HUP0102144A2 - Detergent and cleaning agent composition containing a mixture of amylase and a color transfer inhibitor and the use of the mixture - Google Patents

Abstract

The detergent and cleaning agent preparation according to the invention contains amylase from Bacillus amiloliquefaciens, a mixture of substances that inhibit color transfer and the usual other ingredients compatible with this type of enzyme. The invention also relates to the use of such a mixture to enhance the cleaning effect of washing and cleaning agents, especially aqueous washing and cleaning solutions. The subject of the invention is also the use of such a mixture to prevent the transfer of textile dyes to non-dyed or other colored textiles, if they are washed together, especially in surfactant-containing aqueous solutions. HE

Description

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S.B.G. & K.

International Patent Office H-1062 Budapest, Andrássy út 113. Telephone: 34-24-950, Fax: 34-24-323 •?L:. b ( ···· · ·· ··

71.534/SZE

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Detergent and cleaning agent containing amylase/ and color transfer inhibitor^ t £3 c\. le -ek' Q tktxL^aias<\

The present invention relates to enzyme-containing detergents and cleaning agents which, in addition to the usual ingredients, contain amylase from Bacillus amyoliquefaciens and a certain color transfer inhibitor.

In addition to the essential components for the washing process, such as surfactants and structural materials, detergents usually also contain other ingredients, which can be grouped under the name of washing auxiliaries, and which can belong to different groups of active ingredients, such as foam regulators, greying inhibitors, bleaching agents, bleach activators or colour transfer inhibitors. Such auxiliaries also include substances that improve the performance of surfactants by enzymatically breaking down the dirt on textiles. This effect naturally also applies to hard surfaces. In this process, in addition to proteases that promote protein removal and lipases that break down fat, amylases play an increased role. The role of amylases is to facilitate the removal of starch-containing dirt by catalytic hydrolysis of starch polysaccharides. Due to this ability, amylases have been used for a long time in dishwashing detergents and detergents used for textiles. In most cases,

- 2 The amylase used in most of them is a thermostable amylase from Bacillus licheniformis, which is commercially available, for example, under the name Termamyl®. Recently, genetically modified amylases, i.e. naturally occurring amylases whose amino acid sequence has been altered using genetic engineering methods, have been increasingly used in these agents. The aim of this intervention is to increase the performance of the amylase as well as the stability of the enzyme, especially its stability against oxidizing agents.

A solution developed to achieve this goal is described in International Publication No. WO 94/18314, the essence of which is that amino acids particularly susceptible to oxidation are removed from the amino acids of amylase, such as methionine, tryptophan, cysteine or tyrosine, or they are replaced with other amino acids less susceptible to oxidation.

A similar solution is described in International Publication No. WO 95/21247, according to which at least one of the amino acids of amylase, methionine, is replaced by an amino acid other than methionine or cysteine.

Although such genetic engineering modifications may result in improved amylase stability under certain circumstances, they do not improve the washing or cleaning performance of the amylase-containing agent in question.

- 3 Surprisingly, we have found that a combination of a naturally occurring α-amylase and a color transfer inhibitor results in unexpected, synergistic performance improvements when these combinations are used in detergents or cleaning agents.

Accordingly, the invention provides an amylase-containing detergent or cleaning agent comprising α-amylase derived from Bacillus amyloliquefaciens and a percarboxylic acid or alkali salt thereof together with conventional components compatible with such components.

The invention also relates to the use of such a suitable combination to increase the performance of detergents and cleaning agents, especially for starch-containing soils, when used in aqueous detergents and cleaning solutions.

A further object of the invention is to use a suitable combination to prevent the transfer of colorants from colored textiles to uncolored or differently colored textiles when they are washed together, especially in aqueous solutions containing surfactants.

α-Amylase from Bacillus amyloliquefaciens has been known for a long time, for example, such a material is described in US Patent No. 1,227,374, which amylase is commercially available under the name Amylase BAN®.

- 4 The agent according to the invention preferably contains 0.001 to 0.5 mg, especially 0.02 to 0.3 mg of amylolytic protein per 2 g of the total agent. The protein concentration can be determined by known methods, such as the bicinchoninic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the Biuret method (A.G. Gornall, C.S. Bardawill and M.m. David, J. Biol. Chem. 177, 751-766, 1948).

A composition according to the invention preferably contains 0.1-2% by weight, in particular 0.2-1% by weight, of a color transfer inhibitor, which according to a preferred embodiment of the invention is a vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide polymer or a copolymer of these materials. In addition, polyvinylpyrrolidones with a molecular weight of 15,000-50,000 known from European patent specification EP 0 262 897; polyvinylpyrrolidones with a molecular weight of over 1,000,000, in particular 1,500,000-4,000,000 known from international publication WO 95/06098; polyvinylpyrrolidones with a molecular weight of DE 28 14 287 or DE 38 03 630. N-vinylimidazole/N-vinylpyrrolidone copolymers known from German patent applications and international publications WO 94/10281, WO94/6796, WO 95/03388 and WO 95/03382; polyvinyl oxazolidones known from German patent specification DE 28 14 329; vinyl monomer and carboxylic acid amide-based copolymers known from European patent application EP 610 846; polyesters and polyamides containing pyrrolidone groups known from international publication WO 95/09194; grafted polyamidoamines or polyethyleneimines known from international publication WO 94/29422; German patent DE 43 28 254

- polymers containing amide groups derived from secondary amines, as known from WO 94/02579 or EP 0135 217; polyamine-N-oxide polymers, as known from WO 94/02579 or EP 0135 217; and copolymers based on acrylamido-alkylenesulfonic acid, as known from EP 0 584 738. Enzymatic systems containing a peroxidase and hydrogen peroxide or a compound that yields hydrogen peroxide in water, as described, for example, in WO 92/18687 and WO 91/05839, may also be used. A substance acting as a mediator for peroxidases may be preferred, such as, for example, a compound described in WO 96/10079. acetosyringone known from international publication document WO 96/12845, a phenol derivative known from international publication document WO 96/12845, or a phenothiazine described in international publication document WO 96/12846, together with which further polymeric, colour transfer-inhibiting active ingredients mentioned above can also be used. The average molecular weight of polyvinylpyrrolidone used in the compounds according to the invention ranges from 10,000 to 60,000, in particular from 25,000 to 50,000. Copolymers preferably consist of vinylpyrrolidone and vinylimidazole, the molar ratio of which is in the range of 5:1 to 1:1, and the average molecular weight of which is in the range of 5,000 to 50,000, in particular from 10,000 to 20,000.

The detergents or cleaning agents according to the invention, which may be in particular in the form of a powdered solid, a post-concentrated particle, a homogeneous solution or a suspension, may contain, in addition to the enzyme combination used according to the invention, essentially any of the substances present in such agents.

- 6 may contain ingredients used in a particular manner. The agents according to the invention may thus contain, in particular, builders, surface-active surfactants, organic and/or inorganic peroxy compound-based bleaching agents, bleach activators, water-miscible organic solvents, further enzymes, precipitants, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, anti-darkening agents, anti-foaming agents and colorants and fragrances.

The agents according to the invention may contain one or more surfactants, which are in particular anionic surfactants, nonionic surfactants or mixtures thereof, but may also be cationic, bound ionic or amphoteric surfactants.

Suitable nonionic surfactants for the purposes of the invention are in particular alkyl glycosides, or alkyl glycosides or straight or branched chain alcohols having 12-18 carbon atoms in the alkyl moiety and 3-20, preferably 4-10 alkyl ether groups. Suitable ethoxylation and/or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides, which are identical in their alkyl moiety to the aforementioned long-chain alcohol derivatives, can also be used.

As nonionic surfactants, preferably alkoxylated, preferably ethoxylated, especially primary alcohols having 8-18 carbon atoms, containing an average of 1-12 moles of EO per mole, can be used, in which the alcohol moiety

- 7 linear, or preferably in the 2-position, methyl group, or which may contain a mixture of linear and methyl side chains, as is generally the case with oxoalkyl groups. However, alcohol ethoxylates derived from linear, naturally occurring alcohols with 12 to 18 carbon atoms, such as coconut, palm, tallow or oleyl alcohol, and having 2 to 8 EO per mole, are particularly preferred.

Preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 or 4 EO, C9-11 alcohols with 7 EO, C13-15 alcohols with 3, 5, or 8 EO, C12-18 alcohols with 3, 5, or 7 EO, and mixtures thereof, such as a mixture of a C12-14 alcohol with 3 EO and a C12-18 alcohol with 7 EO.

The stated degrees of ethoxylation are statistical averages, which can be whole or fractional numbers for a particular product.

Preferred alcohol ethoxylates have a limited homolog distribution (narrow range ethoxylates, NRE).

In addition to the nonionic surfactants mentioned, fatty alcohols with more than 12 EO can also be used. Such fatty alcohols include, for example, (tallow) fatty alcohols with 14, 16, 20, 25, 30 or 40 EO. In practice, the extremely low-foaming compounds are used, in particular, in detergents suitable for machine dishwashing.

- 8 zak. This group preferably includes alkyl poly(ethylene glycol) poly(propylene glycol) ethers with 12-18 carbon atoms, which may contain up to 8 EO or propylene oxide units (PO) per molecule. However, other known, low-foaming nonionic surfactants can also be used, such as end-capped alkyl poly(alkylene glycol) mixed ethers.

Alkoxylated alcohols with hydroxyl groups, the so-called hydroxy-mixed ethers, such as those described in European patent EP 0 300 305, are particularly preferred. Nonionic surfactants also include alkyl glycosides of the general formula RO(G), in which

R is an aliphatic group with a primary straight carbon chain or methyl side chains, especially a methyl group in the 2-position, having 8 to 22 carbon atoms, but preferably 12 to 18 carbon atoms, and

G is a 5 or 6 carbon glucose unit, preferably glucose.

The degree of oligomerization "x", which shows the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a value that can be determined analytically, can also be a fractional number - between 1 and 10, but preferably has a value of 1.2-1.4.

Also suitable compounds are polyhydroxy fatty acid amides of the general formula (II), in which

RiCO means an aliphatic acyl group of 6-22 carbon atoms,

R ² represents a hydrogen atom, a C 1-4 alkyl group, a C 1-4 hydroxyalkyl group, and

- 9 [Z] represents a linear or branched polyhydroxyalkyl group having 3-10 carbon atoms.

Polyhydroxy fatty acid amides can be derived preferably from reducing sugars having 5-6 carbon atoms, in particular glucose. Polyhydroxy fatty acid amides also include compounds of the general formula (III), in which

R ³ is a straight or branched alkyl or alkylene group having 7-12 carbon atoms,

R ⁴ is a linear, branched or cyclic alkyl, aryl or oxyalkyl group having 1-8 carbon atoms, of which alkyl groups having 1-4 carbon atoms are preferred, and

[Z] is a linear polyhydroxyalkyl group, the alkyl chain of which is substituted by at least two hydroxyl groups; or alkoxylated, preferably ethoxylated or propoxylated derivatives of these groups.

The formation of the [Z] substituent can advantageously be carried out, for example, by reductive amination of a sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.

The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst, as taught in WO 95/073331.

A further, preferably used group of nonionic surfactants are those which are either used as single nonionic surfactants or in combination with other nonionic surfactants.

- 10 are used in combination with surfactants, in particular alkoxylated fatty alcohols and/or alkyl glycosides, such alkoxylated, preferably ethoxylated or ethoxylated and propoxylated compounds containing 1-4 carbon atoms in the alkyl chain, preferably fatty acid methyl esters, which are described, for example, in Japanese patent No. JP 58/217598, or which can be prepared preferably according to the process described in international publication No. WO 90/13533. Suitable nonionic surfactants of the amine oxide type may be, such as N-coco alkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, as well as fatty acid alkanolamines. The amount of nonionic surfactants is preferably not more than the amount of ethoxylated fatty alcohols, preferably not more than half of it.

Other suitable surfactants are the so-called Gemini surfactants. This generally refers to compounds that contain two hydrophilic groups per molecule. These groups are usually separated from each other by a so-called “spacer”. This spacer is usually a carbon chain that is long enough for the hydrophilic groups to be at a suitable distance from each other and to react independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and by their ability to significantly reduce the surface tension of water. In exceptional cases, Gemini surfactants include not only such “dimers”, but also the corresponding “trimer” surfactants.

Suitable Gemini surfactants include, for example, the sulfated hydroxy mixed ethers described in German Patent Specification DE 43 21 022 or the dimer alcohol bis- and trimer alcohol tris-sulfates and ether sulfates described in German Patent Specification DE 193 03 061.

The end-capped dimer and trimer mixed ethers described in German patent DE 195 13 391 are particularly distinguished by their bi- or multifunctionality. For example, these end-capped surfactants have good crosslinking properties and are low-foaming, which makes them particularly suitable for use in machine washing and cleaning processes. Gemini polyhydroxy fatty acid amides or poly(polyhydroxy fatty acid amides) can also be used, as described in international publications WO 95/19953, WO 95/19954 and WO 95/19955.

Anionic surfactants which can be used in the compositions according to the invention are, in particular, soaps and those which contain sulphate or sulphonate groups. As sulphonate-type surfactants, it is preferable to use C9-C13 alkylbenzene sulphonates, olefin sulphonates, i.e. mixtures of alkene and hydroxyalkanesulphonates and disulphonates, which can be prepared, for example, by sulphonating a C12-C18 monoolefin containing both terminal and internal double bonds with gaseous sulphur trioxide, and then subjecting the product obtained as a result of the sulphonation to alkaline or acidic hydrolysis. Alkyl sulphonates which can be prepared from C12-C18 alkanes, for example, by sulphochlorination or sulphoxidation followed by hydrolysis or neutralisation, can also be used. In addition, esters of α-sulfo fatty acids (estersulfonates) can be used, such as α-sulfonated methyl esters of hydrated coconut, palm kernel or tallow fatty acids, which can be prepared by sulfonating methyl esters of fatty acids of vegetable or animal origin containing 8 to 20 carbon atoms in the fatty acid molecule and subsequently neutralizing them to form a water-soluble monosalt. α-sulfonated esters of hydrated coconut, palm kernel or tallow fatty acids, which may also contain unsaturated fatty acids, such as oleic acid, in small amounts, preferably less than 2-3% by weight, can be used. Sulfo fatty acid alkyl esters, whose ester group contains an alkyl chain containing no more than 4 carbon atoms, such as methyl ester, ethyl ester, propyl ester or butyl ester, are particularly preferred. Particularly preferred compounds are methyl esters of sulfofatty acids (MES) or their saponified disalts. Further suitable anionic surfactants are, for example, sulfonated fatty acid glycerol esters, which may be in the form of mono-, di- or triesters, or mixtures thereof, which can be prepared by esterifying a monoglycerol with 1-3 mol of fatty acid or by transesterifying triglycerides with 0.3-2 mol of glycerol. Preferred alk(en)ylene sulfates are fatty alcohols having 12-18 carbon atoms, such as coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or sodium salts of sulfuric acid half-esters of oxoalcohols having 10-20 carbon atoms or similar types of half-esters of secondary alcohols of this chain length.

Furthermore, those alk(en)yl sulfates of the aforementioned chain length are preferred which are a straight chain of a synthetic, petrochemically produced

- They contain a 13-carbon alkyl group, which has similar degradation properties to raw materials produced on a corresponding fat chemical basis.

From a washing technical point of view, the compounds which can be used preferably are the alkyl sulfates with 12-16 carbon atoms and the alkyl sulfates with 12-15 carbon atoms, while the alkyl sulfates with 14-15 carbon atoms are particularly preferably used. The 2,3-alkyl sulfates prepared as described in US 3,234,258 or US 5,075,041, which are commercially available under the name DAN® by Shell Oil Company, can also be used as anionic surfactants. Also suitable are the straight or branched carbon-7-21 alcohols ethoxylated with 1-6 ethylene oxide (EO), such as the alcohols with 9-11 carbon atoms having 2 methyl groups and an average of 3.5 moles of EO or the fatty alcohols with 12-18 carbon atoms having 1-4 moles of EO.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, also called sulfosuccinates or sulfosuccinic acid esters, and the mono- or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain fatty alcohols having 8 to 18 carbon atoms or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol group which can be derived from ethoxylated fatty alcohols which themselves can be considered nonionic surfactants. Of these, again, ethoxylated fatty alcohols with a limited homologous distribution

Fatty alcohol groups derived from -14 fatty alcohols are particularly preferred groups.

Alk(en)yl succinic acids or salts thereof, preferably containing 8-18 carbon atoms in the alk(en)yl group, can also be used.

Further anionic surfactants which can be used are, for example, fatty acid derivatives (taurides or sarcosides) of amino acids, such as N-methyltaurine and/or N-methylglycine. Sarcosides or sarcosinates are particularly preferred, especially those of higher carbon number, optionally mono- or polyunsaturated fatty acids, such as their sarcosinates, such as oleyl sarcosinate.

Soaps are particularly suitable as further anionic surfactants. Particularly suitable for this purpose are saturated fatty acid soaps, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrated erucic acid, behenic acid, and in particular soap mixtures derived from natural fatty acids, such as coconut, palm kernel or tallow fatty acids. The known alkenyl succinic acid salts can also be used together with the aforementioned soaps or as supplements to these soaps.

Anionic surfactants, including soaps, can be present in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases, such as mono-, di- or triethanolamine. Anionic surfactants are preferably used in the form of their sodium or potassium salts, especially in the form of their sodium salts.

- 15 In the detergents according to the invention, the surfactants are preferably present in an amount of 5-50% by weight, particularly preferably 8-30% by weight, while in the detergents according to the invention suitable for machine cleaning of hard surfaces - in particular dishes - a lower amount of surfactant of up to 10% by weight, particularly up to 5% by weight, and particularly preferably 0.5-3% by weight is used.

An inventive agent preferably comprises at least one water-soluble and/or water-insoluble organic and/or inorganic structural material. Water-soluble organic structural materials may be, for example, polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, as well as polyaspartic acid; polyphosphonic acids, in particular aminotris-(methylenephosphonic acid), ethylenediaminetetrakis-(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid; polymeric hydroxy compounds, such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates prepared by oxidation of polysaccharides or dextrins, which are described in EP 0 625 992. European patent and WO 92/18542 az. international publication document and EP 0 232 202. European patent; and polymeric acrylic acids. methacrylic acids, maleic acids, and mixed polymers derived from these, which in polymerized form may also contain small amounts of polymerizable substances without carboxylic acid groups. The relative molecular weight of homopolymeric, unsaturated carboxylic acids is generally between 3000 and 200000, and that of copolymers is

- 162,000 to 200,000, preferably between 30,000 and 120,000. These values are in each case values based on the free acid.

One particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of between 30,000 and 100,000. Commercially available products include SOKALAN® CP 5, CP 10, and PA 30 manufactured by BASF. Suitable, although less preferred, compounds of this type are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether; vinyl ester, ethylene, propylene, or styrene, having an acid content of at least 50% by weight.

Terpolymers which contain two unsaturated acids and/or their salts as monomers and vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate as third monomers can also be used as water-soluble organic structural materials. The first acidic monomer or its salt can be derived from a monoethylenically unsaturated monocarboxylic acid having 3-8 carbon atoms, preferably 3-4 carbon atoms, in particular (meth)acrylic acid. The second acidic monomer or its salt can be, for example, a dicarboxylic acid derivative having 3-4 carbon atoms, particularly preferably a maleic acid derivative and/or an allylsulfonic acid derivative, where the allylsulfonic acid is substituted in the 2-position by an alkyl group or an aryl group. Such polymers can be prepared in particular by processes which are described in German Patent No. DE 42 21 381 and in German Patent No. DE 43 00 772. The relative molecular weight of these polymers is between 1000 and 200000. Further preferred copolymers are compounds which are described in German Patent Nos. DE 43 03 320 and DE 44 17 734.

- 17, and which preferably contain acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers.

The organic building materials can be used in particular for the preparation of compositions in the form of liquid, aqueous solutions, preferably 30 to 50% by weight aqueous solutions. The aforementioned acids are generally used in the form of their water-soluble salts, in particular their alkali salts.

Such organic building materials may optionally be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Amounts close to the upper limit are preferably used in compositions according to the invention which are in the form of pastes or liquids, in particular containing water.

Suitable water-soluble inorganic building materials are alkali silicates, alkali carbonates or alkali phosphates, which can also be present in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of such materials include trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with a degree of oligomerization of 5-1000, in particular 5-50, and the corresponding potassium salts or mixtures of sodium or potassium salts.

As water-insoluble, water-dispersible inorganic structural materials, crystalline or amorphous alkali aluminosilicates can be used in particular, up to 50% by weight, preferably not more than 40% by weight.

%, in particular in the case of liquid preparations in an amount of 1-5% by weight. Of these, sodium aluminosilicates of detergent quality are preferably used, in particular Zeolith A, P and optionally X separately or in a mixture, for example as a co-crystallized product of Zeolith A and Zeolith X (commercially available as Vegobond® AX from Condea Augusta S. p. A.). Amounts close to the upper limit are preferably used in the form of solid particles. Suitable aluminosilicates in particular do not contain particles larger than 30 μιη and contain at least 80% by weight of particles smaller than 10 μιη. The calcium binding capacity of these compounds, which can be determined according to the methods described in German patent DE 24 12 837, is usually around 100-200 mg CaO/g compound.

Suitable substitutes or partial substitutes for aluminosilicates are, for example, crystalline alkali silicates, which may be present alone or in the form of a mixture with amorphous silicates. The alkali silicates which may be used as framework materials in the compositions according to the invention have a molar ratio of alkali oxide to SiO ₂ of less than 0.95, in particular 1:1.1 to 1:12, and these compounds may be amorphous or crystalline. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates having a molar ratio of 1:2 to 1:2.8 Na ₂ O:SiO ₂ . Such materials having a molar ratio of 1:1.9 to 1:2.8 Na ₂ O:SiO ₂ can be prepared according to the teachings of European Patent Application EP 0 425 427 .

- 19Crystalline silicates, which can be used either separately or in a mixture with amorphous silicates, are preferably crystalline layered silicates of the general formula Na2Si _x O2x+iy H2O, in which x, i.e. the so-called modulus, is a number from 1.9 to 22, in particular from 1.9 to 4, and y is a number from 0 to 33, and where x is preferably 2, 3 or 4. Processes for preparing crystalline layered silicates of this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those compounds in which the value of x in the aforementioned general formula is 2 or 3. Particularly preferred are both β- and δ-sodium disilicates, which can be characterized by the general formula Na2S12Os.yH2O, and which β-sodium silicates can be prepared, for example, as described in International Publication No. WO 91/08171.

δ-sodium silicates having a modulus of 1.9 to 3.2 can be prepared as described in Japanese Patent Application No. JP 04/238 809 or JP 04/260 610. Furthermore, substantially anhydrous crystalline alkali silicates having the above general formula, prepared from amorphous alkali silicates, in which x is a number from 1.9 to 2.1, the preparation of which compounds is described in European Patent Specifications EP 0 548 599, EP 0 502 325 and EP 0 452 428, can be used in the compositions of the invention.

In a further preferred embodiment of the compositions according to the invention, a crystalline sodium layered silicate having a modulus of 2 to 3 is used, as described in European Patent Application EP 0 436 835.

- 20badalmi report describes, in which the layered silicate in question is produced from sand and soda.

In another preferred embodiment of the invention, crystalline sodium silicates having a modulus of 1.9 to 3.5, prepared according to European Patent Specifications EP 0 164 552 and/or EP 0 294 753, are used.

The above-mentioned layered silicates with the general formula (I) are manufactured and marketed by Clariant GmbH (Germany) under the name Na-SKS, such preparations are, for example, Na-SKS-1 (Na ₂ SÍ22O45.xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Sii ₄ O ₂ 9.xH ₂ O, magadiite), Na-SKS-3 (Na ₂ SieOi7.xH ₂ O) and Na-SKS-4 (Na ₂ SÍ4Og.xH ₂ O, makatiite). Among the compounds belonging to the aforementioned group, the most suitable compounds are Na-SKS-5 (a-Na ₂ Si ₂ Os), Na-SKS-7 (p-Na ₂ Si ₂ O5, natrosilite), Na-SKS-9 (NaHSi ₂ O5.H ₂ O), Na-SKS-10 (NaHSi ₂ Os.3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O5), and Na-SKS-13 (NaHSi ₂ Os), Na-SKS-6 (0-Na ₂ Si ₂ Os) is particularly suitable.

A comprehensive overview of crystalline layered silicates can be found, for example, in the articles published on pages 33-38 of the publication “Hoechst High Chem Magazin 14/1993” and on pages 805-808 of the publication “Seifen-Öle-Fette-Wachse, 116. Jahrgang, Nr. 20/1990”.

In a further preferred embodiment of the compositions according to the invention, a granule consisting of a crystalline layered silicate and citrate, and a crystalline layered silicate and (co-)polymeric polycarboxylic acid is formed.

- A mixture of 21 livers, as described in German patent application DE 198 19 187, or, for example, as described in international publication WO 95/22592, a mixture of alkali silicate and alkali carbonate, the latter being commercially available under the name Nabion® 15, is used.

The builders may optionally be present in the compositions according to the invention in an amount of up to 90% by weight, but are preferably used in an amount of up to 75% by weight. In the detergents according to the invention, these materials are particularly present in an amount of 5-50% by weight.

Among the peroxide compounds suitable for use in the compositions according to the invention, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, diperdodecane diacid salts, hydrogen peroxide, or organic salts which release hydrogen peroxide under washing conditions, such as perborate, percarbonate, persilicate and/or persulfate, such as caroate, are particularly suitable. If solid peroxide compounds are used, they can be used in the form of powders or granules, which can also be coated in a known manner. If a peroxide compound is also present in a composition according to the invention, it is preferably present in an amount of up to 50% by weight, in particular 5-30% by weight. It may be expedient to add small amounts of known bleach stabilizers, such as phosphonates, borates or metaborates and metasilicates or magnesium salts, such as magnesium sulfate.

- 22Bleaching activators include compounds which, under perhydrolysis conditions, yield aliphatic percarboxylic acids, preferably having 1-10 carbon atoms, in particular 2-4 carbon atoms, and/or optionally substituted perbenzoic acids. Also suitable are substances which carry O- or N-acyl groups with the aforementioned number of carbon atoms and/or optionally substituted benzoyl groups.

Preferred compounds include multiply acylated alkylenediamines, especially tetraacetylethyldiamine (TAED); acylated triazine derivatives, especially 2,4-dioxohexahydro-1,3,5-triazine (DADHT); acylated glycolurils, especially tetraacetyl glycoluril (TAGU; N-acylimides, especially N-nonanoyl succinimide (NOSI); acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS); carboxylic acid anhydrides, especially phthalic acid anhydride; acylated polyhydric alcohols, especially triacetin or ethylene glycol diacetate; 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German Patents DE 196 16 693 and DE 196 16 767 and acetylated sorbitol and mannitol, or mixtures of these compounds described in European Patent EP 0 525 239 (SORMAN); acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose; and acetylated, optionally N-alkylated glucamine and gluconolactone; and/or N-acetylated lactams, such as N-benzoylcaprolactam, which compounds are disclosed in WO 94/27970, WO 94/28102, WO

- 2394/28103, WO 95/00626, WO 95/14759 and WO 95/14798.

Also preferably used compounds are the acyl lactams described in German patent specification DE 196 16 770 and in international publication WO 95/14075. Combinations of conventional bleach activators known from German patent specification DE 44 43 ₁₇₇ can also be used. Such bleach activators are generally used in the usual amounts, preferably 0.5 to 10, in particular 1 to 8% by weight, based on the weight of the total composition, but such substances are not present at all when the percarboxylic acids according to the invention are used.

In addition to or instead of traditional bleaching activators, sulfonimines and/or transition metal salts or transition metal complexes that enhance the bleaching effect, the so-called bleaching catalysts, as described in European patents EP 0 446 982 and EP 0 453 003, can also be used.

In addition to the amylase of the invention, enzymes that can be used in the agents of the invention include lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, lactases and peroxidases, or mixtures thereof. In addition, such compounds other than the amylases of the invention may also be present. Particularly suitable are, for example, enzymes derived from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformes, Streptomyces griseus, Humicola lanuginosa, Humicola insolens,

- 24Enzymatic active ingredients derived from Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus. The amylases according to the invention and the enzymes optionally used as additives can be bound to carriers or coated in shell materials in order to prevent premature inactivation, as described, for example, in WO 92/11347 or WO 94/23005. These enzymes can preferably be present in the detergent or cleaning agent compositions according to the invention in an amount of up to 5% by weight, in particular in an amount of 0.2 to 4% by weight.

If the composition according to the invention contains a protease, the proteolytic activity of the composition is preferably between 100 PE/g and 10,000 PE/g, (PE=protease unit), in particular between 300 and 8,000 PE/g. If several enzymes are used in the compositions according to the invention, this can be done in the form of two enzymes that are separate from each other or that are packaged separately in a known manner, or in the form of enzymes that are packaged together in one granule - as described, for example, in international publications WO 96/00772 or WO 96/0773.

In the compositions according to the invention, especially in the liquid or pasty compositions, organic solvents which can be used in addition to water include, for example, alcohols having 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures thereof and ethers derived from these groups of compounds. Such water-miscible solvents are suitable for the compositions according to the invention.

- 25 are preferably used in an amount of not more than 30% by weight, in particular 6-20% by weight.

In order to adjust a desired pH value that is not achieved by mixing the usual components, the agents according to the invention can contain acids that are not harmful to the system or the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, such as, for example, sulfuric acid or bases, in particular ammonium or alkali hydroxides. Such pH regulators are preferably present in the compositions according to the invention in an amount of not more than 20% by weight, in particular 1.2 to 17% by weight.

The role of the anti-greying agents used in the compositions according to the invention is to keep the impurities dissolved from the fibres suspended in the supernatant. Water-soluble colloids, mostly of an organic nature, such as starches, glues, gelatins, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acid sulfuric acid esters of starch or cellulose are suitable for this purpose. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, other compounds other than the above-mentioned starch derivatives, such as aldehyde starches, can also be used. Preferred compounds are cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose; and cellulose mixed ethers, such as methylhydroxyethyl cellulose, methylhydroxypropyl cellulose, methylcarbohydrate cellulose, etc.

- 26-carboxymethylcellulose and mixtures thereof, which may be present in the compounds of the invention in an amount of 0.1-5% by weight, based on the weight of the total composition.

The textile detergents according to the invention may contain diamino-stilbene-disulfonic acid derivatives or their alkali metal salts as optical brighteners. Such a suitable compound may be, for example, 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,21-disulfonic acid or compounds of similar structure, which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group in place of the morpholino group. Compounds of the substituted diphenylstyryl type may also be present as brightening agents, such as 4,4'-bis-(2-sulfostyryl)-diphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl or the alkali metal salts of 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the aforementioned optical brightening agents may also be used.

In particular, in machine washing processes, it may be advantageous to add conventional antifoaming agents to the compositions according to the invention. Such antifoaming agents may be, for example, soaps of natural or synthetic origin which contain a significant amount of fatty acids having 18 to 24 carbon atoms. Suitable non-surfactant antifoaming agents may be, for example, organopolysiloxanes and mixtures of these substances with microfine, optionally silanized silica, or paraffins, waxes and microcrystalline waxes and mixtures thereof with silanized silica or bis-fatty acid alkylene diamide. Various

- 27also mixtures of antifoaming agents, such as mixtures of silicones, paraffins or waxes. The antifoaming agents, in particular silicone- and/or paraffin-containing antifoaming agents, are bound to a granular, water-soluble or dispersible carrier. Mixtures of paraffins and bis-stearyl ethylene diamide are particularly preferred in this respect.

The solid compositions according to the invention are prepared without any difficulty and can be carried out in a known manner, for example by spray drying or granulation, during which processes the enzymes and other heat-sensitive ingredients, such as bleaching agents, are optionally added separately later. A preferred process for preparing compositions according to the invention with an increased dry matter content, in particular with a dry matter content of 650 to 950 g/l, which also includes an extrusion step is known from European patent EP 0 486 592.

A further preferred production method involving a granulation process is described in European Patent EP 0 642 576.

The preparation of the single-phase or multi-phase, single-color or multi-color, and in particular single-layer or multi-layer tablet preparations according to the invention can advantageously be carried out by mixing all the components - optionally with respect to each layer - in a mixer, and then pressing the mixture thus obtained into tablets on a conventional tabletting machine, such as an eccentric press or a roller press, with a force of 50 - 100 kN, preferably 60 - 70 kN. In particular,

- 28* '< b In the case of multilayer tablets, it may be advantageous to pre-compress at least one layer. This can preferably be done with a force of 5-20 kN, in particular 10-15 kN. This results in tablets that are resistant to breakage without any difficulty, but dissolve sufficiently quickly under the conditions of use, with a breaking or bending strength of 100-200 N under normal conditions, preferably over 150 N. A tablet produced in this way may preferably have a mass of 10-50 g, in particular 15-40 g. The spatial design of the tablet may be arbitrary, for example round, oval or square or even a shape corresponding to the transition between these. The corners and edges are preferably rounded. The round tablets preferably have a diameter of 30-40 mm. In particular, the size of angular or rectangular tablets - which tablets are predominantly fed through a dosing device of a dishwasher, for example - may also depend on the geometry and capacity of the dosing device. For example, some preferred embodiments may have a surface area of (20-30 mm) x (34-40 mm), but in particular 26 x 36 mm or 24 x 38 mm.

In the production of liquid or pasty detergents or cleaning agents according to the invention in the form of solutions containing conventional solvents, the general procedure is to simply mix the ingredients, which mixture can be processed into the compositions according to the invention either immediately or after dissolving, as a solution, by placing it in an automatic mixer.

Claims (11)

- 29PATENT CLAIMS 1. An amylase-containing detergent or cleaner containing amylase derived from Bacillus amyloliquefaciens, a color transfer inhibitor, and other ingredients commonly compatible with enzymes of this type. 2. The agent according to claim 1, characterized in that it contains amylase in an amount of 0.001 to 0.5 g, in particular 0.02 to 0.3 mg/g of product. 3. The agent according to claim 1 or 2, characterized in that it contains 0.1-2% by weight, in particular 0.2-1% by weight, of a color transfer inhibitor. 4. The agent according to any one of claims 1-3, characterized in that the color transfer inhibitor is a vinylpyrrolidone, vinylimidazole, or vinylpyridine-N-oxide polymer or a copolymer thereof. 5. The agent according to any one of claims 1-4, characterized in that polyvinylpyrrolidone having a molecular weight in the range of 10,000 to 60,000, in particular in the range of 25,000 to 50,000, is used as the color transfer inhibitor. - 30s i ^J . J, 6. The agent according to any one of claims 1-4, characterized in that the color transfer inhibitor is a copolymer of vinylpyrrolidone and vinylimidazole with a molar ratio in the range of 5:1 to 1:1 and a molecular weight in the range of 5000 to 50000, in particular 1000 to 20000. 7. The agent according to any one of claims 1-3, characterized in that a system containing peroxidase and hydrogen peroxide or a compound that gives hydrogen peroxide in water is used as a color transfer inhibitor. 8. The agent according to claim 7, characterized in that the system also contains an additional substance acting as a mediator compound for peroxidases. 9. The agent according to claim 7 or 8, characterized in that the system further comprises a vinylpyrrolidone, vinylimidazole or vinylpyridine-N-oxide polymer or a copolymer thereof as a material. 10. Use of a combination of amylase from Bacillus amyloliquefaciens and a color transfer inhibitor for enhancing the cleaning effect of detergents and cleaning agents, especially when used in aqueous detergent or cleaning solutions. 11. Use of a combination of amylase from Bacillus amyloliquefaciens and a color transfer inhibitor to prevent the transfer of colorants from colored textiles to uncolored or differently colored textiles when they are washed together, especially in aqueous solutions containing surfactants. The authorized representative, Adém Szentpéteri Jr., patent attorney, I R Nerfizetk'öii ’®zalMialm\lrodiMagja \ Phone: d4-24-950; Tax: 34-2++ / Γ 3· yfí’CeX SJt ¹