WO2015169793A1 - Detergent - Google Patents

Abstract

The invention concerns a cleaning agent or detergent containing an enzyme and a hybrid polymer, and the use thereof.

Description

"Cleaning supplies"

The invention relates to a detergent or cleaning agent containing enzyme and hybrid polymer, as well as its use ng.

Conventional washing or cleaning agents of the prior art have difficulty removing stains from organic substances such as blood, egg or starch. The complete removal of dirt in the dishwasher is desired by the customer. However, as this is not always guaranteed, many consumers treat the dishes to be cleaned or deal with the stains. However, this is not very user-friendly or reduces customer satisfaction. Removal of the stains from the washing process is preferred by customers.

US 201 1/0028371 A1 and EP 2 230 261 A1 describe hybrid copolymers.

 DE 10 2012 206 571 A1 describes storage-stable washing and cleaning agents.

 WO 201 3/1 82508 A1 describes a dishwashing detergent.

 WO 201 0/063689 A1 describes a dishwasher tablet.

 WO 201 0/063688 A1 describes a cleaning agent.

 EP 2 235 153 B 1 and EP 2 1 15 1 13 B 1 describe cleaning agents.

The object of the present invention is to better remove stains from biological materials, proteins or starch. The object underlying the invention is achieved in a first embodiment by a process for increasing the protease activity in detergents or cleaners, characterized in that protease is used in combination with a hybrid polymer.

The object underlying the invention is achieved in a further embodiment by the use of hybrid polymer to increase the protease performance in detergents or cleaners.

In the process according to the invention or in the use according to the invention, it is additionally possible to use fatty alcohol alkoxylate, fatty alcohol ether sulfate and / or fatty alcohol sulphonate in an amount of from 10 to 30% by weight, more preferably in a range of from 16 to 25% by weight. based on the total weight of the detergent or cleaning agent.

The object underlying the invention is contained in a further embodiment by a washing or cleaning agent i. Enzyme, and

 ii. hybrid polymer

solved.

Enzyme in the sense of the invention can mean a single enzyme or else a mixture of different enzymes.

Hybrid polymer in the sense of the invention is a polymer which contains in the same molecule repeating units derived from hydroxyl-containing biomolecules, in particular derived from the polymer class of polysaccharides, and repeating units derived from ethylenically unsaturated compounds (preferably acrylic polymer component). Preferred polysaccharides are starch and / or dextrins. Thus, in the context of the invention, the hybrid polymer can be, for example, a synthetic polymer, preferably a polyacrylate, having a hydroxyl group-containing biomolecule, for example a starch residue, at the chain end.

The washing or cleaning agent according to the invention can be used for the process according to the invention or the use according to the invention. The following preferred embodiments for the washing or cleaning agent thus also apply to the process according to the invention or the use according to the invention.

It has surprisingly been found that the combination of these ingredients according to the invention shows improved washing performance on greasy and enzymatic soiling.

The weight ratio between enzyme and hybrid polymer is preferably in a range from 1: 1, 3 to 1: 6, most preferably in a range from 1: 3 to 1: 4. Advantageously, enzyme is protease and / or amylase. The enzyme or mixture of enzymes may also be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. In the wash liquor, ie under application conditions, the enzyme is then released and can develop its catalytic action.

A protease contained in a washing or cleaning agent according to the invention preferably has a proteolytic activity, that is, it is capable of hydrolysing peptide bonds of a polypeptide or protein. It is therefore preferably an enzyme which catalyzes the hydrolysis of peptide bonds and thereby is able to cleave peptides or proteins. It is especially a subtilase and most preferably a subtilisin. For amylases, synonymous terms may be used, for example, 1,4-alpha-D-glucan glucanohydrolase or glycogenase. According to the invention be prepared amylases are preferably α-amylases. Crucial for determining whether an enzyme is an α-amylase according to the invention is its ability to hydrolyse α- (1 -4) -glycoside bonds in the amylose of the starch.

Amylases which can be synthesized according to the invention are, for example, the α-amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus, and in particular also their further developments improved for use in detergents or cleaners. The enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl® and from the company Danisco / Genencor under the name Pu rastar®ST. Further development products of this α-amylase are from the company Novozymes under the trade name Du ramyl® and Termamyl®u ltra, from the company Danisco / Genencor under the name Purastar®OxAm and from the company Daiwa Seiko I nc. , Tokyo, Japan, available as Keistase®. The α-amylase from Bacillus amyloliquefaciens is sold by the company Novozymes under the name BAN®, derived variants of the Bacillus stearothermophilus α-amylase under the name BSG® and Novamyl® also from the company Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the α-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable. Further advantageously usable Handelsprodu kte are, for example, the Amylase-LT®, Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred amylases are disclosed in International Publication Nos. WO 00/60060, WO 03/00271 1, WO 03/054177 and WO 07/079938, the disclosure of which is therefore expressly referred to or their relative disclosure is expressly incorporated in the present patent application ng is involved.

Advantageously, enzyme is present in an amount in the range of 0.1 to 10% by weight, more preferably in the range of 0.1 to 10% by weight, most preferably in the range of 0.25 to 5% by weight. , most preferably in a range of 3 to 4, 8 wt.% Contained. Preferably, enzyme stabilizers may be included. These may be selected from the group of amino alcohols, for example mono-, di-, triethanol- and -propanolamine and their mixtures, C 1-4 -monocarboxylic acids and their salts, C 1-4 -dicarboxylic acids and their salts. Hydroxycarbonsäu ren and salts thereof, Borsäu re, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, potassium salts, such as potassium chloride, potassium acetate, potassium lactate, calcium salts, for example Calciu mformiat, calcium nitrate, magnesium salts, sulfur-containing Red uktionsmittel and mixtures thereof.

Advantageously, the hybrid polymer is a copolymer of polysaccharides and synthetic monomers, the synthetic monomers most preferably being acrylate monomers.

Advantageously, the hybrid polymer is contained in an amount in a range of 1 to 30 wt%, more preferably in a range of 5 to 20 wt%, most preferably in a range of 15 to 19.5 wt%.

Preferably, fatty alcohol alkoxylate, fatty alcohol ether sulfate and / or fatty alcohol sulfonate are contained in an amount in a range of 10 to 30 wt.%, Particularly preferably in a range of 16 to 25 wt.%.

Preferably, nonionic surfactant is present, selected from Fettalkylpolyglykosiden, Fettalkylpolyalkoxylaten, in particular ethoxylates and / or - propoxylates, fatty acid polyhyd roxyamiden and / or ethoxylation and / or propoxylation of fatty alkylamines, vicinalen diols, fatty acid alkylesters and / or fatty acid amides and mixtures thereof, in particular in an amount ranging from 2% to 25% by weight.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is usually between 1 and 20 degrees, preferably between 3 and 10 degrees. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, corresponding alkoxylation products are of Alkylamines, vicinal diols and carboxylic acid amides, which correspond to the alcohols mentioned with respect to the alkyl part, bar. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid repolyhydroxyamides are also suitable. For incorporation into the compositions according to the invention, suitable so-called alkyl polyglycosides are compounds of the general formula (G) _n - OR ² in which R ^{2 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, Include arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called degree of oligomerization n. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 1 0, with the glycosides preferably used below a value of 1, 5, in particular between 1, 2 and 1, 4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{2 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can be used to prepare useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ² = dodecyl and R ² = tetradecyl.

Nonionic surfactant is present in compositions according to the invention which contain the active ingredients described or are used together or are used in a method according to the invention, preferably in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight. With amounts in the upper part of this range being more likely to be found in liquid detergents / cleaners and particulate detergents / cleaners preferably containing rather lower amounts of up to 5% by weight.

The agents may instead or additionally comprise further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, which include, for example, the abovementioned alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight. to 18% by weight, in each case based on the total agent. Synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms which are an alkali metal , Ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation, call. Preference is given to the derivatives of fatty alcohols containing in particular 12 to 18 C atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a customary sulfate reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium bases. Sulfur-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the reaction of fatty acid esters with sulfur trioxide and subsequent neutralization of available [alpha] sulfofluoroesters, in particular those of fatty acids containing 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative Su lfonieru ngsprodukte, as well as d the formal saponification of these resulting Su lfofettsäu ren. Preferred anionic surfactants are also the salts of Sulfobernsteinsäurestern, which also lfosuccinate as Alkylsu or dialkylsulfosuccinates, and the monoesters or diesters of succinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols represent. Preferred sulfosuccinates contain C8 to C18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. In this case, su lfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.

Advantageously, citric acid or a salt of citric acid, especially sodium citrate, in an amount in a range of 1 1 to 30 wt.%, Particularly preferably in a range of 17 to 23 wt.% Contain.

The detergent according to the invention preferably also contains phosphoric acid or phosphonate. These may be added as complexing agents. Phosphorsäu re or phosphonate are present in an amount of 3 to 1 0 wt.%, Preferably from 5.5 to 9 wt. Present.

Phosphonates are salts and organic compounds, in particular esters, of phosphonic acid. In the context of the present invention, complex-forming organic P-substituted phosphonates, ie having a phosphorus-carbon bond (phosphorus-organic compounds), are used. Their general structure is RP (O) (OR ² ) ₂ , with R and / or R ² = alkyl, aryl or H, where the alkyl or aryl radicals have further substitutions or may carry further chemical groups. Organic P-substituted phosphonates are formed, for example, by the Michaelis-Arbusov reaction. Many of these phosphonates are soluble in water. Some industrially important phosphonates also carry amino group (s) of the type NR- (CH 2) x-PO (OH) 2 (R = alkyl, aryl or H). Some of these aminophosphonates have structural similarities to complexing agents such as EDTA, NTA or DTPA and have a similar function. This property of Komplexbildu ng can be used according to the invention.

A preferred washing or cleaning agent in the context of this application contains one or more phosphonate (s) from the group

 a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof;

 b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof; c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof;

 d) 1-hydroxy ethane-1, 1-diphosphonic acid (HEDP) and / or salts thereof;

 e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;

 f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof;

 g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particularly preferred are agents which contain as phosphonates 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), with DTPMP being very particularly preferred. Furthermore, the washing or cleaning agents according to the invention may contain two or more different phosphonates.

The weight ratio of on the one hand citric acid or its salt and on the other hand phosphoric acid or phosphonates is preferably in a range from 1: 1 to 7: 1, more preferably in a range from 1, 5: 1 to 4: 1.

Detergents or cleaning compositions according to the invention which contain or are used together with the active substances described or are used in a process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the active ingredients essential to the invention.

To the known polyester-active soil release polymers, which can be used in addition to the erfindu ng essential agents include copolyesters of dicarboxylic acids, such as adipic acid, phthalic acid or terephthalic acid, diols, for example, ethylene glycol or Propylene glycol, and polydiols, for example, polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR-) _a OH, also known as a polymeric diol H- (0- (CHR -) _a ) bOH may be present. Therein, Ph is an o-, m- or p-phenylene radical which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -0- (CHR-) _a O- and also polymeric diol units - (0- (CHR -) _a ) bO-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight, the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyesters is in the range from 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, metilitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Preferred diols HO- (CHR-) _a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 C atoms, in particular 1 to 3 carbon atoms is selected. Among the latter diols, those of the formula HO-CH 2 -CHR ¹¹ -OH, in which R has the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1,4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of from 1,000 g / mol to 6,000 g / mol. Preferably, these polyesters composed as described above may also be terminally capped, alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. Alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 C atoms, in particular 5 to 18 C atoms, can be present in the end groups formed by ester bonds. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidinic acid, oleic acid, linoleic acid, linolaidic acid , Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, the 1 to 5 Su substituents having a total of up to 25 carbon atoms, in particular 1 to 12 C. -Atomen can carry, for example tert-butylbenzoic acid. Hydroxymonocarboxylic acids having 5 to 22 carbon atoms may also be present in the terminal groups, examples of which include hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, hydrogenation products thereof, hydroxystearic acid, and o-, m- and p-hydroxybenzoic acids. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene is Lycol units have molecular weights of 750 g / mol to 5,000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90: 10, used in combination with a erfindung ng essential agent.

Advantageously, the inventive detergent or cleaning agent is solid at room temperature. The washing or cleaning agent according to the invention is particularly preferably a detergent tablet. The ingredients are more preferably distributed to at least three different spacial sections or phases, most preferably only one spatial segment or phase containing enzyme and all of the spatial segments or phases containing hybrid polymer.

The washing or cleaning agent used, for example, in the detergent tablets according to the invention preferably comprises 15 to 89.8% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 84.8% by weight of citrate or citric acid. The washing or cleaning agent according to the invention is preferably a single-phase or multi-phase, phosphate-free detergent or detergent tablet, characterized in that the phase or one of the phases, based on their total weight, contains a) 15 to 89, 8% by weight of sodium carbonate. 10 to 84, 8 wt.% Citrate c) contains 0.05 to 20 wt.% Of washing or cleaning active polymer, is free from bleach and, based on the total weight of the phase, contains less than 1 wt.% Citric acid ,

For the preparation of compositions according to the invention in tablet form, which may be single-phase or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - if appropriate one layer each - mixed in a mixer with each other and the mixture by means of conventional tablet presses, such as eccentric presses or Ru rotter presses, with pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-pressed. This is preferably done at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. Thus, fracture-resistant, yet non-breakable, tablets with breaking and bending strengths of normally 100 to 200 N, but preferably more than 150 N, are obtained without problems. Preferably, a tablet produced in this way has a weight of from 10 g to 50 g, in particular from 15 g to 40 g. The Rau mform of the tablets is arbitrary and may be ru nd, oval or square, with intermediate forms are possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are predominantly introduced via the metering device-for example the dishwasher-depends on the geometry and volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) ^* (34 to 40 mm), in particular of 26 ^* 36 mm or of 24 ^* 38 mm.

Preferably, a sodium silicate is contained in an amount ranging from 1 to 3% by weight, more preferably in a spatial portion containing no enzyme. The object underlying the invention is achieved in a further embodiment by the use of the washing or cleaning agent according to the invention for washing hard objects made of plastic, porcelain, stoneware, glass and / or metal, in particular crockery or cutlery.

The object underlying the invention is achieved in a further embodiment by a method for cleaning of hard objects made of plastic, porcelain, stoneware, glass and / or metal, dad urch in that in at least one Process step, a washing or cleaning agent according to any one of claims 1 to 9 is applied.

This includes both manual and mechanical processes, with mechanical processes being preferred on account of their more precise controllability, for example with regard to the quantities and reaction times used. Processes for the cleaning of dishes are generally distinguished by the fact that various cleaning-active substances are applied to the cleaning product in several process steps and washed off after the reaction time, or that the cleaning agent is otherwise mixed with a detergent or a solution or solvent Dilution of this agent is treated. The same applies to methods for cleaning all other materials than dishes, especially soft surfaces. All conceivable washing or cleaning methods can be enriched in at least one of the method steps to the application of a washing or cleaning agent according to the invention and then represent embodiments of the present invention. All facts, objects and embodiments, ie for washing according to the invention. or detergents are also applicable to this subject of the invention. Therefore, reference is hereby expressly made to the disclosure in the appropriate place, with the reference that this disclosure also applies to the above methods according to the invention.

The object underlying the invention is achieved in a further embodiment by a method for increasing the cleaning performance of an enzyme-containing washing or cleaning agent, characterized in that a hybrid polymer is added to the agent.

In the context of the invention, cleaning performance means the ability of the washing or cleaning agent to remove an existing soiling partially or completely when the agent is used. Examples of Geschirranschmutzungen are milk / meat / sausage / chocolate pudding on dishes. For dishwashing detergents, cleaning performance describes the ability of the dishwashing detergent to remove an existing soiling from the hard surface of the dishware. Examples of scrape dirt are milk, minced meat, egg yolk, oatmeal and starch. In the context of the invention, both the washing or cleaning agent, which comprises the protease and the polymer and optionally the complexing agent, or the wash liquor formed by this agent, as well as the protease itself, have a respective cleaning performance. The cleaning performance of the enzyme thus contributes to the cleaning performance of the agent or of the wash liquor formed by the agent. The proteolytic cleaning performance refers to the cleaning performance of the agent on protease-sensitive stains, in particular of milk, minced meat, egg yolk, Oatmeal and starch. The cleaning performance is determined in a customary manner, preferably as indicated below.

embodiment

The following three-phase (blue, red, core / blue) cleaning tablets were prepared in the usual way:

Example 1 :

 Phase weight% composition weight% g / job

Blue 61.49

 Na-percarbonate 15.00 3000

Tetraacetylethylenediamine 0.50 0.100

Bleach 1.10 0.220 aq. Polycarboxylate solution 0.75 0.150

Na citrate 2H20 11.50 2.300

Soda heavy 14.25 2,850

Sodium phosphonate 4.50 0.900

Hybrid polymer 9.00 1.800

Fatty alcohol polyglycol ether 4.50 0.900

Total dye blue 0.40 0.008

 61.49 12,30

Phase weight% composition weight% g / job

Red 27.52

 aq. Polycarboxylate solution 0.30 0.060

Enzme, incl. Protease 4,80 0,960

Na citrate anhydrous 6,35 1,270

Citric acid anhydrous 3.00 0.600

Tetraacetylethylenediamine 3.50 .700

Fatty alcohol polyglycol ether 1.50 0.300

Dye red 0.30 0.060

Zn acetate anhydrous 0.20 0.040

Perfume 0.07 0.015

Sodium phosphonate 2.50 0.500

Total hybrid polymer 5.00 1.000

 27.52 5.50

Phase weight% composition weight% g / job Core 10.50

 aq. Polycarboxylate solution 0.25 0.050

Na citrate 2H20 1, 84 0.368

Soda heavy 2.90 0.580

Hybrid polymer 2.47 0.494

Fatty alcohol polyglycol ether 0.26 0.053

Water 0.20 0.040

Dye blue 0.09 0.01 9

Na disilicate polymer 1, 84 0.368

Sodium phosphonate 0.65 0, 130

Total 10.50 2, 1 0

Klebst. 0, 50 adhesive 0.50 0, 10

Total 100,00 100,00 20, 00

The hybrid polymer used was Alcoguard H 5240 from AkzoNobel, which is formed from starch and synthetic monomers (acrylate).

The cleaning performance in this test was determined in a Miele G698 in Normal 50 ° program according to the IKW method.

 In the formulation, the hybrid polymer Alcog uard H 5240 was used instead of the known synthetic polymers (Na acrylate or AA / AMPS copolymers or terpolymers). The amount of enzyme was light in all experiments.

The result is shown in the following table:

Cleaning performance (Miele 698, Normal 50, 21 ° dH)

 Tea milk minced yolk oatmeal starch

Example 1 o. 9.6 6.9 9.9 7.6 8.0 7.9 Hybrid polymer

 Example 1 with 10.0 6.8 1 0.0 7.6 7.7 8.6 synthetic polymer

 (Acusol 590 and

Acusol 902) Example 1 with 10.0 7, 1 9.6 8.6 7.4 8.9 Alcog uard 5240

 Example 1 with 10.0 7.2 1 0.0 8.6 7.8 8.4 Alcog uard 5240 and

 enzyme

The scale of the rating goes from 0 = very bad to 10 = very good.

As can be seen, the use of Alcoguard 5240 showed an improvement in protease performance, although in all cases the same amount of protease (see Example 1) was used. The performance was independent of the builder system and works with phosphonate and / or MGDA.

The features of the invention disclosed in the present description and in the claims may be essential both individually and in any desired combinations for the realization of the invention in its various embodiments. The invention is not limited to the described embodiments. It can be varied within the scope of the claims and under consideration of the knowledge of the person skilled in the art.

Claims

claims 1 . Process for increasing protease activity in detergents or cleaners, characterized in that protease is used in combination with a hybrid polymer. 2. Use of hybrid polymer to increase the protease performance in detergents or cleaning agents. 3. The method according to claim 1 or use according to claim 2, characterized in that in addition also fatty alcohol alkoxylate, fatty alcohol ether sulfate and / or fatty alcohol sulfonate in an amount in a range of 1 0 to 30 wt.%, Particularly preferably in a range of 16 to 25 % By weight based on the total weight of the washing or cleaning agent. 4. Washing or cleaning agent containing  a. Enzyme, and  b. Hybrid polymer. 5. washing or cleaning agent according to claim 4, dad urch in that Enzyme is contained in an amount in a range of 0, 1 to 10 wt.%, Particularly preferably in a range of 0, 25 to 5 wt.%, Most preferably in a range of 3 to 4.8 wt.%. 6. washing or cleaning agent according to any one of claims 4 to 5, characterized in that the hybrid polymer is a copolymer of polysaccharides and synthetic monomers, wherein the synthetic monomers are particularly preferably acrylate monomers. 7. washing or cleaning agent according to any one of claims 4 to 6, characterized in that the hybrid polymer in an amount in a range of 1 to 30 wt.%, Particularly preferably in a range of 5 to 20 wt.%, Whole is more preferably contained in a range of 15 to 19, 5 wt.%. 8. washing or cleaning agent according to any one of claims 4 to 7, characterized in that fatty alcohol alkoxylate, fatty alcohol ether sulfate and / or fatty alcohol sulfonate in an amount in a range of 10 to 30 wt.%, Particularly preferably in a range of 16 to 25 wt .% is included. 9. washing or cleaning agent according to any one of claims 4 to 8, characterized in that it is solid, particularly preferably a cleaning agent tablet, the ingredients are particularly preferably distributed over at least three different spatial sections or phases, with very particular preference only contains a spatial section or a phase enzyme and all spatial sections or phases contain hybrid polymer. 10. washing or cleaning agent according to any one of claims 4 to 9, characterized in that Natriu meitrat or citric acid in an amount ranging from 1 1 to 30 wt.%, Particularly preferably in a range of 17 to 23 wt.% Contain is. 1 1. A washing or cleaning composition according to any one of claims 4 to 10, characterized in that a sodium silicate is contained in an amount ranging from 1 to 3% by weight, more preferably in a spatial portion containing no enzyme , 12. Use of the washing or cleaning agent according to any one of claims 4 to 1 1 for washing hard objects made of plastic, porcelain, earthenware, glass and / or metal, in particular of crockery or cutlery. 13. A process for the cleaning of hard objects made of plastic, porcelain, stoneware, glass and / or metal, dad urch in that in at least one process step, a washing or Reinigu ngsmittel is applied according to one of claims 4 to 1 1. 14. A method for increasing the cleaning performance of an enzyme-containing washing or cleaning agent, characterized in that the agent is added to a hybrid polymer.