EP1456334B1 - Cleaning agent composition comprising polymers containing nitrogen - Google Patents

Abstract

A cleaner composition which comprises at least one surfactant, at least one builder and at least one nitrogen-containing polymer is described. The nitrogen-containing polymer is, for example, an alkoxylated polyvinylamine, an alkoxylated, acylated or alkylated polyaminoamide or a polyurethane-urea with tertiary amino groups. The nitrogen-containing polymers facilitate soil release.

Description

The present invention relates to a detergent composition containing at least one surfactant, at least one builder and at least one nitrogen-containing polymer, and to methods for cleaning hard surfaces.

Articles made of synthetic materials, such as thermosetting or thermoplastic plastics, such as plastic dishes, generally have hydrophobic surface properties. Hydrophobic dirt, such as carotenoids, is persistently adsorbed on the surface of these objects and can only be removed incompletely with surfactant-containing detergents. Furthermore, the water film should drain during rinsing without repolishing and leave no disturbing traces, for example, by water hardness. The known cleaning agents are in this respect still in need of improvement.

There is therefore a need for cleaning and pretreatment agents that will temporarily or permanently alter the surface of articles of hydrophobic materials to reduce the adhesion of soils and facilitate cleaning.

The unpublished German patent application P 100 29 027.2 describes the use of alkoxylated polyvinylamines, the unpublished German patent application P 101 15 256.6 describes the use of polyaminoamides, the unpublished German patent application P 100 29 026.4 and P 101 15 255.8 the use of cationic polymers, the urethane - And / or urea groups, to increase the surface hydrophilicity of hydrophobic structures.

US 4,676,921 discloses ethoxylated amine polymers having stain removal and anti-redeposition properties in detergent compositions.

1. A) wenigstens ein Tensid,
2. B) wenigstens einen Builder und
3. C) wenigstens ein stickstoffhaltiges Polymer mit Wiederholungseinheiten der allgemeinen Formel I, II oder III,
   
   

worin

R¹

für C₂-C₈-Alkandiyl steht,

R²

für eine chemische Bindung oder C₁-C₂₀-Alkandiyl steht, das gegebenenfalls von einer Doppelbindung und/oder einer Iminogruppe unterbrochen und/oder gegebenenfalls ganz oder teilweise Bestandteil eines oder mehrerer gesättigter oder ungesättigter carbocyclischer 5- bis 8-gliedriger Ringe ist, wobei das Alkandiyl eine oder mehrere Hydroxylgruppen und/oder Aminogruppen tragen kann,

R³

für C₂-C₈-Alkandiyl oder für

steht,

X

für O, NH oder C₁-C₆-Alkylimino steht,

Z¹

für Wasserstoff oder für

steht, wobei wenigstens ein Teil der Reste Z¹ von Wasserstoff verschieden ist,

Z²

für Wasserstoff, R⁵CO, R⁶- oder

steht, wobei wenigstens ein Teil der Reste Z² von Wasserstoff verschieden ist,

Z³

für C₁-C₆-Alkyl, Phenyl oder Phenyl-C₁-C₄-alkyl steht oder, wenn k = 0, zusammen mit N-R³-X einen 5- bis 7-gliedrigen gesättigten heterocyclischen Ring mit 2 Stickstoffatomen bilden kann oder, wenn k = 1, die beiden Reste Z³ zusammen mit N-CH₂-CH₂-N einen 5- bis 7-gliedrigen gesättigten heterocyclischen Ring mit 2 Stickstoffatomen bilden können,

R⁴

für C₁-C₁₀-Alkyl steht,

R⁵

für C₄-C₂₇-Alkyl oder C₄-C₂₇-Alkenyl steht, wobei die Alkyl-oder Alkenylgruppen einen oder mehrere Substituenten tragen können, die unter Hydroxy, Alkoxy, Alkoxycarbonyl oder NE₁E₂ ausgewählt sind, worin E₁ und E₂ gleich oder verschieden sein können und für Wasserstoff, Alkyl oder Acyl stehen;

R⁶

für C₄-C₂₇-Alkyl oder C₄-C₂₇-Alkenyl steht, wobei die Alkyl-oder Alkenylgruppen einen oder mehrere Substituenten tragen können, die unter Hydroxy, Alkoxy, Alkoxycarbonyl oder NE₁E₂ ausgewählt sind, worin E₁ und E₂ gleich oder verschieden sein können und für Wasserstoff, Alkyl oder Acyl stehen;

p

für eine Zahl von 1 bis 20 steht,

q

für eine Zahl von 1 bis 20 steht,

k

für 0 oder 1 steht;

oder dessen Umsetzungsprodukte mit Neutralisierungsmitteln oder Quarternierungsmitteln.The invention relates to a detergent formulation containing

1. A) at least one surfactant,
2. B) at least one builder and
3. C) at least one nitrogen-containing polymer having repeating units of the general formula I, II or III,
   
   

wherein

R ¹

represents C ₂ -C ₈ -alkanediyl,

R ²

is a chemical bond or C ₁ -C ₂₀ alkanediyl, which is optionally interrupted by a double bond and / or an imino group and / or optionally fully or partially part of one or more saturated or unsaturated carbocyclic 5- to 8-membered rings, wherein the alkanediyl may carry one or more hydroxyl groups and / or amino groups,

R ³

for C ₂ -C ₈ alkanediyl or for

stands,

X

is O, NH or C ₁ -C ₆ -alkylimino,

Z ¹

for hydrogen or for

wherein at least part of the radicals Z ^{1 is} different from hydrogen,

Z ²

for hydrogen, R ⁵ CO, R ⁶ - or

wherein at least part of the radicals Z ^{2 is} different from hydrogen,

Z ³

is C ₁ -C ₆ -alkyl, phenyl or phenyl-C ₁ -C ₄ -alkyl or, when k = 0, together with NR ³ -X can form a 5- to 7-membered saturated heterocyclic ring having 2 nitrogen atoms, or if k = 1, the two radicals Z ³ together with N-CH ₂ -CH ₂ -N can form a 5- to 7-membered saturated heterocyclic ring having 2 nitrogen atoms,

R ⁴

is C ₁ -C ₁₀ -alkyl,

R ⁵

is C ₄ -C ₂₇ alkyl or C ₄ -C ₂₇ alkenyl, wherein the alkyl or alkenyl groups may carry one or more substituents selected from hydroxy, alkoxy, alkoxycarbonyl or NE ₁ E ₂ , wherein E ₁ and E _{2 may be the} same or different and represent hydrogen, alkyl or acyl;

R ⁶

is C ₄ -C ₂₇ alkyl or C ₄ -C ₂₇ alkenyl, wherein the alkyl or alkenyl groups may carry one or more substituents selected from hydroxy, alkoxy, alkoxycarbonyl or NE ₁ E ₂ , wherein E ₁ and E _{2 may be the} same or different and represent hydrogen, alkyl or acyl;

p

is a number from 1 to 20,

q

is a number from 1 to 20,

k

stands for 0 or 1;

or its reaction products with neutralizing agents or quaternizing agents.

1. (A) 0,5 bis 40 Gew.-%, vorzugsweise 5 bis 30, insbesondere 10 bis 25 Gew.-% Tensid,
2. (B) 1 bis 60 Gew.-%, vorzugsweise 1 bis 40 Gew.-% , insbesondere 2 bis 15 Gew.-% Builder,
3. (C) 0,01 bis 50 Gew.-%, vorzugsweise 0,1 bis 25 Gew.-%, insbesondere 0,5 bis 5 Gew.-% stickstoffhaltiges Polymer,

bezogen auf das Gesamtgewicht der Reinigungsmittelzusammensetzung.The detergent composition of the invention generally contains

1. (A) 0.5 to 40% by weight, preferably 5 to 30, in particular 10 to 25% by weight of surfactant,
2. (B) 1 to 60% by weight, preferably 1 to 40% by weight, in particular 2 to 15% by weight of builder,
3. (C) 0.01 to 50% by weight, preferably 0.1 to 25% by weight, in particular 0.5 to 5% by weight of nitrogen-containing polymer,

based on the total weight of the detergent composition.

Nitrogen-containing polymers having repeating units of the formula I are derived from alkoxylated polyvinylamines.

Polyvinylamines are partially or completely understood to be composed of repeating units which are derived formally from N-vinylamine. These polymers can be obtained by (open) chain-chain N-vinylcarboxamides alone or together with other monoethylenically unsaturated comonomers and then from the copolymerized open-chain N-vinylcarboxamide units the formyl or alkylcarbonyl group by the action of acids, bases or enzymes Cleaves formation of vinylamine units. Polyvinylamines are known, cf. For example, US-A-4,217,214, EP-A-0 071 050 and EP-A-0 216 387.

Examples of open-chain N-vinylcarboxamides are: N-vinylformamide, N-vinylacetamide and N-vinylpropionamide. To prepare the polyvinylamines, the monomers mentioned can be polymerized either alone, in mixture with one another or together with other monoethylenically unsaturated monomers.

Suitable comonomers are monoethylenically unsaturated monomers, in particular vinyl esters of saturated carboxylic acids having 1 to 6 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate; ethylenically unsaturated C ₃ - to C ₆ -carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinylacetic acid and their alkali metal and alkaline earth metal salts, esters, amides and nitriles, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate; Esters of ethylenically unsaturated carboxylic acids with aminoalcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminomethylmethacrylate, dimethylaminopropylacrylate, dimethylaminopropylmethacrylate, diethylaminopropylacrylate, dimethylaminobutylacrylate and diethylaminobutylacrylate, the amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide , N-ethylacrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylamides, such as. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide.

Further suitable comonomers are: N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and also substituted N-vinylimidazoles, such as N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, and N-vinylimidazolines, such as. For example, vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethyl-imidazoline. N-vinylimidazoles and N-vinylimidazolines are also used, except in the form of the free bases, in neutralized or quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.

Also suitable as comonomers are sulfo-containing monomers, such as, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate.

The polyvinylamine is preferably derived from homopolymers of N-vinylformamide or from copolymers which, in addition to N-vinylformamide, also contain, in copolymerized form, vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile and / or N-vinylpyrrolidone.

The homopolymers of the monomers and their copolymers with the monomers can be hydrolyzed to 0.1 to 100, preferably 10 to 100 mol%, in particular 50 to 99 mol%. The degree of hydrolysis of the polymers is equivalent to the content of polyvinylamines in vinylamine units, based on the vinylamide units used.

The alkoxylated polyvinylamines are preferably derived from polyvinylamines having a K value in the range from 10 to 200, preferably from 20 to 100. The K values are determined according to H. Fikentscher in 5% aqueous common salt solution at pH 7, a temperature of 25 ° C. and a polymer concentration of 0.5% by weight, cf. Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932).

The alkoxylated polyvinylamines are prepared by reacting the polyvinylamines described above with an epoxide of the formula IV in which R ^{4 is} hydrogen or C ₁ -C ₁₀ -alkyl.

Examples of preferred epoxides of formula IV are the epoxides of ethylene, propene, 1-butene. In this case, side chains of the formula Z ¹ are formed on all or part of the amino groups of the polyvinylamine. The mean q of q is determined by the molar Amount of epoxide, based on the available amine nitrogen atoms in the polyvinylamine. In preferred embodiments q in the range of 1 to 15, in particular 1 to 10, particularly preferably 1 to 6.

To obtain alkoxylated polyvinylamines, wherein the mean q 1, the polyvinylamines are usually reacted with an epoxide in the absence of a catalyst. It is expedient to use an aqueous solution of polyvinylamine. To obtain alkoxylated polyvinylamines, wherein q greater than 1, the polyvinylamine is reacted with the epoxide in an anhydrous solvent. Preferably, the reaction is then carried out in the presence of a base. Examples of suitable bases are alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alcoholates such as sodium methoxide and sodium ethoxide, sodium hydride and calcium hydride. Preferred bases are the alkali metal hydroxides and especially sodium hydroxide.

Suitable solvents are C ₁ -C ₄ -alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, ethers such as tetrahydrofuran, dioxane, amides such as dimethylformamide and mixtures thereof. It is also possible to use aliphatic or aromatic hydrocarbons, such as hexane, cyclohexane, toluene, xylenes, and similar solvents.

The reaction temperature is usually more than 70 ° C and is preferably 70 to 150 ° C, in particular 75 to 110 ° C. The reaction can take place in the customary reactors. The application of increased pressure is basically not required. However, it can be advantageous in the case of conversion of volatile components. The reaction pressure can then be up to 50 bar, preferably up to 10 bar. The epoxide may be added in one portion or over a period of time ranging from several minutes to several hours.

For working up the alkoxylated polyvinylamine obtained in the reaction with the epoxide, the organic solvent is generally removed and replaced by water. This gives aqueous solutions of the desired alkoxylated polyvinylamines, which can be used directly in the detergent composition according to the invention. Of course, it is also possible to isolate the alkoxylated polyvinylamines as a solid by removing the volatiles of the reaction.

Depending on their degree of alkoxylation, the alkoxylated polyvinylamines according to the invention have molar masses M _w (determined by the method of light scattering) of from 1000 to 10 000 000, preferably from 10 000 to 2 000 000. The K values of the alkoxylated polyvinylamines according to the invention are in the range from 20 to 300, preferably in the range of 30 to 200. The K values were determined according to H. Fikentscher in 5% strength by weight aqueous sodium chloride solution at pH 7 and a temperature of 25 ° C. and a polymer concentration of 0.5% by weight. % determined (see above).

Nitrogen-containing polymers having repeating units of the formula II are derived from modified polyaminoamides.

Polyaminoamides are polymers whose backbone chain contains both amine and amide functionalities. They are obtainable by reacting polyalkylenepolyamines with dicarboxylic acids, preferably in a molar ratio of 1: 0.5 to 1: 2.

By polyalkylenepolyamines is meant compounds consisting of a saturated hydrocarbon chain having terminal amino functions interrupted by at least one secondary amino group. Suitable polyalkylenepolyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diaminopropylethylenediamine (= N, N'-bis (3-aminopropyl) -1,2-diaminoethane), ethylene-propylenetriamine, 3- (2-aminoethyl) aminopropylamine, dipropylenetriamine and polyethyleneimines with molecular weights of preferably from 300 to 20,000, in particular from 300 to 5,000. Preference is given to poly-C ₂ -C ₃ -alkyleneamines having from 3 to 10 nitrogen atoms. Of these, diethylenetriamine, 3- (2-aminoethyl) aminopropylamine, dipropylenetriamine and diaminopropylethylenediamine are particularly preferred. Of course, the polyalkylenepolyamines can be used in a mixture with one another.

Suitable dicarboxylic acids are in particular those having 2 to 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, itaconic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, phthalic acid and terephthalic acid. Also suitable are dibasic amino acids, such as iminodiacetic acid, aspartic acid and glutamic acid. Preferred acids are adipic acid, glutaric acid, aspartic acid and iminodiacetic acid. Of course, the dicarboxylic acids can be used in a mixture with each other.

The dicarboxylic acids can be used in the form of the free acids or as carboxylic acid derivatives, such as anhydrides, esters, amides or acid halides, especially chlorides. examples for such derivatives are anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride and itaconic anhydride; adipic acid; Esters with preferably C ₁ -C ₂ -alcohols, such as dimethyl adipate, diethyl adipate, dimethyl tartrate and Iminodiessigsäuredimethylester; Amides, such as adipamide, adipic acid monoamide and glutaric acid diamide. Preferably, the free carboxylic acids or the carboxylic anhydrides are used.

The polycondensation of the polyamine and the dicarboxylic acid is carried out in a customary manner by heating the polyamine and the dicarboxylic acid, for. B. to temperatures of 100 to 250 ° C, preferably 120 to 200 ° C, and distilling off the water of reaction formed in the condensation. When using the said carboxylic acid derivatives, the condensation can also be carried out at temperatures lower than those stated. The preparation of the polyaminoamides can be carried out without addition of a catalyst or else using an acidic or basic catalyst. Suitable acidic catalysts are for example acids, such as Lewis acids, for. Sulfuric acid, p-toluenesulfonic acid, phosphorous acid, hypophosphorous acid, phosphoric acid, methanesulfonic acid, boric acid, aluminum chloride, boron trifluoride, tetraethyl orthotitanate, tin dioxide, tin butyl dilaurate or mixtures thereof. Suitable basic catalysts are, for example, alkoxides, such as sodium methylate or sodium ethylate, alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide or lithium hydroxide, alkaline earth metal oxides, such as magnesium oxide or calcium oxide, alkali metal and alkaline earth metal carbonates, such as sodium, potassium and calcium carbonate, phosphates, such as potassium phosphate and complex metal hydrides, like sodium borohydride. The catalyst, if used, is generally used in an amount of 0.05 to 10% by weight, preferably 0.5 to 1% by weight, based on the total amount of the starting materials.

The reaction can be carried out in a suitable solvent or preferably solvent-free. When using a solvent, for example, hydrocarbons such as toluene or xylene, nitriles such as acetonitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, ethers such as diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate and the like are suitable. In general, the solvent is distilled off during the reaction or after completion of the reaction. This distillation may optionally be carried out under protective gas, such as nitrogen or argon.

steht, sind durch Umsetzung der Polyaminoamide mit Epoxiden der Formel IV erhältlich. Hierbei bilden sich an allen oder einem Teil der Aminogruppen der Polyaminoamide alkoxilierte Seitenketten. Der Mittelwert q von q bestimmt sich nach der molaren Menge an Epoxid, bezogen auf die zur Verfügung stehenden Amin-Stickstoffatome im Polyaminoamid.Polyaminoamides having side chains of the formula Z ² , wherein Z ^{2 is} for

can be obtained by reacting the polyaminoamides with epoxides of the formula IV. Here, alkoxilated side chains are formed on all or part of the amino groups of the polyaminoamides. The mean q of q is determined by the molar amount of epoxide, based on the available amine nitrogen atoms in the polyaminoamide.

Suitable epoxides are, for example, the epoxides of ethene, propene, 1-butene, 1-pentene. With respect to the alkoxylation, reference is made to the above with regard to the alkoxylation of polyvinylamines. In preferred embodiments q in the range of 1 to 15, in particular 1 to 10, particularly preferably 1 to 6.

Preferably, about 5 to 100%, in particular 15 to 90%, of the amino nitrogen atoms in the polyaminoamide are alkoxylated.

Polyaminoamides in which Z ^{2 is} R ⁵ CO can be obtained by reacting polyaminoamides with a compound of the formula R ⁵ -CO-X, where R ^{5 has} the meaning already indicated. X represents a nucleophilically displaceable leaving group, in particular hydroxyl, alkoxy, acyloxy or halogen, in particular chlorine. The compound of the formula R ⁵ -CO-X is therefore a carboxylic acid of the formula R ⁵ -COOH or an ester, in particular an anhydride or a halide, in particular a chloride thereof.

The amidation can be carried out under conventional conditions without the addition of a catalyst or using an acidic or basic catalyst. Suitable catalysts are those mentioned above with respect to the preparation of the underlying polyaminoamides. The reaction can be carried out in a suitable solvent or preferably solvent-free. Suitable solvents and reaction conditions are those mentioned above with respect to the preparation of the underlying polyaminoamides.

Preferably, about 5 to 100%, in particular 15 to 90%, of the amino nitrogen atoms in the polyaminoamide are acylated.

Instead of reacting the preformed polyaminoamide with the carboxylic acid R ⁵ COOH or a derivative thereof, these can alternatively be added in the preparation of the polyaminoamide. Polyaminoamides which can be used according to the invention and have side chains of the formula Z ² , wherein Z ^{2 is} R ⁵ CO, are therefore obtainable by polycondensation of a polyamine with a dicarboxylic acid and a monocarboxylic acid of the formula R ⁵ COOH. The dicarboxylic acid or the monocarboxylic acid of the formula R ⁵ COOH can be used as such or in the form of a derivative, such as an anhydride, ester or halide. Preferably, the polyalkylenepolyamine, dicarboxylic acid and monocarboxylic acid are reacted in a molar ratio of 1: (0.5-1.5) :( 0.05-3).

Further alternatively, before the preparation of the polyaminoamide, the polyamine can be partially amidated with a monocarboxylic acid of the formula R ⁵ COOH or a derivative thereof and then with a dicarboxylic acid or a derivative thereof to a polyaminoamide having side chains of the formula Z ² which can be used according to the invention, where Z ^{2 is} R ⁵ CO, react.

Polyaminoamides having side chains of the formula Z ² , wherein Z ^{2 is} R ⁶ , are obtainable by reacting a polyaminoamide with an alkylating agent of the formula R ⁶ -Y, wherein R ^{6 has} the meaning already indicated and Y is a nucleophilically displaceable leaving group, such as halogen , in particular chlorine, bromine or iodine, or an activated hydroxyl group, such as tosyloxy.

Suitable polyaminoamides are also obtained by reacting polyaminoamides, in which the amine nitrogen atoms in part carry side chains with Z ² equal to R ⁵ CO and / or R ⁶ , as described with ethylene oxide, propylene oxide, butylene oxide or longer-chain Alkylepoxiden.

Insofar as the modified polyaminoamide contains protonated or quaternizable nitrogen atoms, these can be reacted with protonation or quaternizing agents, as described further below.

Nitrogen-containing polymers having repeating units of the formula III are urethane and / or urea groups and polymers containing tertiary amino groups.

They are obtainable by reacting (i) at least one difunctional isocyanate and (ii) at least one compound having isocyanate-reactive groups and additionally at least one tertiary amino group.

Component (i) is preferably selected from diisocyanates, isocyanate prepolymers having 2 isocyanate groups and mixtures thereof. Also suitable are compounds which, instead of free isocyanate groups, have functional groups which Release isocyanate groups or react as isocyanate groups. These include z. B. capped isocyanate groups, uretdione groups, isocyanurate groups and / or biuret-containing compounds.

Diisocyanates suitable as component (i) may be aliphatic, cycloaliphatic or aromatic. Aliphatic diisocyanates preferably have a hydrocarbon radical having 4 to 12 carbon atoms. Suitable diisocyanates are, for. Tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,3,3-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), 2,2-bis (4-isocyanatocyclohexyl) propane, 1, 4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI) and their isomer mixtures (eg 80% 2,4- and 20% 2,6-isomer), 2,4- and 4,4 ' Diphenylmethane diisocyanate (MDI), o- and m-xylylene diisocyanate (XDI), 1,5-naphthylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-isocyanatocyclohexyl) methane, such as. The trans / trans, cis / cis and cis / trans isomers and mixtures thereof.

The isocyanate-reactive groups of the compounds of component (ii) are selected from hydroxyl groups, primary and secondary amino groups. Depending on these groups, polymers resulting in urethane groups and / or urea groups result. Suitable compounds (ii) are, for. B. tertiary amines in which the amine nitrogen has two hydroxyalkyl and / or aminoalkyl groups and another group which is selected from C ₁ -C ₆ alkyl, phenyl and phenyl-C ₁ -C ₄ alkyl.

worin

• R³ unabhängig voneinander für C₂-C₈-Alkandiyl stehen und
• Z³ für C₁-C₆-Alkyl, Phenyl, Phenyl-C₁-C₄-alkyl steht.

Preferably, component (ii) comprises at least one compound of the general formulas

wherein

• R ³ independently of one another are C ₂ -C ₈ -alkanediyl and
• Z ^{3 is} C ₁ -C ₆ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl.

Particularly preferred compounds (ii) are bis (aminopropyl) methylamine, bis (aminopropyl) piperazine, methyldiethanolamine and mixtures thereof.

Suitable compounds (ii) are furthermore polyethers which have at least one tertiary nitrogen atom and two isocyanate-reactive groups, preferably two hydroxyl groups. These are z. B. by alkoxylation of primary amines, such as. As methylamine by conventional, known in the art process available. Preferably, the number average molecular weight of the polyethers ranges from 500 to 6000 g / mol.

The nitrogen-containing polymers having repeating units of the formula III may contain, in addition to the components (i) and (ii), further components which are customary for the preparation of polyurethanes or polyureas. These include z. Example of the component (ii) different compounds having at least two isocyanate-reactive groups, such as are commonly used as chain extenders. Preferably no chain extenders are used.

The nitrogen-containing polymers having repeating units of the formula III may additionally contain at least one further compound with an isocyanate-reactive group (stopper) incorporated. This group is preferably a hydroxyl or a primary or secondary amino group. Suitable compounds having an isocyanate-reactive group are, for. As monofunctional alcohols, such as methanol, ethanol, n-propanol, isopropanol, etc. Also suitable are amines having a primary or secondary amino group, such as. For example, methylamine, ethylamine, n-propylamine, isopropylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, etc. are also stopper having an isocyanate-reactive group and at least one tertiary amino and / or ammonium group. Examples are z. N, N-dialkylamino alcohols or amines.

Preferred are polymers which have a number average molecular weight in the range of about 1000 to 50,000, preferably 2000 to 20,000.

The content of urethane and / or urea groups is preferably in a range from 2 to 8 mol / kg, more preferably 3 to 8 mol / kg, in particular 4 to 8 mol / kg.

Quaternary groups can be prepared from the tertiary amine nitrogens of the compounds of component (ii) or of the polymers which incorporate component (ii), e.g. B. either by protonation, z. As with carboxylic acids such as lactic acid, or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, for. B. with alkylating agents, such as C ₁ -C ₄ alkyl halides or sulfates, benzyl halides, etc. produce. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. The neutralization and / or quaternization, depending on the application partially, z. B. to 10 to 90%, or completely, ie 100% done. The neutralization can take place before, during or after the polyaddition.

The preparation of the polymers having repeating units of the general formula III is carried out by reacting at least one diisocyanate (i) with at least one compound of component (ii) and optionally additional compounds having isocyanate-reactive groups. In this case, the ratio of NCO equivalent of component (i) to equivalent active hydrogen atom of component (ii) and optionally additional compounds is generally in a range from about 0.6: 1 to 1.4: 1, preferably 0.9: 1 to 1.1: 1, in particular 0.9: 1 to 1: 1. The reaction can be carried out without solvent or in a suitable inert solvent or solvent mixture. Preference is given to solvents which are immiscible with water indefinitely. Also preferred are solvents which have a boiling point at atmospheric pressure in the range of about 40 to 100 ° C. Suitable aprotic polar solvents, eg. For example, tetrahydrofuran, ethyl acetate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and preferably ketones, such as acetone and methyl ethyl ketone. If desired, the reaction under an inert gas atmosphere, such as. B. under nitrogen, take place. Furthermore, the reaction is preferably carried out at ambient pressure or under elevated pressure, in particular the autogenous pressure of the reactants under the reaction conditions. The reaction temperature is preferably in a range of about 5 to 180 ° C, especially 20 to 150 ° C. If, as component (ii) and optionally as additional components, predominantly compounds are used which have primary amino groups as groups reactive toward isocyanate groups, the reaction can, if desired, be carried out in a solvent or solvent mixture which can have active hydrogen atoms. In addition to the aforementioned then preferably used alcohols such as methanol and ethanol, mixtures of alcohols and water, mixtures of ketones and water and mixtures of alcohols and the aforementioned ketones.

Suitable polymerization apparatuses are known to the person skilled in the art. These include z. B. stirred tank, which are optionally equipped with devices for removing the heat of reaction. If an organic solvent is used in the preparation of the polymers, then this can be followed by conventional methods known to the person skilled in the art, eg. B. by distillation at reduced pressure can be removed. Before separating off the solvent, water may additionally be added to the polymer. If desired, high-boiling solvents may also remain in the solution, but their proportion should preferably be not more than 10% by weight, based on the weight of the polymer.

The detergent compositions contain at least one surfactant as component A). The surfactants commonly used in detergents are suitable. The surfactants used may be anionic, nonionic, amphoteric or cationic.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 8 to 18 carbon atoms, for. As C ₉ -C ₁₁ alcohol sulfates, C ₁₂ -C ₁₃ alcohol sulfates, C ₁₄ -C ₁₈ alcohol sulfates such as lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate or tallow fatty alcohol sulfate.

Further suitable anionic surfactants are sulfated ethoxylated C ₈ -C ₂₂ -alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C ₈ -C ₂₂ -alcohol, preferably a C ₁₀ -C ₁₈ -alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out with propylene oxide alone and optionally butylene oxide. Also suitable are those alkoxylated C ₈ -C ₂₂ -alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. The alkoxylated C ₈ -C ₂₂ -alcohols may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in static distribution.

Other suitable anionic surfactants are alkanesulfonates such as C ₈ -C ₂₄ -, preferably C ₁₀ -C ₁₈ -Alkansulfonate and soaps such as the Na and K salts of C ₈ -C ₂₄ carboxylic acids.

Further suitable anionic surfactants are C ₈ -C ₂₀ -linear-alkylbenzenesulfonates (LAS), preferably linear C ₉ -C ₁₃ -alkylbenzenesulfonates and -alkyltoluenesulfonates.

Also suitable as anionic surfactants are C ₈ -C ₂₄ -olefinsulfonates and -disulfonates, which may also be mixtures of alkene and hydroxyalkanesulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates of about 20 to 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyltaurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids or their half-esters or hemiamides, alkylsulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids, acylsarcosinates, sulfated alkylpolyglycosides, Alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

Suitable anionic surfactants are also alkyl phosphates.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts are alkali metal salts such as sodium, potassium and lithium and ammonium salts such as e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts. It is possible to use individual anionic surfactants or a combination of different anionic surfactants. It is possible to use anionic surfactants of only one class, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use surfactant mixtures of various classes, eg. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.

Preferred anionic surfactants are alkyl ether sulfates, alkyl sulfates and alkyl phosphates.

Suitable nonionic surfactants are, for example, alkoxylated C ₈ -C ₂₂ -alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. Suitable surfactants are all alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added. Here, too, come block polymers of ethylene oxide, propylene oxide and / or butylene oxide or addition products which contain said alkylene oxides in static distribution. From 2 to 50, preferably from 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. Preferably used as alkylene oxide ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of suitable nonionic surfactants are alkylphenol ethoxylates having C ₆ -C ₁₄ alkyl chains and from 5 to 30 moles of ethylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units. Another class of nonionic surfactants are N-alkylglucamides.

Suitable nonionic surfactants are, for example, alkylamine alkoxides or alkylamide ethoxylates.

Preferably, the cleaning agents according to the invention with 3 to 12 moles of ethylene oxide ethoxylated C ₁₀ -C ₁₆ alcohols, more preferably ethoxylated fatty alcohols as nonionic surfactants. Preference is also alkylpolyglycosides, Alkylaminalkoxilate or Alkylamidethoxilate.

It is possible to use individual nonionic surfactants or a combination of different nonionic surfactants, in particular only alkoxylated C ₈ -C ₂₂ -alcohols, but it is also possible to use surfactant mixtures from different classes.

Typical examples of amphoteric surfactants are alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates or amphoteric imidazolium compounds. Preferred examples are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate and cocoamphoacetate.

Suitable cationic surfactants are substituted or unsubstituted, straight-chain or branched quaternary ammonium salts, for example C ₈ - to C ₁₆ -dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.

The detergent formulations contain as component B) at least one builder. Builders include inorganic builders and organic (co) builders.

Suitable inorganic builders are all customary inorganic builders, such as aluminosilicates, silicates, carbonates, phosphates and phosphonates.

Suitable inorganic builders are e.g. Aluminosilicates having ion-exchanging properties, e.g. Zeolites. Various types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially exchanged with other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in EP-A 0 038 591, EP-A 0 021 491, EP-A 0 087 035, US 4,604,224, GB-A 20 13 259, EP-A 0 522 726, EP-A 0 384 070 and WO-A-94/24 251. Aluminosilicate builders are preferred.

Other suitable inorganic builders are e.g. amorphous or crystalline silicates such as e.g. amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst). The silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Preferably, Na, Li and Mg silicates are used.

Amorphous silicates such as sodium metasilicate having a polymeric structure or amorphous disilicate (Britesil® H 20 manufactured by Akzo) are also useful.

Suitable inorganic builders are also carbonates, including bicarbonates and sesquicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate.

Suitable inorganic builders are also alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphate, pyrophosphate and glassy polymeric metaphosphates and phosphonates.

The inorganic builders can be used individually or in mixtures with one another.

• C₄-C₂₀-Di-, -Tri- und -Tetracarbonsäuren wie z.B. Bernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure und Alkyl- und Alkylenbernsteinsäuren mit C₂-C₁₆-Alkyl- bzw. -Alkylen-Resten;
• C₄-C₂₀-Hydroxycarbonsäuren wie z.B. Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Citronensäure, Lactobionsäure und Saccharosemono-, -di- und -tricarbonsäure;

Suitable low molecular weight polycarboxylates as organic cobuilders are, for example:

• C ₄ -C ₂₀ -di-, -tri- and -Tetracarbonsäuren such as succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic and alkyl and Alkylenbernsteinsäuren with C ₂ -C ₁₆ alkyl or -alkylene radicals;
• C ₄ -C ₂₀ -hydroxycarboxylic acids such as, for example, malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;

Aminopolycarboxylates such as e.g. Nitrilotriacetic acid, methylglycinediacetic acid, alaninediacetic acid, ethylenediaminetetraacetic acid and serinediacetic acid; Aminopolycarboxylates are commercially available, for example, under the name Trilon®.

Salts of phosphonic acids, e.g. Hydroxyethanediphosphonic acid, ethylenediaminetetra (methylenephosphonate) and diethylenetriaminepenta (methylenephosphonate).

Suitable oligomeric or polymeric polycarboxylates as organic cobuilders are, for example:

Oligomaleeinsäuren, as described for example in EP-A 0 451 508 and EP-A 0396303;

• aus der Gruppe (α) in Mengen von bis zu 95 Gew.-%
• aus der Gruppe (β) in Mengen von bis 60 Gew.-%
• aus der Gruppe (γ) in Mengen von bis zu 20 Gew.-%

einpolymerisiert enthalten sein können.Co- and terpolymers of unsaturated C ₄ -C ₈ -dicarboxylic acids, wherein as comonomers monoethylenically unsaturated monomers

• from the group (α) in amounts of up to 95% by weight
• from the group (β) in amounts of up to 60% by weight
• from the group (γ) in amounts of up to 20% by weight

may be included in copolymerized form.

Examples of suitable unsaturated C ₄ -C ₈ -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.

The group (α) comprises monoethylenically unsaturated C ₃ -C ₉ monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. From the group (α), preference is given to using acrylic acid and methacrylic acid.

The group (β) comprises monoethylenically unsaturated C ₂ -C ₂₂ -olefins, vinylalkyl ethers having C ₁ -C ₈ -alkyl groups, styrene, vinyl esters of C ₁ -C ₈ -carboxylic acids, (meth) acrylamide and vinylpyrrolidone. Prefers are used from the group (β) C ₂ -C ₆ olefins, vinyl alkyl ethers having C ₁ -C ₄ alkyl groups, vinyl acetate and vinyl propionate.

The group (γ) comprises (meth) acrylic esters of C ₁ -C ₈ -alcohols, (meth) acrylonitrile, (meth) acrylamides, (meth) acrylamides of C ₁ -C ₈ -amines, N-vinylformamide and vinylimidazole.

If the polymers of group (β) contain copolymerized vinyl esters, these may also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 43 13 909.

• Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 10:90 bis 95:5, insbesondere bevorzugt solche im Gewichtsverhältnis 30:70 bis 90:10 mit Molmassen von 10000 bis 150000;
• Terpolymere aus Maleinsäure, Acrylsäure und einem Vinylester einer C₁-C₃-Carbonsäure im Gewichtsverhältnis 10 (Maleinsäure) : 90 (Acrylsäure + Vinylester) bis 95 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gew.-Verhältnis von Acrylsäure zu Vinylester im Bereich von 20:80 bis 80:20 variieren kann, und besonders bevorzugt.
• Terpolymere aus Maleinsäure, Acrylsäure und Vinylacetat oder Vinylpropionat im Gewichtsverhältnis 20 (Maleinsäure) : 80 (Acrylsäure + Vinylester) bis 90 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gew.-Verhältnis von Acrylsäure zum Vinylester im Bereich von 30:70 bis 70:30 variieren kann;
• Copolymere von Maleinsäure mit C₂-C₈-Olefinen im Molverhältnis 40:60 bis 80:20, wobei Copolymere von Maleinsäure mit Ethylen, Propylen oder Isobuten im Molverhältnis 50:50 besonders bevorzugt sind.
• Pfropfpolymere ungesättigter Carbonsäuren auf niedermolekulare Kohlenhydrate oder hydrierte Kohlenhydrate, vgl. US 5,227,446, DE-A 44 15 623, DE-A 43 13 909, sind ebenfalls als organische Cobuilder geeignet.

Suitable copolymers of dicarboxylic acids as organic cobuilders are preferably:

• Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 10,000 to 150,000;
• Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), wherein the weight ratio of acrylic acid to vinyl esters in the range of from 20:80 to 80:20, and more preferred.
• Terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in the weight ratio 20 (maleic acid): 80 (acrylic acid + vinyl ester) to 90 (maleic acid): 10 (acrylic acid + vinyl ester), wherein the ratio by weight of acrylic acid to vinyl ester in the range of 30: 70 to 70:30 may vary;
• Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, with copolymers of maleic acid with ethylene, propylene or isobutene in the molar ratio 50:50 are particularly preferred.
• Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US 5,227,446, DE-A 44 15 623, DE-A 43 13 909, are also suitable as organic cobuilders.

Examples of suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.

For modification, in addition up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers may be present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of the groups (β) and (γ).

As a graft base degraded polysaccharides such as acidic or enzymatically degraded starches, inuline or cellulose, reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and glucamine are suitable as well as polyalkylene with molecular weights up to M _w = 5000 such as polyethylene glycols, Ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers, random ethylene oxide / propylene oxide or ethylene oxide / butylene oxide copolymers, alkoxylated mono- or polyhydric C ₁ -C ₂₂ -alcohols, cf. US 4,746,456.

Grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization. For grafting, a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used.

Polyglyoxylic acids as organic cobuilders are described, for example, in EP-B 0 001 004, US Pat. No. 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the polyglyoxylic acids may have different structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic cobuilders are known, for example, from EP-A 0 454 126, EP-B 0 511 037, WO-A 94/01486 and EP-A 0 581 452.

Polyaspartic acid or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ -mono- or -dicarboxylic acids and / or C ₄ -C ₂₅ -mono- or -diamines are preferably also used as organic cobuilders. Particularly preferred are prepared in phosphorus-containing acids, with C ₆ -C ₂₂ mono- or dicarboxylic acids or with C ₆ -C ₂₂ mono- or diamines modified polyaspartic acids used.

Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as organic cobuilders are e.g. known from WO-A 93/22362 and WO-A 92/16493. Such condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.

The detergent formulations may be powder, granular, paste, gel or liquid.

In a preferred embodiment, the detergent composition according to the invention contains conventional ingredients which are selected from soil release polymers, enzymes, foam boosters, foam inhibitors or foam inhibitors, biocides, bleach systems, tarnish and / or corrosion inhibitors, suspending agents, dyes, fillers, inorganic adjusters, disinfectants , pH regulators, hydrotropes, antioxidants, enzyme stabilizers, perfumes, solvents, solubilizers, dispersants, processing aids, solubilizers, plasticizers and antistatic agents.

• Polyester aus Polyethylenoxiden mit Ethylenglycol und/oder Propylenglycol und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren;
• Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei- und/oder mehrwertigen Alkoholen und Dicarbonsäure. Derartige Polyester sind bekannt, beispielsweise aus US 3,557,039, GB-A 11 54 730, EP-A 0 185 427, EP-A 0 241 984, EP-A 0 241 985, EP-A 0 272 033 und US-A 5,142,020.

Suitable soil release polymers for detergent compositions are, for example:

• Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
• Polyesters of unilaterally end-capped polyethylene oxides with dihydric and / or polyhydric alcohols and dicarboxylic acid. Such polyesters are known, for example from US 3,557,039, GB-A 11 54 730, EP-A 0 185 427, EP-A 0 241 984, EP-A 0 241 985, EP-A 0 272 033 and US-A 5,142,020.

Further suitable soil-release polymers are amphiphilic graft copolymers or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (compare US Pat. Nos. 4,746,456, 4,846,995, DE-A 37 11 299, 4,904,408, 4,846,994 and 4,849,126) or modified celluloses such as Methylcellulose, hydroxypropylcellulose or carboxymethylcellulose.

Suitable enzymes are proteases, lipases, amylases and cellulases. The enzyme system may be limited to a single one of the enzymes or may include a combination of different enzymes. Examples of suitable foam suppressants or foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica

Suitable biocides are, for example, isothiazolinones, 2-bromo-2-nitro-1,3-propanediol.

Suitable bleaching systems consist, for example, of bleaching agents and bleach activators

Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents. Use as oxygen bleach find alkali metal perborates and their hydrates and alkali metal percarbonates. Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Also usable as oxygen bleaching agents are persulfates and hydrogen peroxide. Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.

In addition, the following oxygen bleaches can also be used in the detergent composition: Cationic peroxyacids described in the patent applications US 5,422,028, US 5,294,362 and US 5,292,447; Sulfonyl peroxyacids, which are described in the patent application US 5,039,447.

Oxygen bleaching agents are used in amounts of 0.5 to 30 wt .-%, preferably from 1 to 20 wt .-%, particularly preferably from 3 to 15 wt .-%, based on the total detergent composition.

Chlorine-containing bleaches as well as the combination of chlorine-containing bleach with peroxide-containing bleaches can also be used. Known chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfondichloroamide or trichloroethylamine. Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate.

Chlorine-containing bleaching agents are used in amounts of 0.1 to 20 wt .-%, preferably from 0.1 to 10 wt .-%, particularly preferably from 0.3 to 8 wt .-%, based on the total detergent composition.

Furthermore, bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.

Bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid. Suitable compounds are those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides such as N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates such as n-nonanoyl or isononanoyloxybenzenesulfonates (n- or n-nonanoyl) iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA).

Also suitable as bleach activators are nitrile quats, such as, for example, N-methyl-morpholinium-acetonitrile salts (MMA salts) or trimethylammonium acetonitrile salts (TMAQ salts).

Bleach activators are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ. Furthermore, the following substances can be used as bleach activators in the detergent composition: Carboxylic anhydrides such as phthalic anhydride; acylated polyhydric alcohols such as triacetin, ethylene glycol diacetate or 2,5-diacetoxy-2,5-dihydrofuran; the enol esters known from DE-A 196 16 693 and DE-A 196 16 767 and also acetylated sorbitol and mannitol or their mixtures described in EP-A 525 239; acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and also acetylated, optionally N-alkylated, glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are described in WO 94/27 970, WO 94/28 102, WO 94/28 103, WO 95/00626, WO 95/14759 and WO 95/17498 are known; the hydrophilic substituted listed in DE-A 196 16 769 Acyl acetals and the acyl lactams described in DE-A 196 16 770 and WO 95/14075 can be used as well as the known from DE-A 44 43 177 combinations of conventional bleach activators.

Bleach activators are used in amounts of from 0.1 to 10% by weight, preferably from 1 to 8% by weight, particularly preferably from 1.5 to 6% by weight, based on the total detergent formulation.

In addition to the conventional bleach activators listed above or in their place, the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from EP-A 446 982 and EP-A 453 003 may also be present as so-called bleach catalysts in the detergent compositions.

Suitable transition metal compounds include, for example, the manganese, iron, cobalt, ruthenium or molydane selenium complexes known from DE-A 195 29 905 and their N-analogues known from DE-A 196 20 267, which A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, the described in DE-A 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-ammine complexes known from DE-A 196 20 411, the manganese, copper and cobalt complexes described in DE-A 44 16 43 8, the cobalt complexes described in EP-A 272 030, the manganese complexes known from EPA 693 550, the manganese, iron, cobalt and copper complexes known from EP-A 392 592 and / or those disclosed in EP-A 443,651, EP-A 458 397, EP-A 458 398, EP-A 549 271, EP-A 549 272, EP-A 544 490 and EP-A 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from DE-A 196 13 103 and WO 95/27 775.

Bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes are preferably suitable. The cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate are particularly preferably suitable.

Bleach catalysts are used in amounts of 0.0001 to 5 wt .-%, preferably from 0.0025 to 1 wt .-%, particularly preferably from 0.01 to 0.25 wt .-%, based on the total detergent composition.

Examples of suitable corrosion inhibitors are silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes.

A suitable inorganic adjusting agent is, for example, sodium sulfate.

Suitable pH-regulating substances are, for example, alkalis such as NaOH, KOH, pentasodium metasilicate or acids such as hydrochloric acid, phosphoric acid, amidosulfuric acid, citric acid.

Suitable solvents are, for example, short-chain alkyl oligoglycols such as butyl glycol, butyl diglycol, propylene glycol monomethyl ether, hexylglycols, alcohols such as ethanol or i-propanol, aromatic solvents such as toluene, xylene, N-alkylpyrrolidone, alkylene carbonates.

Suitable dispersants are, for example, naphthalenesulfonic acid condensates, polycarboxylates.

Suitable solubilizers are, for example, cumene sulfonates, toluenesulfonates, short-chain fatty acids, alkyl phosphates / aryl esters, hexylglycols.

As a detergent composition according to the invention are, for example, machine cleaners, metal degreaser, glass cleaner, floor cleaner, all-purpose cleaner, high pressure cleaner, alkaline cleaner, acidic cleaner, Spritzentfetter, dairy cleaner, rinse aid, dishwashing detergent, etc. into consideration.

A solid detergent composition according to the invention is usually in the form of powder or granules or in extrudate or tablet form.

Powdery or granular detergent compositions according to the invention may contain up to 60% by weight of inorganic setting agents. Usually, sodium sulfate is used for this purpose. However, the detergent compositions according to the invention are preferably low in leveling agents and contain only up to 20% by weight, more preferably up to 8% by weight, of setting agents, in particular in the case of compact or ultra-compact detergent compositions. The solid detergent compositions according to the invention may have different bulk densities in the range of 300 to 1300 g / l, in particular of 550 to 1200 g / l. Modern compact detergents generally have high bulk densities and show a granular structure. To the desired compression The detergent compositions can be any of those commonly used in the art.

Tablet-form detergent compositions according to the invention furthermore generally comprise tabletting aids, such as polyethylene glycols having molecular weights greater than 1000 g / mol, polymer dispersions and tablet disintegrating agents, such as cellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinked polyacrylates or combinations of acids, such as citric acid and sodium bicarbonate.

The detergent composition of the invention is prepared by conventional methods and optionally formulated.

1. a) wenigstens ein Tensid und
2. b) wenigstens ein stickstoffhaltiges Polymer mit Wiederholungseinheiten der allgemeinen Formel I, II oder III,
   
   
   oder dessen Umsetzungsprodukte mit Neutralisierungsmitteln oder Quarternierungsmitteln, worin die Variablen R¹, R², R³, Z¹, Z², Z³, k und p die zuvor genannten Bedeutungen aufweisen, sowie gegebenenfalls wenigstens einen Builder enthält,
   in Kontakt bringt, den Überschuss entfernt und/oder abspült.

Another object of the present invention is a method for cleaning hard surfaces, wherein the hard surface with an aqueous solution of a detergent composition, the

1. a) at least one surfactant and
2. b) at least one nitrogen-containing polymer having repeating units of the general formula I, II or III,
   
   
   or its reaction products with neutralizing agents or quaternizing agents, wherein the variables R ¹ , R ² , R ³ , Z ¹ , Z ² , Z ³ , k and p have the meanings given above, and optionally at least one builder,
   contact, remove the excess and / or rinsed off.

The term "hard surface" is generally understood to mean surfaces of objects made of plastic, glass, stainless steel, enamel or surfaces of tiles and painted surfaces. In general, treat the hard surface with a diluted, preferably aqueous solution of the detergent composition in a typical for the type of surface, for. As by rinsing, spraying, wiping or similar methods, as is commonly used for cleaning hard-surface objects use. The rinsing can be done for example by machine or by hand. The "bringing into contact" usually takes place during the cleaning process. The amount of nitrogen-containing polymer required for hydrophilization with repeating units of the formula I, II or III is adsorbed by the surface and adheres as a thin film on the surface. The amount necessary to achieve a hydrophilization sets itself automatically and remains sticking after drying. For example, an excess may be rinsed with water or wiped away with an absorbent material such as cloth.

The detergent compositions according to the invention are used, for example, for cleaning work surfaces, tiles, bath facilities, kitchen furniture such as tables, chairs, cupboards, kitchen appliances such as refrigerators, stoves or extractor hoods, furniture made of plastics, dishes, glasses, windows or blinds.

The nitrogen-containing polymers having repeating units of the formula I, II or III used in the detergent compositions have a cleaning-enhancing action. The detergent composition according to the invention appreciably facilitates the removal of dirt. In particular, with regular use, the adhesion of dirt is permanently reduced.

Application examples show that it is possible with the nitrogen-containing polymers according to the invention used in the detergent compositions with repeating units of the formula I, II or III to effectively hydrophilize hard surfaces.

The following examples are intended to illustrate the invention without limiting it.

I. Preparation Examples Example 1: Butoxylated polyvinylamine ( q = 2)

496.6 g of an aqueous polyvinylamine solution (K value = 45, polymer content = 8.3% by weight, number of amino groups per 100 g of solution = 182.1 mmol / 100 g, amino groups in the reaction n = 0.904 mol) and 1300 g of xylene were placed in a 5 1 metal reactor and then rendered inert three times with 5 bar nitrogen. Of the The reactor contents were heated to 90 ° C and then metered over a period of 120 minutes 130.2 g of butylene oxide until a pressure of 5 bar was reached. The mixture was then stirred until the pressure remained constant. After cooling and venting the reactor, a butoxylated polyvinylamine mixture having a moderate degree of butoxylation was added q received from 2.

Example 2: Propoxylated polyaminoamide (about 50% of the amine nitrogens reacted)

2982 g of a 57% aqueous polyaminoamide solution (adipic acid-diethylenetriamine 1: 1 condensate, amino groups in the reaction n = 8.02 mol) were charged at 70 ° C in a 5 1 metal reactor and then three times with 5 bar Nitrogen inertized. The reactor contents were heated to 80 ° C and then metered 233 g (4.01 mol) of propene oxide until a pressure of 5 bar was reached. The mixture was then stirred until the pressure remained constant. After cooling and venting the reactor and degassing on a rotary evaporator at 50 ° C and 500 mbar, a propoxylated polyaminoamide was obtained in which every other amine was modified.

Example 3: polyaminoamide modified with hexanoic acid

103.3 g of diethylenetriamine were introduced into a 1 l stirred apparatus and heated to 120 ° C. under nitrogen. Upon reaching this temperature, 116.2 g of hexanoic acid were added dropwise and then heated to 170 ° C. Resulting water of reaction distilled off. After reaching an acid number of about 10 mmol KOH / g was allowed to cool to 140 ° C and added 146.2 g of adipic acid. After renewed heating to 170 ° C, water of reaction was distilled off until an acid number of 21.2 mg KOH / g and an amine value of 0.61 mmol N / g were reached. After cooling, a 40% solution of the hexanoic acid-modified polyaminoamide was prepared by adding deionized water.

Example 4: Polyurea from isophorone diisocyanate and bis (aminopropyl) piperazine

In a four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, 20.0 g (0.1 mol) of bis (aminopropyl) piperazine was dissolved in 200 g of acetone. For this purpose, 22.2 g (0.1 mol) of isophorone diisocyanate were added dropwise so that the temperature did not rise above 30 ° C. The reaction mixture was stirred for a further hour at reflux and then 110 g of HCl (1 N) and 100 g of water were added. Subsequently, the acetone was distilled off under reduced pressure. A polyurea solution was obtained with a solids content of 16.7% by weight and a pH of 7.2. The ammonium content of the polymer was 2.61 mol / kg. The urea content of the polymer was 4.74 mol / kg.

Example 5: Polyurea from isophorone diisocyanate and bis (aminopropyl) methylamine

Analogously to the preparation procedure for the polyurea 1, a polyurea was prepared from 14.5 g (0.1 mol) of bis (aminopropyl) methylamine and 22.2 g (0.1 mol) of isophorone diisocyanate. A polyurea solution having a solids content of 25.5% by weight and a pH after acidification with lactic acid of 7.7 was obtained. The ammonium content of the polymer was 2.72 mol / kg. The urea content of the polymer was 5.45 mol / kg.

Example 6: Polyurethane from isophorone diisocyanate and methyldiethanolamine

In a four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, 11.92 g (0.1 mol) of methyldiethanolamine were dissolved in 200 g of acetone. For this purpose, 22.2 g (0.1 mol) of isophorone diisocyanate were added dropwise so that the temperature did not rise above 30 ° C. The reaction mixture was stirred for a further 8 hours at reflux. Then, 100 g of HCl (1 N) were added and the acetone was distilled off under reduced pressure. A polyurethane solution having a solids content of 29.7% by weight and a pH of 7.2 was obtained. The ammonium content of the polymer was 2.93 mol / kg. The urethane content of the polymer was 5.86 mol / kg.

Example 7: Polyurea from isophorone diisocyanate and bis (aminopropyl) methylamine

In a four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, 174 g (1.2 moles) of bis (aminopropyl) methylamine were dissolved in 1200 g of acetone and neutralized with 1140 g of HCl (1 N). To this reaction mixture was added dropwise within 20 minutes 266.4 g (1.2 mol) of isophorone diisocyanate. The reaction mixture was stirred for a further hour at reflux and then distilled off the acetone under reduced pressure. A polyurea solution having a solids content of 36.3% by weight and a pH of 7.3 was obtained. The ammonium content of the polymer was 2.59 mol / kg. The urea content of the polymer was 5.45 mol / kg.

Example 8: Polyurea from hexamethylene diisocyanate and bis (aminopropyl) methylamine

Analogously to polyurea 4, a polyurea was prepared from 7.25 g (0.05 mol) of bis (aminopropyl) methylamine and 8.41 g (0.05 mol) of hexamethylene diisocyanate. A polyurea solution having a solids content of 40.3% by weight and a pH of 7.4 was obtained. The ammonium content of the polymer was 3.19 mol / kg. The urea content of the polymer was 6.39 mol / kg.

Example 9: Polyurea from isophorone diisocyanate and bis (aminopropyl) methylamine

In a four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, 29.0 g (0.2 mol) of bis (aminopropyl) methylamine in a mixture of 180 g of water, 200 g of acetone and 20 g of 90% lactic acid solved. For this purpose, 44.4 g (0.2 mol) of isophorone diisocyanate were added dropwise over a period of 20 minutes. The reaction mixture was stirred for a further hour at reflux and then distilled off the acetone under reduced pressure. A polyurea solution having a solids content of 36.4% by weight was obtained. The ammonium content of the polymer was 2.72 mol / kg. The urea content of the polymer was 5.45 mol / kg.

II. Application examples

The following compositions were prepared:
Detergent Composition 1 (comparative) 11% by weight C ₁₂ -C ₁₈ fatty alcohol ethoxylate (Lutensol A7N) 3% by weight C ₁₂ -C ₁₈ fatty alcohol ethoxylate (Lutensol A4N) 6% by weight Combination of anionic / nonionic surfactants (Lutensit A-LBN 50) ad 100% by weight water

Detergent Composition 2

11% by weight Lutensol A7N 3% by weight Lutensol A4N 6% by weight Lutensit A-LBN 50 3% by weight Propoxylated polyaminoamide from Example 2 ad 100% by weight water

Detergent Composition 3

11% by weight Lutensol A7N 3% by weight Lutensol A4N 6% by weight Lutensit A-LBN 50 3% by weight with hexanoic acid modified polyaminoamide from Example 3 ad 100% by weight water

Detergent Composition 4

11% by weight Lutensol A7N 3% by weight Lutensol A4N 6% by weight Lutensit A-LBN 50 3% by weight Polyurea from isophorone diisocyanate and bis (aminopropyl) methylamine from Example 5 ad 100% by weight water

The detergent compositions were adjusted to pH = 9 with acetic acid or sodium hydroxide solution. Thereafter, the above-described detergent compositions were diluted with water such that the ready-to-use solution had an active content of about 1%.

The peelability of colored mineral oil of polyethylene test pieces (size: 1.5 x 8 cm) was investigated.

PE specimens were pretreated as indicated in the tables below. Subsequently, the pretreated test specimens were each coated with 0.1 g of mineral oil. To determine the oil release capacity, the test specimens were immersed in one of the above diluted detergent compositions. The test specimens were weighted with a grid rack to prevent emergence. The dive time was 8 minutes each. After removal, the test pieces were dried for at least 3 hours at 50.degree. The weight of the specimens was determined and the percentage of mineral oil remaining was calculated. The results are given in the tables below. The measurements were each carried out as a duplicate determination. The mean value of two measurements was given. Table 1: Cleaning with detergent composition 1 (comparison) Pretreatment with Residual oil in% Detergent Composition 1 33.3 Detergent composition 1, then rinsed off 18.0 untreated 16.3 Pretreatment with Residual oil in% Detergent Composition 2 1.1 Detergent composition 2, then rinsed off 1.4 untreated 25.0 Pretreatment with Residual oil in% Detergent composition 3, 2.0 Detergent composition 3, then rinsed off 4.3 untreated 22.1 Pretreatment with Residual oil in% Detergent Composition 4 7.1 Detergent composition 4, then rinsed off 4.7 untreated 33.4

The results show that the application of the detergent compositions 2, 3 or 4 leads to a significantly lower tendency of the test specimens to become soiled. The results further show that the agent used for the pretreatment has a great influence on the soiling behavior of the test specimens and may even make subsequent cleaning difficult.

Claims (8)

1. A cleaner composition comprising

   A) at least one surfactant,

   B) at least one builder and

   C) at least one nitrogen-containing polymer with repeat units of the formula I, II or III,

   

   

   in which

   R¹ is C₂-C₈-alkanediyl,

   R² is a chemical bond or C₁-C₂₀-alkanediyl which is optionally interrupted by a double bond and/or an imino group and/or is optionally, completely or partially, a constituent of one or more saturated or unsaturated carbocyclic 5- to 8-membered rings, where the alkanediyl may carry one or more hydroxyl groups and/or amino groups,

   R³ is C₂-C₈-alkanediyl or is

   

   X is O, NH or C₁-C₆-alkylamino,

   Z¹ is hydrogen or is

   

   where at least one part of the radical Z¹ is different from hydrogen,

   Z² is hydrogen, R⁵CO, R⁶- or

   

   where at least one part of the radicals Z² is different from hydrogen,

   Z³ is C₁-C₆-alkyl, phenyl or phenyl-C₁-C₄-alkyl, if k = 0, together with N-R³-X can form a 5- to 7-membered saturated heterocyclic ring having 2 nitrogen atoms or, if k = 1, the two radicals Z³ can together with N-CH₂-CH₂-N form a 5- to 7-membered saturated heterocyclic ring having 2 nitrogen atoms,

   R⁴ is C₁-C₁₀-alkyl,

   R⁵ is C₄-C₂₇-alkyl or C₄-C₂₇-alkenyl, where the alkyl or alkenyl groups may carry one or more substituents which are chosen from hydroxyl, alkoxy, alkoxycarbonyl or NE₁E₂ in which E₁ and E₂ may be identical or different and are hydrogen, alkyl or acyl;

   R⁶ is C₄-C₂₇-alkyl or C₄-C₂₇-alkenyl, where the alkyl or alkenyl groups may carry one or more substituents which are chosen from hydroxyl, alkoxy, alkoxycarbonyl or NE₁E₂, in which E₁ and E₂ may be identical or different and are hydrogen, alkyl or acyl;

   p is a number from 1 to 20,

   q is a number from 1 to 20,

   k is 0 or 1;

   or reaction products thereof with neutralizing agents or quaternizing agents.
2. The cleaner composition according to claim 1, comprising a nitrogen-containing polymer with repeat units of the formula I or II, where 5 to 100 mol% of the radical Z¹ or Z² are different from hydrogen.
3. The cleaner composition according to claim 1 or 2, comprising a nitrogen-containing polymer with repeat units of the formula II in which R¹ is C₂-C₃-alkylene.
4. The cleaner composition according to claim 1 or 2, comprising a nitrogen-containing polymer with repeat units of the formula II, in which R² is C₂-C₁₂-alkanediyl which may optionally be interrupted by an imino group or be substituted by an amino group.
5. The cleaner composition according to claim 1, comprising a nitrogen-containing polymer with repeat units of the formula III, in which R² is C₂-C₁₂-alkanediyl,

   
6. The cleaner composition according to any of the preceding claims, comprising

   (A) 0.5 to 40% by weight of surfactant,

   (B) 1 to 60% by weight of builder,

   (C) 0.01 to 50% by weight of nitrogen-containing polymer, based on the total weight of the cleaner composition.
7. The cleaner composition according to any of the preceding claims, in which the builder is chosen from polyphosphates, phosphonates, silicates, carbonates, aluminosilicates, polycarboxyl compounds and complexing agents.
8. A method of cleaning hard surfaces, which comprises bringing the hard surface into contact with an aqueous solution of a cleaner composition comprising

   a) at least one surfactant,

   b) at least one nitrogen-containing polymer with repeat units of the formula I, II or III,

   

   

   in which the variables R¹, R², R³, Z¹, Z², Z³, k and p have the meanings given in claim 1, and removing and/or rinsing off the excess.