weight, E) 0 to 10% by weight of at least one customary additive, such as pH regulators, adjusting agents, enzymes, polycarboxylic acids, perfumes, corrosion inhibitors, waxes, silicone oils, brighteners, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and F) water to make up to 100% by weight contain. 10. Liquid impregnation agent for textile surfaces, leather, hard surfaces and porous surfaces A) 0.05 to 15% by weight of at least one amphoteric polymer according to claim 1, B) 0 to 20% by weight of at least one nonionic, cationic, amphoteric and / or anionic surfactant, C) 0 to 10% by weight of at least one complexing agent, D) 0 to 1.5% by weight of at least one cationic polymer and / or 0 to 5% by weight of at least one water-soluble salt of Mg, Ca, Zn and / or Al, the proportion of the cationic components (D) together is not more than 5% by weight E) 0 to 10% by weight of at least one customary additive, such as pH regulators, adjusting agents, enzymes, polycarboxylic acids, perfumes, corrosion inhibitors, waxes, silicone oils, brighteners, light stabilizers, dyes, non-aqueous solvents, hydrotropes, thickeners and / or alkanolamines, and F) water to make up to 100% by weight contain. 11. Amphoteric statistical polymers that a) 30 to 90% by weight of at least one monoethylenically unsaturated carboxylic acid, b) as a cationic, ethylenically unsaturated monomer c) (b ') 10 to 50% by weight of at least one quaternary monomer from the group of the N-alkyl-N'-vinylimidazolium salts, N, N, N-trialkylammoniumalkyl (meth) acrylamide salts and N, N-dialkyl-N, N-diallylammonium salts or d) (b ") 10 to 70% by weight of at least one quaternary monomer from the group of the N, N, N-trialkylammoniumalkyl (meth) acrylic ester salts or e) (b ''') 20 to 70% by weight of at least one monomer from the group of the N, N-dialkylaminoalkyl (meth) acrylic esters, N, N-dialkylaminoalkyl (meth) acrylamides, N-alkyl-N, N- diallylamines and N-vinylimidazoles, f) 0 to 50% by weight of further nonionic or amphoteric monoethylenically unsaturated monomers, g) 0 to 20% by weight of further acidic monoethylenically unsaturated monomers and h) 0 to 10 wt .-% polyunsaturated monomers contain in copolymerized form, have an isoelectric point of 3 to 11 and an average molecular weight M _W of 5,000 to 5,000,000.