EP1456334A1 - 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

Detergent composition comprising nitrogen-containing polymers

description

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

Objects made of synthetic materials, such as thermosetting or thermoplastic plastics, for example plastic dishes, generally have hydrophobic surface properties. Hydrophobic dirt, such as carotenoids, is stubbornly adsorbed on the surface of these objects and can only be removed incompletely with detergent-containing cleaning agents. Furthermore, the water film should run off during rinsing without polishing and should not leave any annoying traces, for example due to water hardness. The known cleaning agents are still in need of improvement in this regard.

There is therefore a need for cleaning and pretreatment agents which temporarily or permanently change the surface of objects made of hydrophobic materials in such a way that the adhesion of dirt is reduced and cleaning is made easier.

The unpublished German patent application P 100 29 027.2 describes the use of alkoxylated polyvinylamines, the unpublished German patent application P 101 15 256.6 describes the use of polyamine amides, the unpublished German patent application P 100 29 026.4 and P 101 15 255.8 the use of cationic polymers which Have urethane and / or urea groups to increase the surface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

The invention relates to a cleaning agent preparation which contains

A) at least one surfactant,

B) at least one builder and C) at least one nitrogen-containing polymer with repeating units of the general formula I, II or III,

(i) (II)

wherein

R ^{1 represents} C ₂ -Cg alkanediyl,

R ^{2 stands} for a chemical bond or C ₁ -C ₂ -alkanediyl, which is optionally interrupted by a double bond and / or an imino group and / or is wholly or partly part of one or more saturated or unsaturated carbocyclic 5- to 8th is a membered ring, where the alkanediyl can carry one or more hydroxyl groups and / or amino groups,

R ³ for C ₂ -C ₈ alkanediyl or for

- CH ₂ - CHR ⁴ - (- 0 - CH ₂ - CHR ⁴

stands,

represents 0, NH or Ci-Cg-alkylimino,

Z ¹ for hydrogen or for

- (- CH ₂ CHR ⁴ 0 -) - H q

stands, at least some of the Z ¹ radicals being different from hydrogen,

Z ² for hydrogen, R ⁵ C0, R ⁶ - or CH-; CHR ⁴ H

where at least some of the Z ² radicals are different from hydrogen,

Z ^{3 represents} Ci-Cβ-alkyl, phenyl or phenyl -CC-C -alkyl or, if k = 0, together with NR ³ -X can form a 5- to 7-membered saturated heterocyclic ring with 2 nitrogen atoms or if k = 1, the two Z ³ radicals together with N-CH -CH ₂ -N can form a 5- to 7-membered saturated heterocyclic ring with 2 nitrogen atoms,

R ^{4 represents} hydrogen or -CC-alkyl,

R ^{5 represents} C4-C ₂ -alkyl or C ₄ -C ₂ -alkenyl, where the alkyl or alkenyl groups can carry one or more substituents which are selected from hydroxy, alkoxy, alkoxycarbonyl or NEχE ₂ , in which E and E ₂ can be the same or different and represent hydrogen, alkyl or acyl;

R6 represents C ₄ -C alkyl or C ₄ -C ₂ alkenyl, where the alkyl or alkenyl groups can carry one or more substituents which are selected from hydroxy, alkoxy, alkoxycarbonyl or NEχE, wherein Ei and E are identical or different can be and represent hydrogen, alkyl or acyl;

p stands for a number from 1 to 20, q stands for a number from 1 to 20, k stands for 0 or 1;

or its reaction products with neutralizing agents or quaternizing agents.

The detergent composition according to the invention generally contains

(A) 0.5 to 40% by weight, preferably 5 to 30, in particular 10 to 25% by weight of surfactant,

(B) 1 to 60% by weight, preferably 1 to 40% by weight, in particular 2 to 15% by weight, builder,

(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 with repeating units of the formula I are derived from alkoxylated polyvinylamines.

Polyvinylamines are understood to mean polymers partially or completely composed of repeat units which are formally derived from N-vinylamine. These polymers are obtainable by polymerizing open-chain N-vinylcarboxamides alone or together with other monoethylenically unsaturated comonomers (co) and then using the polymerized open-chain N-vinylcarboxamide units to formol or alkylcarbonyl groups by the action of Cleaves acids, bases or enzymes to form 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, as a 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 _ö carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl acetic acid as well as 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 amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethyl aminomethyl methacrylate, dimethylaminopropylacrylate, dimethylamino propyl methacrylate, diethylaminopropyl acrylate, methylacrylamyl acrylate, methylacryl amyl acrylate, methylacryl amyl acrylate, methylacryl amyl acrylate, , N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylamides, such as. B. dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylair d, diethylaminopropylacrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.

Other suitable comonomers are: N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and 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. B. vinyl imidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethyl imidazoline. In addition to the free bases, N-vinylimidazoles and N-vinylimidazolines are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.

Monomers containing sulfo groups, such as, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylic acid are also suitable as comonomers.

The polyvinylamine is preferably derived from homopolymers of N-vinylformamide or from copolymers which, in addition to N-vinylformamide, also contain copolymerized 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 synonymous with the content of vinylamine units in the polyvinylamines, based on the vinylamide units used.

The alkoxylated polyvinylamines are preferably derived from polyvinylamines with a K value in the range from 10 to 200, preferably 20 to 100. The K values are determined according to H. Fiken Scher in 5% aqueous saline solution at pH 7, a temperature of 25 ° C and a polymer concentration of 0.5% by weight, cf. Cellulose-Chemie, Volume 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 8 -alkyl.

Examples of preferred epoxides of the formula IV are the epoxides of ethylene, propene and 1-butene. 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 according to the molar Ren amount of epoxy, based on the available amine nitrogen atoms in the polyvinylamine. In preferred embodiments, q is in the range from 1 to 15, in particular 1 to 10, particularly preferably 1 to 6.

To obtain alkoxylated polyvinylamines in which the mean q is 1, the polyvinylamines are generally reacted with an epoxide in the absence of a catalyst. For this purpose, an aqueous solution of the polyvinylamine is expediently used. To obtain alkoxylated polyvinylamines in which q is greater than 1, the polyvinylamine is reacted with the epoxide in an anhydrous solvent. The reaction is then preferably 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 ethanolate, as well as sodium hydride and calcium hydride. Preferred bases are the alkali metal hydroxides and especially sodium hydroxide.

Suitable solvents are -CC 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 their mixtures. Aliphatic or aromatic hydrocarbons, such as hexane, cyclohexane, toluene, xylenes, and similar solvents can also be used.

The reaction temperature is generally more than 70 ° C. and is preferably 70 to 150 ° C., in particular 75 to 110 ° C. The reaction can take place in the usual reactors. The application of increased pressure is generally not necessary. However, it can be of advantage when converting volatile components. The reaction pressure can then be up to 50 bar, preferably up to 10 bar. The epoxy can be added in one portion or over a period of time, which can be from a few minutes to several hours.

To work up the alkoxylated polyvinylamine obtained in the reaction with the epoxy, the organic solvent is generally removed and replaced with water. This gives aqueous solutions of the desired alkoxylated polyvinylamines which can be used directly in the cleaning agent preparation according to the invention. Of course, it is also possible to isolate the alkoxylated polyvinylamines as a solid by removing the volatile constituents of the reaction. Depending on their degree of alkoxylation, the alkoxylated polyvinylamines according to the invention have molar masses M _w (determined by the light scattering method) 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 from 30 to 200. According to H. Fikentscher, the K values were in 5% by weight aqueous saline solution at pH 7 and a temperature of 25 ° C. and a polymer concentration of 0.5% .-% determined (see above).

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

Polyaminoamides are polymers whose skeleton chain contains both amine and amide functionalities. They can be obtained by reacting polyalkylene polyamines with dicarboxylic acids, preferably in a molar ratio of 1: 0.5 to 1: 2.

Polyalkylene polyamines are taken to mean compounds which consist of a saturated hydrocarbon chain with terminal amino functions which is interrupted by at least one secondary amino group. Suitable polyalkylene polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, diaminopropylethylene diamine (= N, N'-bis (3-aminopropyl) -1, 2-diaminoethane), ethylene propylene triamine, 3- (2-aminoethyl) aminopropylamine, diprop as well as polyethyleneimines with molecular weights of preferably 300 to 20,000, in particular 300 to 5000. Poly-C ₂ -C ₃ -alkylene amines having 3 to 10 nitrogen atoms are preferred. Of these, diethylenetriamine, 3- (2-aminoethyl) aminopropylamine, dipropylenetriamine and diaminopropylethylenediamine are particularly preferred. Of course, the polyalkylene polyamines 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. Dibasic amino acids such as iminodiacetic acid, aspartic acid and glutamic acid are also suitable. Preferred acids are adipic acid, glutaric acid, aspartic acid and iminodiacetic acid. The dicarboxylic acids can of course be used in a mixture with one another.

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, in particular chlorides. examples for δ 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 tartar and dimethyl iminodiacetate; Amides such as adipic acid diamide, adipic acid monoamide and glutaric acid diamide. The free carboxylic acids or the carboxylic anhydrides are preferably used.

The polycondensation of the polyamine and the dicarboxylic acid is carried out in a conventional manner by heating the polyamine and the dicarboxylic acid, e.g. B. to temperatures of 100 to 250 ° C, preferably 120 to 200 ° C, and distilling off the water of reaction formed during the condensation. When using the carboxylic acid derivatives mentioned, the condensation can also be carried out at temperatures lower than the stated temperatures. The polyaminoamides can be prepared without the addition of a catalyst or using an acidic or basic catalyst. Suitable acidic catalysts are, for example, acids such as Lewis acids, e.g. B. 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, alcoholates, 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 such as sodium borohydride. If used, the catalyst 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 suitable. In general, the solvent is distilled off during the reaction or after the reaction has ended. This distillation can optionally be carried out under a protective gas such as nitrogen or argon.

Polyaminoamides with side chains of the formula Z ² , wherein Z ² for - (- CH ₂ CHR ⁴ 0 -) - H q

is available by reacting the polyaminoamides with epoxides of the formula IV. Here, alkoxylated side chains form 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 amine nitrogen atoms available in the polyamino amide.

Suitable epoxides are, for example, the epoxides of ethene, propene, 1-butene, 1-pentene. With regard to alkoxylation, reference is made to what has been said above regarding the alkoxylation of polyvinylamines. In preferred embodiments, q is in the range from 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 polyamino amide are alkoxylated.

Polyaminoamides in which Z ^{2 stands} for R ⁵ CO can be obtained by reacting polyaminoamides with a compound of the formula R ⁵ -CO-X, in which R ^{5 has} the meaning already given. X stands for a nucleophilically displaceable leaving group, such as in particular hydroxyl, alkoxy, acyloxy or halogen, in particular chlorine. The compound of the formula R ⁵ -C0-X is therefore a carboxylic acid of the formula R ⁵ -C00H 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 reference to the preparation of the polyaminoamides on which they are based. The reaction can be carried out in a suitable solvent or preferably solvent-free. Suitable solvents and reaction conditions are those mentioned above in relation to the preparation of the polyaminoamides on which they are based.

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

Instead of reacting the preformed polyaminoamide with the carboxylic acid R ⁵ C00H or a derivative thereof, these can alternatively be added during the production of the polyamino amide. Polyaminoamides with side chains of the formula that can be used according to the invention Z ² , in which Z ^{2 stands} for R ⁵ CO, can accordingly be obtained by polycondensation of a polyamine with a dicarboxylic acid and a monocarboxylic acid of the formula R ⁵ C00H. The dicarboxylic acid or the monocarboxylic acid of the formula R ⁵ C00H can be used as such or in the form of a derivative, such as an anhydride, ester or halide. The polyalkylene polyamine, the dicarboxylic acid and the monocarboxylic acid are preferably reacted in a molar ratio of 1: (0.5-1.5): (0.05-3).

Further alternatively, before the polyaminoamide is prepared, the polyamine can be partially amidated with a monocarboxylic acid of the formula R ⁵ C00H or a derivative thereof and then with a dicarboxylic acid or a derivative thereof to give a polyaminoamide with side chains of the formula Z ² which can be used according to the invention, in which Z ^{2 is} R ⁵ C0 stands, implement.

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

Suitable polyaminoamides are also obtained if polaminoamides in which the amine nitrogen atoms in some cases carry side chains with Z ² equal to R ⁵ CO and / or R ⁶ are reacted with ethylene oxide, propylene oxide, butylene oxide or longer-chain alkyl epoxides as described ,

If the modified polyaminoamide contains protonatable or quaternizable nitrogen atoms, these can be reacted with protonating or quaternizing agents, as described below.

Polymers containing nitrogen with repeating units of the formula III are urethane and / or urea groups and polymers containing tertiary Aird.no groups.

They can be obtained by reacting (i) at least one difunctional isocyanate and (ii) at least one compound with groups reactive toward isocyanate groups and additionally at least one tertiary amino group.

Component (i) is preferably selected from diisocyanates, isocyanate prepolymers with 2 isocyanate groups and mixtures thereof. Compounds which have functional groups instead of free isocyanate groups are also suitable Release isocyanate groups or react like isocyanate groups. These include e.g. B. capped isocyanate groups, uretdione groups, isocyanurate groups and / or compounds containing biuret groups.

Diisocyanates suitable as component (i) can be aliphatic, cycloaliphatic or aromatic. Aliphatic diisocyanates preferably have a hydrocarbon radical with 4 to 12 carbon atoms. Suitable diisocyanates are e.g. B. 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 (2,2-bis) 4-isocyanatocyclohexyl) propane, 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI). and their isomer mixtures (e.g. 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. B. the trans / trans, the cis / cis and the cis / trans isomer and mixtures thereof.

The groups of the compounds of component (ii) which are reactive toward isocyanate groups are selected from hydroxyl groups, primary and secondary amino groups. Depending on these groups, polymers result which have urethane groups and / or urea groups. Suitable compounds (ii) are e.g. B. tertiary A ine, in which the amine nitrogen has two hydroxyalkyl and / or aminoalkyl groups and a further group which is selected from Ci-Cg-alkyl, phenyl and phenyl -CC ₄ -alkyl.

Component (ii) preferably comprises at least one compound of the general formulas

Z ³ Z ³ HO R ³ NR ³ OH, H ₂ NR ³ NR ³ NH ₂

HO R ³ N NH _r H ₂ R ³ N NH

H0- _R 3. • N N- _R 3 OH H ₂ NR ³ - N N- R ³ NH ₂ wherein

R ³ independently of one another represent C ₂ -C ₈ alkanediyl and Z ^{3 represents} 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 groups which are reactive toward isocyanate groups, preferably two hydroxyl groups. These are e.g. B. by alkoxylation of primary amines, such as. B. methylamine by customary methods known to those skilled in the art. The number average molecular weight of the polyethers is preferably in a range from 500 to 6000 g / mol.

The nitrogen-containing polymers having repeating units of the formula III can contain, in addition to components (i) and (ii), further components, as are customary for the production of polyurethanes or polyureas. These include e.g. B. from component (ii) different compounds with at least two groups reactive toward isocyanate groups, as are usually used as chain extenders. Preferably no chain extenders are used.

The nitrogen-containing polymers with repeating units of the formula III can additionally contain at least one further compound having a group which is reactive toward isocyanate groups (stoppers). This group is preferably a hydroxyl or a primary or secondary amino group. Suitable compounds with a group reactive toward isocyanate groups are e.g. B. monofunctional alcohols, such as methanol, ethanol, n-propanol, isopropanol, etc. Also suitable are amines with a primary or secondary amino group, such as. B. methylamine, ethylamine, n-propylamine, isopropylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine etc. Also suitable are stoppers which have a group reactive toward isocyanate groups and at least one tertiary amino and / or ammonium group exhibit. Examples of this are e.g. B. N, N-Dialky- lao alcohols or amines.

Preferred are polymers which have a number average molecular weight in the range from about 1000 to 50,000, preferably 2,000 to 20,000. The content of urethane and / or urea groups is preferably in a range from 2 to 8 mol / kg, particularly preferably 3 to 8 mol / kg, in particular 4 to 8 mol / kg.

Quaternary groups can be derived from the tertiary amine nitrogen of the compounds of component (ii) or of the polymers which contain component (ii), e.g. B. either by protonation, e.g. B. 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. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Depending on the application, the neutralization and / or quaternization can be partial, e.g. B. 10 to 90%, or completely, ie 100%. The neutralization can take place before, during or after the polyaddition.

The polymers with repeating units of the general formula III are prepared by reacting at least one diisocyanate (i) with at least one compound of component (ii) and, if appropriate, additional compounds with groups reactive toward isocyanate groups. The ratio of the NCO equivalent of component (i) to the equivalent of the active hydrogen atom of component (ii) and any 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 a solvent or in a suitable inert solvent or solvent mixture. Solvents which are infinitely miscible with water are preferred. Also preferred are solvents which have a boiling point at normal pressure in the range from about 40 to 100.degree. Aprotic polar solvents, e.g. B. tetrahydrofuran, ethyl acetate, N-methylpyrrolidone, dimethylformamide, dimethyl acetamide and preferably ketones, such as acetone and methyl ethyl ketone. If desired, the reaction can be carried out under an inert gas atmosphere, such as. B. under nitrogen. Furthermore, the reaction is preferably carried out at ambient pressure or under elevated pressure, in particular the internal pressure of the reactants under the reaction conditions. The reaction temperature is preferably in a range from about 5 to 180 ° C., in particular 20 to 150 ° C. If predominantly compounds are used as component (ii) and, if appropriate, as additional components, which have primary arrondro groups as groups reactive toward isocyanate groups, the reaction can, if desired, take place in a solvent or solvent mixture which can have active hydrogen atoms. In addition to the ones mentioned above then alcohols such as methanol and ethanol, mixtures of alcohols and water, mixtures of ketones and water and mixtures of alcohols and the aforementioned ketones are preferably used.

5 Suitable polymerizers are known to the person skilled in the art. These include e.g. B. stirred kettle, which are optionally equipped with devices for removing the heat of reaction. If an organic solvent is used in the preparation of the polymers, this can subsequently be made by customary, the person skilled in the art

10 known methods, e.g. B. by distillation at reduced

Pressure to be removed. Before the solvent is separated off, water can additionally be added to the polymer. If desired, high-boiling solvents can also remain in the solution, but their proportion is preferably not more than

15 10 wt .-%, based on the weight of the polymer.

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

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols with 8 to 22, preferably 8 to 18 carbon atoms, e.g. B. C ₉ -Cn alcohol sulfates, C ₂ -C ₃ alcohol sulfates, C 1 -C ₈ alcohol sulfates such as lauryl sulfate, cetyl sulfate, myristyle sulfate, palmitylsulfate, stearyl sulfate or tallow fatty alcohol sulfate.

0 Other 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 Cs-C ₂₂ , preferably a Cio-Cis 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 using propylene oxide alone and, if appropriate, butylene oxide. Also suitable are those alkoxylated Cs-C ₂₂ alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. The alkoxylated Cs-C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in a static distribution. 5 Other suitable anionic surfactants are alkanesulfonates such as C ₈ -C ₂₄ -, preferably C ₁₀ -C ₈ -alkanesulfonates and soaps such as the Na and K salts of C ₈ -C ₂₄ carboxylic acids.

Further suitable anionic surfactants are C ₈ -C o-linear alkylbenzenesulfonates (LAS), preferably linear C ₉ -Cχ ₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Also suitable as anionic surfactants are C ₈ -C ₂₄ -olefin sulfonates and disulfonates, which can also be mixtures of alkene and hydroxyalkanesulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkylglycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates with approx. 20 to 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkyl succinic acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides or their amides and diesters of sulfosuccinic acids, acyl sarcosinates, sulfated alkyl polyglycosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

Suitable anionic surfactants are also alkyl phosphates.

The anionic surfactants are preferably added to the cleaning agent 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.

Individual anionic surfactants or a combination of different anionic surfactants can be used. Anionic surfactants from only one class can be used, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but one can also use surfactant mixtures from different classes, e.g. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.

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

Examples of suitable nonionic surfactants are alkoxylated C ₈ -C ₂₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here, too, block polymers of ethylene oxide, propylene xide and / or butylene oxide or adducts which contain the alkylene oxides mentioned in a static distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. Ethylene oxide is preferably used as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of suitable nonionic surfactants are alkyl phenol ethoxylates with C ₆ -C ₄ alkyl chains and 5 to 30 moles of ethylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 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-alkyl glucamides.

Examples of suitable nonionic surfactants are alkylamine alkoxylates or alkylamide ethoxylates.

The cleaning agents according to the invention preferably contain 3 to 12 moles of ethylene oxide ethoxylated C 1 -C ₆ -alcohols, particularly preferably ethoxylated fatty alcohols as nonionic surfactants. In addition, alkyl polyglycosides, alkyl aminoxiloxates or alkyl amide ethoxylates are preferred.

Individual nonionic surfactants or a combination of different nonionic surfactants can be used, in particular only alkoxylated Cs-C ₂₂ alcohols, but surfactant mixtures from different classes can also be used.

Typical examples of amphoteric surfactants are alkyl betaines, alkylamide betaines, 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 Cs to Ci ₆ -dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with long-chain alkyl radical.

The detergent preparations contain at least one builder as component B). The builders include inorganic builders and organic (co) builders. All customary inorganic builders such as aluminosilicates, silicates, carbonates, phosphates and phosphonates are suitable as inorganic builder substances.

Suitable inorganic builders are e.g. Alumosilicates with ion exchange properties such as Zeolites. Different 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 replaced by 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. Alumosilicate builders are preferred.

Other suitable inorganic builders are e.g. amorphous or crystalline silicates such as e.g. amorphous disilicates, crystalline silicates 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. Na, Li and Mg silicates are preferably used.

Amorphous silicates such as sodium metasilicate, which has a polymeric structure, or amorphous disilicate (Britsil® H 20 manufacturer: Akzo) can also be used.

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. Na, Li and Mg carbonates or hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbonate, are preferably used.

Suitable inorganic builders are also alkali metal, 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.

Examples of suitable low molecular weight polycarboxylates as organic cobuilders are: C ₄ -C o-di-, tri- and tetracarboxylic acids such as succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentantetracarboxylic acid and alkyl and alkylene succinic acids with C ₂ -Ci ₆ alkyl or alkylene radicals;

C ₄ -C ₂ o-hydroxycarboxylic acids such as 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, methylglycine diacetic acid, alaninediacetic acid, ethylenediaminetetraacetic acid and serinediacetic acid; Aminopolycarboxylates are commercially available, for example, under the name Trilon®.

Salts of phosphonic acids such as e.g. Hydroxyethane diphosphonic acid, ethylenedia intetra (methylene phosphonate) and diethylene triamine penta (methylene phosphonate).

Examples of suitable oligomeric or polymeric polycarboxylates as organic cobuilders are:

Oligomaleic acids as described, for example, in EP-A 0 451 508 and EP-A 0 396 303;

Copolymers and terpolymers of unsaturated C ₄ -C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers

from group () in quantities of up to 95% by weight from group (ß) in quantities of up to 60% by weight from group (γ) in quantities of up to 20% by weight

polymerized may be included.

Examples of suitable unsaturated C ₄ -C ₈ dicarboxylic acids here are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

The group (α) includes monoethylenically unsaturated C ₃ -Cs-monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From the group (α) acrylic acid and methacrylic acid are preferably used.

The group (ß) includes monoethylenically unsaturated C ₂ -C ₂₂ -01e- fine, vinyl alkyl ethers with C ₈ -C ₈ alkyl groups, styrene, vinyl esters of C ₈ -C ₈ carboxylic acids, (meth) acrylic id and vinyl pyrrolidone. loading from the group (ß) C ₂ -C ₆ -01efins, vinyl alkyl ethers with C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate are preferably used,

The group (γ) includes (meth) acrylic esters of Ci-Cs alcohols, (meth) acrylonitrile, (meth) acrylamides, (meth) acrylamides of Ci-Cs amines, N-vinylformamide and vinylimidazole.

If the polymers of group (β) contain vinyl esters in copolymerized form, these can 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.

Suitable copolymers of dicarboxylic acids as organic co-builders 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 ₃ -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), the weight ratio of acrylic acid to Vinyl esters can vary in the range from 20:80 to 80:20, and particularly preferred.

Terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in a weight ratio

20 (maleic acid): 80 (acrylic acid + vinyl ester) to 90 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to vinyl ester varying in the range from 30:70 to 70:30;

Copolymers of maleic acid with C ₂ -Cg-01efins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being 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 co-builders. Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid and mixtures of acrylic acid and maleic acid, which are grafted on in amounts of 40 to 95% by weight, based on the component to be grafted.

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

Degraded polysaccharides such as acidic or enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and glucamine and polyalkylene glycols with molecular weights up to M _w = 5000 such as polyethylene glycols are suitable as a graft base. Ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers, statistical ethylene oxide / propylene oxide or ethylene oxide / butylene oxide copolymers, alkoxylated mono- or polyvalent C ₁ -C ₂ -alcohols, cf. US 4,746,456.

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

Polyglyoxylic acids as organic cobuilders are described, for example, in EP-B 0 001 004, US 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the polyglyoxylic acids can 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 co-condensates 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 also preferably used as organic cobuilders. Particularly preferred are produced in phosphorus-containing acids, with C ₆ -C ₂ mono- or -dicarbon- acids or polyaspartic acids modified with C ₆ -C ₂₂ mono- or diamines.

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. Condensates containing such carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.

The detergent formulations can be in powder, granule, paste, gel or liquid form.

In a preferred embodiment, the detergent composition according to the invention contains customary ingredients, which are selected from soil release polymers, enzymes, foam boosters, foam dampers or foam inhibitors, biocides, bleaching systems, tarnishing and / or corrosion inhibitors, suspending agents, dyes, fillers, inorganic fillers , Disinfectants, pH regulating substances, hydrotropic compounds, antioxidants, enzyme stabilizers, perfumes, solvents, solubilizers, dispersants, processing aids, solubilizers, plasticizers and antistatic agents.

Suitable soil release polymers for detergent compositions include:

Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;

Polyester made of polyethylene oxides end capped on one side with di- 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.

Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US Pat. No. 4,746,456, US Pat. No. 4,846,995, DE-A 37 11 299, US Pat. No. 4,904,408, US Pat. No. 4,846,994 and US Pat. No. 4,849,126) or modified celluloses such as Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Suitable enzymes are proteases, lipases, amylases and cellules. The enzyme system may be limited to a single one of the enzymes or may include a combination of different enzymes. Suitable foam dampers or foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures 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 divided into oxygen bleaching agents and chlorine-containing bleaching agents. Alkali metal perborates and their hydrates and alkali metal percarbonates are used as oxygen bleaches. Preferred bleaching agents are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Persulphates and hydrogen peroxide can also be used as oxygen bleaching agents. Typical oxygen bleaching agents 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-decanedoxoxy diacid.

The following oxygen bleaching agents can also be used in the detergent composition: cationic peroxyacids, which are described in the patent applications US Pat. No. 5,422,028, US Pat. No. 5,294,362 and US Pat. No. 5,292,447; Sulfonyl peroxy acids, which are described in the patent application US 5,039,447.

Oxygen bleaches are used in amounts of 0.5 to 30% by weight, preferably 1 to 20% by weight, particularly preferably 3 to 15% by weight, based on the total detergent composition.

Chlorine-containing bleaches and the combination of chlorine-containing bleaches with peroxide-containing bleaches can also be used. Known chlorine-containing bleaches are, for example, 1,3-dichloro-5, 5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoyl urea, p-toluenesulfone dichloroamide or trichloroethylamine. Preferred chlorine-containing bleaches 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% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.3 to 8% by weight, based on the total detergent composition.

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

Bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid. Compounds are suitable which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylene diamine (TAED), tetraacetylmethylene diamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylene diamine (TAHD), N-acylimides, such as N-nonanoylsuccinimide (NOSI), acylated phenolsulfonyl, for example or isononanoyloxybenzenesulfonates (n- or iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-l, 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 from the group consisting of multiply acylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, particularly preferably n- or iso-NOBS, MMA and TMAQ are suitable. The following substances can also 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 as well as acetylated sorbitol and mannitol or their mixtures described in EP-A 525 239; acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated, glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam 94 from WO / 27 970, WO 94/28

102, WO 94/28 103, WO 95/00 626, WO 95/14 759 and WO 95/17 498 are known; the hydrophilic sub-listed in DE-A 196 16 769 Substituted acylacetals and the acyl lactams described in DE-A 196 16 770 and WO 95/14 075 can be used just like the combinations of conventional bleach activators known from DE-A 44 43 177. 5

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

10 In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from EP-A 446 982 and EP-A 453 003 can also be used as bleaching catalysts in the detergent compositions.

15 settlements are included.

The transition metal compounds in question include, for example, the manganese, iron, cobalt, ruthenium or molydane selenium complexes known from DE-A 195 29 905 and those from DE-A

20 196 20 267 known N-analogue compounds, the manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from DE-A 195 36 082, the manganese, iron described in DE-A 196 05 688 , Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which from DE-A

25 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes, 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 compounds known from EP-A 392 592

30 plexes and / or the manganese described 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 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.

35

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 (ace-

40 tat) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.

Bleaching catalysts are used in amounts of 0.0001 to 5% by weight, preferably 0.0025 to 1% by weight, particularly preferably 0.01 to 45 0.25% by weight, based on the total detergent composition. Suitable corrosion inhibitors that can be used are, for example, silver protection agents 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, hexyl glycols, 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, phosphoric acid alkyl / aryl esters, hexyl glycols.

Examples of suitable cleaning agent compositions according to the invention are machine cleaners, metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high-pressure cleaners, alkaline cleaners, acid cleaners, spray degreasers, dairy cleaners, rinse aids, dishwashing detergents, etc.

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

Powder or granular detergent compositions according to the invention can contain up to 60% by weight of inorganic fillers. Sodium sulfate is usually used for this. However, the cleaning agent compositions according to the invention are preferably low in adjusting agents and contain only up to 20% by weight, particularly preferably up to 8% by weight of adjusting agents, in particular in the case of compact or ultra-compact cleaning agent compositions. The solid cleaning agent compositions according to the invention can have different bulk densities in the range from 300 to 1300 g / 1, in particular from 550 to 1200 g / 1. Modern compact cleaning agents usually have high bulk densities and show a granular structure. To the desired compression The detergent compositions can be used using the methods customary in the art.

Tablet-like detergent compositions according to the invention furthermore generally contain tabletting aids such as polyethylene glycols with molar masses greater than 1000 g / mol, polymer dispersions and tablet disintegrants such as cellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinked polyacrylates or combinations of acids such as citric acid and sodium bicarbonate.

The detergent composition according to the invention is produced by customary methods and, if appropriate, is made up.

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

a) at least one surfactant and

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

NH-CR ² -C-

(I) (II)

or its reaction products with neutralizing agents or quaternizing agents, in which the variables R ¹ , R ² , R ³ , Z ¹ , Z ² , Z ³ , k and p have the meanings given above, and optionally contain at least one builder,

in contact, the excess removed 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. As a rule, the hard surface is treated with a different thin, preferably aqueous solution of the detergent composition in a manner typical of the type of surface, e.g. B. by rinsing, spraying, wiping or similar methods, as is usually used for cleaning objects with hard surfaces. The rinsing can be done, for example, by machine or by hand. "Contacting" is usually done during the cleaning process. The quantity of nitrogen-containing polymer with repeating units of the formula I, II or III required for hydrophilization is adsorbed by the surface and adheres to the surface as a thin film. The amount necessary to achieve hydrophilization is set automatically and remains stuck after drying. An excess can, for example, be rinsed off with water or wiped off with a structure made of an absorbent material, for example a cloth.

The cleaning agent compositions according to the invention are found, for example, in the cleaning of work surfaces, tiles, bathroom furnishings, kitchen furniture such as tables, chairs, cupboards, kitchen appliances such as a refrigerator, stove or extractor hood, and furniture

Plastics, dishes, glasses, windows or blinds application.

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

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

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

I. Manufacturing 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 solution = 182.1 mmol / 100 g; amino groups in the batch n = 0.904 mol) and 1300 g of xylene were placed in a 5 liter metal reactor and then rendered inert three times with 5 bar of nitrogen. The The reactor contents were heated to 90 ° C. and 130.2 g of butylene oxide were then metered in over a period of 120 minutes until a pressure of 5 bar was reached. The mixture was then stirred until the pressure was constant. After the reactor had been cooled and let down, a butoxylated polyvinylamine mixture with an average degree of butoxylation q of 2 was obtained.

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

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

Example 3: Polyaminoamide modified with hexanoic acid

103.3 g of diethylenetriamine were placed in a 1 l stirring apparatus and heated to 120 ° C. under nitrogen. When this temperature was reached, 116.2 g of hexanoic acid were added dropwise and the mixture was then heated to 170.degree. The water of reaction formed distilled off. After reaching an acid number of about 10 mol KOH / g, the mixture was allowed to cool to 140 ° C. and 146.2 g of adipic acid were added. After heating again to 170 ° C., water of reaction was distilled off until an acid number of 21.2 mg KOH / g and an amine number of 0.61 mmol N / g were reached. After cooling, a 40% solution of the polyaminoamide modified with hexanoic acid was prepared by adding demineralized water.

Example 4: Polyurea from isophorone diisocyanate and bis (aminopropy1) iperazine

20.0 g (0.1 mol) of bis (aminopropyl) piperazine were dissolved in 200 g of acetone in a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. 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 at reflux for a further hour and then 110 g of HCl (1N) and 100 g of water were added. The acetone was then distilled off under reduced pressure. You got a poly urea solution 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 (aminopropy1) methylamine

Analogously to the preparation instructions for 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 with 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 made from isophorone diisocyanate and methyl diethanolamine

In a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 11.92 g (0.1 mol) of methyldiethanolamine were dissolved in 200 g of acetone. 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 at reflux for a further 8 hours. 100 g of HCl (1N) were then added and the acetone was distilled off under reduced pressure. A polyurethane solution with 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 (aminopropy1) methylamine

In a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 174 g (1.2 mol) of bis (aminopropy1) methylamine were dissolved in 1200 g of acetone and neutralized with 1140 g of HCl (1 n). 266.4 g (1.2 mol) of isophorone diisocyanate were added dropwise to this reaction mixture within 20 minutes. The reaction mixture was stirred at reflux for a further hour and then the acetone was distilled off under reduced pressure. A polyurea solution with 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 (aminopropy1) 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 with 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 (aminopropy1) methylamine

In a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 29.0 g (0.2 mol) of bis (aminopropyl) ethylamine were mixed in a mixture of 180 g of water, 200 g of acetone and 20 g of 90% lactic acid solved. 44.4 g (0.2 mol) of isophorone diisocyanate were added dropwise over a period of 20 minutes. The reaction mixture was stirred at reflux for a further hour and then the acetone was distilled off under reduced pressure. A polyurea solution with 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. Examples of use

The following compositions were made:

Detergent composition 1 (comparison)

11% by weight of C ₂ -C ₈ fatty alcohol ethoxylate (Lutensol A7N)

3% by weight of C ₂ -C ₈ fatty alcohol ethoxylate (Lutensol A4N) 6% by weight of 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 of propoxylated polyaminoamide from Example 2 to 100% by weight of water Detergent composition 3

11% by weight Lutensol A7N

3% by weight of Lutensol A4N 6% by weight of Lutensit A-LBN 50

3 wt .-% modified with hexanoic acid polyaminoamide

Example 3 ad 100 wt .-% water

Detergent composition 4

11% by weight Lutensol A7N

3% by weight Lutensol A4N

6 wt .-% Lutensit A-LBN 50 3 wt .-% polyurea from isophorone diisocyanate and

Bis (aminopropyl) methylamine from Example 5 ad 100 wt .-% water

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

The detachability of colored mineral oil from test specimens made of polyethylene (size: 1.5 x 8 cm) was investigated.

PE test specimens were pretreated as indicated in the tables below. Then the pretreated test specimens were each coated with 0.1 g mineral oil. In order to determine the 01 detachability, the test specimens were immersed in one of the above diluted detergent compositions. The test specimens were weighted down with a lattice frame to prevent them from appearing. The dive time was 8 minutes each. After removal, the test specimens were dried at 50 ° C. for at least 3 hours. The weight of the test specimens was determined and the remaining percentage of mineral oil was calculated in%. The results are shown in the tables below. The measurements were carried out as double determinations. The mean of two measurements was given in each case. Table 1: Cleaning with detergent composition 1 (comparison)

Table 2: Cleaning with detergent composition 2

Table 3: Cleaning with detergent composition 3

Table 4: Cleaning with detergent composition 4

The results prove that the use of detergent compositions 2, 3 or 4 leads to a significantly lower tendency for soiling of the test specimens. The results also show that the agent used for pretreatment has a major influence on the soiling behavior of the test specimens and can even make subsequent cleaning more difficult.

Claims

claims

1. A detergent composition comprising

A) at least one surfactant,

B) at least one builder and

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

(I) (II)

X_R3_ _N _ ₍ CH ₂ -CH ₂ -N) -R ³ -XC -NH-R -NH-C (III) II kz ³ z ³

wherein

R ^{1 represents} C ₂ -C ₈ alkanediyl,

R ^{2 stands} for a chemical bond or -CC ₂ o-alkanediyl, which is optionally interrupted by a double bond and / or an imino group and / or optionally wholly or partly part of one or more saturated or unsaturated carbocyclic 5- to 8-membered Rings, where the alkanediyl can carry one or more hydroxyl groups and / or amino groups,

R ³ for C ₂ -C ₈ alkanediyl or for

- CH ₂ - CHR ⁴ - (- 0 - CH ₂ - CHR ⁴

stands, X represents 0, NH or Ci-C _δ- alkylimino,

Z ¹ for hydrogen or for - (- CH ₂ CHR ⁴ 0 -) - H q

where at least some of the Z ¹ radicals are different from hydrogen,

Z ² for hydrogen, R ⁵ C0, R ⁶ - or

- (- CH ₂ CHR ⁴ 0 -) - H q

where at least some of the Z ² radicals are different from hydrogen,

Z ^{3 represents} Ci-C _δ- alkyl, phenyl or phenyl -CC-C ₄ -alkyl or, if k = 0, together with NR ³ -X can form a 5- to 7-membered saturated heterocyclic ring with 2 nitrogen atoms or if k = 1, the two Z ³ radicals together with N-CH ₂ -CH-N can form a 5- to 7-membered saturated heterocyclic ring with 2 nitrogen atoms,

R ^{4 represents} hydrogen or -CC-alkyl,

R ^{5 represents} CC ₂₇ -alkyl or C ₄ -C ₂₇ -alkenyl, where the alkyl or alkenyl groups can carry one or more substituents which are selected from hydroxy, alkoxy, alkoxycarbonyl or NEιE ₂ , in which Ei and E ₂ can be the same or different and represent hydrogen, alkyl or acyl;

R ^{6 represents} C ₄ -C ₂₇ alkyl or C ₄ -C ₂ alkenyl, where the alkyl or alkenyl groups can carry one or more substituents which are selected from hydroxy, alkoxy, alkoxycarbonyl or NEχE ₂ , in which Ei and E _{2 may be the} same or different and represent hydrogen, alkyl or acyl;

p stands for a number from 1 to 20, q stands for a number from 1 to 20, k stands for 0 or 1; or its reaction products with neutralizing agents or quaternizing agents.

2. Detergent composition according to claim 1, comprising a nitrogen-containing polymer having repeating units of the formula I or II, where 5 to 100 mol% of the radicals Z ¹ or Z ² are different from hydrogen.

3. Detergent composition according to claim 1 or 2, comprising a nitrogen-containing polymer with repeating units of formula II, wherein R ^{1 is} C ₂ -C ₃ alkylene.

4. Detergent composition according to claim 1 or 2, comprising a nitrogen-containing polymer having repeat units of the formula II, in which R ^{2 is} C ₂ -C ₂ -alkanediyl, which can optionally be interrupted by an imino group or substituted by an amino group.

5. detergent composition according to claim 1, comprising a nitrogen-containing polymer with repeating units of the formula III, wherein R ² for C ₂ -C ₂ alkanediyl,

H ₃ C stands.

6. Cleaning composition according to one of the preceding claims, containing

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

(B) 1 to 60% by weight builder,

(C) 0.01 to 50 wt .-% nitrogenous polymer, based on the total weight of the detergent composition.

Detergent composition according to one of the preceding claims, wherein the builder is selected from polyphosphates, phosphonates, silicates, carbonates, aluminosilicates, polycarboxyl compounds and complexing agents.

Process for cleaning hard surfaces, characterized in that the hard surface is covered with an aqueous solution of a detergent composition

a) at least one surfactant, b) at least one nitrogen-containing polymer with repeating units of the general formula I, II or III,

R ¹ -) - NH-CR ² -C-

(I) (II)

(III)

wherein the variables R ¹ , R ² , R ³ , Z ¹ , Z ² , Z ³ , k and p have the meanings given in claim 1, contact, remove the excess and / or rinse off.