EP1084222A1

EP1084222A1 - Detergents containing amylase and protease

Info

Publication number: EP1084222A1
Application number: EP99926390A
Authority: EP
Inventors: Beatrix Kottwitz; Horst-Dieter Speckmann; Karl-Heinz Maurer; Christian Nitsch
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1998-06-03
Filing date: 1999-05-25
Publication date: 2001-03-21
Also published as: WO1999063040A1; PL344470A1; US6380147B1; HUP0102632A2; PL189327B1; DE19824705A1; JP2002517555A

Abstract

The invention relates to detergents characterized in that they contain α-amylase from Bacillus amyloliquefaciens and protease from Bacillus lentus, optionally modified by genetic engineering, in addition to other usual ingredients compatible with said enzymes.

Description

Detergents and cleaning agents containing amylase and protease

The present invention relates to enzyme-containing detergents and cleaning agents which, in addition to the usual constituents, contain an amylase from Bacillus amyloliquefaciens and a specific protease.

Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and for this purpose have been used for a long time in detergents for dishes, but also in detergents for use in textile washing. For the most part, it was previously a thermostable amylase from Bacillus licheniformis, which is commercially available, for example, under the name Termamyl®. More recently, such agents have increasingly used genetically modified amylases, that is to say with amino acid sequences modified in comparison to naturally occurring amylases with the aid of genetic engineering methods. In addition to increasing their performance, the genetic modification of amylases essentially aims to increase the stability of the enzyme, in particular against the attack of oxidizing agents. One approach to achieve this goal, which was proposed in international patent application WO 94/18314, is to remove amino acids which are particularly susceptible to oxidation, such as methionine. Tryptophan. Cysteine or tyrosine, from the amino acid sequence of the amylase, or its replacement by other, more oxidation-stable amino acids. A similar procedure is also proposed in international patent application WO 95/21247, which recommends that at least one methionine in the amylase amino acid sequence be replaced by an amino acid which is neither methionine nor cysteine.

Although such genetic modifications can lead to improved amylase stability under certain application conditions, they do but not to increase the contribution of the amylase to the washing or cleaning performance of corresponding agents in which the amylase is contained.

In addition to amylases, further enzymes, in particular proteolytic enzymes, are used extensively in detergents, auxiliary washing agents and cleaning agents. Currently, proteases from the subtilisin family are used practically exclusively. These are extracellular proteins with a molecular weight in the range from approximately 20,000 to 45,000. Subtilisins are relatively unspecific enzymes which, in addition to the hydrolytic effect on peptide bonds, also have esterolytic properties (M. Bahn and RD Schmidt, Biotec 1, 119, 1987). Many representatives of the subtilisins are precisely characterized physically and chemically. Their spatial structure is often known in detail through X-ray structure analysis. This provides the prerequisites for molecular modeling and protein engineering in the form of targeted mutagenesis (Kraut, Ann. Rev. Biochem. 46, 331-358, 1977). Genetic modifications of proteases have been widely described; In June 1991, 219 protein variants of the subtilisins obtained by protein engineering were already known (A. Recktenwald et al., J. Biotechnol. 28, 1-23, 1993). Most of these variants were created to improve the stability of the proteases.

A protease from the subtilisin family that is stable and active under strongly alkaline conditions can be produced in Bacillus lentus (DSM 5483) as described in international patent application WO 91/02792. This Bacillus lentus alkaline protease (BLAP) can be produced by fermentation of the Bacillus licheniformis which has been transformed with an expression plasmid which carries the gene for BLAP under the control of the Bacillus licheniformis ATCC 53926 promoter. The composition as well as the spatial structure of BLAP is known (DW Godette et al., J. Mol. Biol. 228, 580-595, 1992). This protease is characterized by the sequence of 269 amino acids described in the cited literature, a calculated molecular weight of 26,823 daltons and a theoretical isoelectric point of 9.7. Variants of this Bacillus lentus DSM 5483 protease accessible by mutation are described in US Pat. No. 5,340,735. Under These are protease enzymes which, in particular when washing textiles made of proteinogenic fibers, for example textile fabrics made of natural silk or wool, repeatedly result in particularly low substance damage or destruction of the fiber dressings without loss of cleaning performance.

Surprisingly, it has now been found that the combination of an optionally genetically modified protease from Bacillus lentus and a naturally occurring α-amylase leads to unexpected synergistic performance improvements when used in detergents or cleaning agents.

The invention therefore relates to an amylase and protease-containing washing or cleaning agent which, in addition to the usual ingredients compatible with such enzymes, contains α-amylase from Bacillus amyloliquefaciens and protease from Bacillus lentus, which may or may not have been genetically modified.

Another object of the invention is the use of a combination of α-amylase from Bacillus amyloliquefaciens and protease from Bacillus lentus, which may have been genetically modified, to increase the cleaning performance of detergents and cleaning agents, in particular against starchy soiling, when used in especially aqueous washing and cleaning solutions.

α-Amylase from Bacillus amyloliquefaciens has long been known, for example from US Pat. No. 1,227,374. For example, it is commercially available under the name Amylase BAN®.

An agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of amylolytic protein per gram of the total agent. The protein concentration can be determined using known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948). The agent preferably has a proteolytic activity in the range from approximately 100 PE / g to approximately 100 OOO PE / g, in particular 300 PE / g to 8000 PE / g. The protease activity is determined according to the standardized method described below, as described in Tenside 7 (1970), 125: A solution containing 12 g / 1 casein and 30 mM sodium tripolyphosphate in water of 15 ° dH hardness (containing 0.058% by weight CaCl ₂ 2 H ₂ O, 0.028% by weight MgCl ₂ 6 H ₂ O and 0.042% by weight NaHCO,) is heated to 70 ° C., the pH is adjusted to 8 by adding 0.1 N NaOH. 5 set at 50 ° C. 200 ml of a solution of the enzyme to be tested in 2% by weight sodium tripolyphosphate buffer solution (pH 8.5) are added to 600 ml of the substrate solution. The reaction mixture is incubated at 50 ° C for 15 minutes. The reaction is then stopped by adding 500 ml of TCA solution (0.44 M trichloroacetic acid and 0.22 M sodium acetate in 3% acetic acid by volume) and cooling (ice bath at 0 ° C., 15 minutes). The TCA-insoluble protein is removed by centrifugation, 900 ml of the supernatant are diluted with 300 ml of 2N NaOH. The absorption of this solution at 290 nm is determined with the aid of an absorption spectrometer, the absorption zero value being obtained by measuring a centrifuged solution which is prepared by mixing 600 ml of the above-mentioned TCA solution with 600 ml of the above-mentioned substrate solution and then adding the enzyme solution determine is. The proteolytic activity of a protease solution, which causes an absorption of 0.500 OD under the specified measurement conditions, is defined as 10 PE (protease units) per ml.

In addition to the naturally occurring protease from Bacillus lentus, the proteases which can be used according to the invention also include genetically modified proteases of the abovementioned BL AP type, in which the amino acid leucine (L in the usual one-letter code) is replaced by aspartic acid (D) or glutamic acid (E) (L211D or L211E). These can be produced as described in international patent application WO 95/23221. Instead or in addition, further changes to the original Bacillus lentus protease, such as, for example, at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I. The use of a variant in which the amino acid exchanges S3T + V4I + V193M + V199I + L211D were carried out is particularly preferred. In the above-described protease nomenclature on the exchange of individual amino acids, it should be noted that the numbering of the amino acid positions in BLAP differs from that which is frequently found for the subtilisin BPN '. The numbering of positions 1 to 35 is identical in subtilisin BPN 'and BLAP; due to the lack of corresponding amino acids, positions 36 to 54 in BLAP correspond to positions 37 to 55 in BPN ', likewise positions 55 to 160 in BLAP correspond to positions 57 to 162 in BPN' and positions 161 to 269 correspond to those from 167 to 275 in BPN '.

The enzymes can, in particular for use in particulate compositions, as described for example in European patent EP 0 564 476 or in international patent application WO 94/23005 for other enzymes, be adsorbed on carriers and / or be embedded in coating substances in order to prevent them from occurring prematurely Protect inactivation. The combination of amylase and genetically modified protease, which is essential to the invention, can be incorporated by incorporating the two separate or, in a known manner, separately assembled enzymes or by protease and amylase assembled together in a granulate, as is known, for example, from international patent applications WO 96/00772 or WO 96/00773 , are used in agents according to the invention.

In addition to the enzyme combination used according to the invention, the washing and cleaning agents according to the invention, which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can in principle contain all known ingredients which are customary in such agents. In particular, the agents according to the invention can contain builder substances, surface-active surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer agents. inhibitors, foam regulators, silver corrosion inhibitors and colorants and fragrances.

The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C _P -C ₈ -monoolefins with a terminal or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkanesulfonates are also suitable. which are obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, as they are produced by esterification with a monoglycerol with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _{] 0} -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing are C -C _I2 _I6 - alkyl sulfates and _{_C12-I5} alkyl sulfates and C ₄ -C _{| 5} alkyl sulfates are particularly preferred. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂ alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl branched C ₉ -C alcohols with an average of 3.5 mol ethylene oxide (EO) or C. ₁₂ -C ₁₈ fatty alcohols with 1 to 4 EO. Because of their high foaming behavior, they are normally only used in relatively small amounts in detergents, for example in amounts of 1 to 5% by weight. used. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Other anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and or of N-methylglycine (sarcosides). The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-. Di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and also of alkyl phenols with 5 to 12 carbon atoms in the alkyl radical, can be used.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 C- Atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C _M alcohols with 7 EO, C _I3 -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C, ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Extremely low-foaming compounds are usually used in particular in cleaning agents for use in machine dishwashing processes. These preferably include C ₂ -C ₁₈ alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But one can also use other known low-foaming nonionic surfactants such as C _I2 -C ₁₈ -Alkylpolyethy- glycol-polybutylene glycol ethers containing up to 8 moles of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European patent application EP 0 300 305, so-called hydroxy mixed ethers. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R'CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear one or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

R ²

I.

R'-CO-N- [Z] (I)

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ⁴ -OR ⁵

I (ii)

R ³ -CO-N- [Z]

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{3 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here 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, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkylglycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533 . Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean “dimeric” in this way, but also correspondingly “trimeric” surfactants. Surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE 195 03 061. End group-blocked dimer and trimeric mixed ethers according to German patent application DE 195 13 391 itself i n especially by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used. Surfactants are present in detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, whereas agents for cleaning hard surfaces, in particular for machine cleaning of dishes , have lower surfactant contents of up to 10% by weight, in particular up to 5% by weight and preferably in the range from 0.5% by weight to 3% by weight.

An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphinephosphonic acid), ethylenediaminethoxy (meth) ethylenediaminethoxy (meth) ethylenediaminethoxy (meth) ethylenediamine (1) 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of the European patent EP 0 625 992 or the international patent application WO 92/18542 or the European patent EP 0 232 202, which are accessible by oxidation of polysaccharides or dextrins , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also polymerize small amounts of polymerizable substances without carboxylic acid functionality can hold. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances, the monomers being two unsaturated acids and / or their salts and as the third monomer vinyl alcohol and / or contain an esterified vinyl alcohol or a carbohydrate. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical . Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing agents according to the invention.

Particularly suitable water-soluble inorganic builder materials are alkali silicates, alkali carbonates and alkali phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric

Trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and Potassium salts. In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. %, used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA), are preferred . Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _{2x + 1} y H ₂ O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 22, especially 1, 9 to 4 and y is a number from 0 to 33 and are preferred values for x 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 described, can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 294 753, are used in a further preferred embodiment of agents according to the invention. Crystalline layered silicates of the formula (I) given above are sold by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ xH ₂ O, Kenyait), Na- SKS-2 (Na ₂ Si ₁₄ O ₂₉ xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O, ₇ xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ xH ₂ O , Makatit). Of these, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ 3H ₂ O, Kanemit), Na-SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline layered silicates is given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33 - 38 and in "Soap-oil-fat-waxes, 116 year, No. 20/1990" on pages 805 - 808 published articles. In a preferred embodiment of agents according to the invention, a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the (co) polymeric polycarboxylic acid mentioned above, as described for example in German patent application DE 198 19 187, or of alkali silicate and alkali carbonate is used as described, for example, in international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15. Builder substances can optionally be contained in the agents according to the invention in amounts of up to 90% by weight. They are preferably contained in amounts of up to 75% by weight. Detergents according to the invention have builder contents of in particular 5% by weight to 50% by weight. In agents according to the invention for cleaning hard surfaces, in particular for machine cleaning of dishes, the builder substance content is in particular 5% by weight to 88% by weight, with such agents preferably not using water-insoluble builder materials. In a preferred embodiment of agents according to the invention for in particular machine cleaning of dishes, 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight of alkali carbonate and 20% by weight to Contain 40 wt .-% alkali disilicate.

Suitable peroxygen compounds for use in agents according to the invention are, in particular, organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, including perborate, percarbonate, persilicate and / or Persulfate such as caroate should be considered. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. If an agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be useful.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG ), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylie Third glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95 / 17498 are known. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type can be present in the customary quantitative range, preferably in amounts of 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, based on the total agent.

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 European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. Enzymes which can be used in the agents in addition to the protease / amylase combination which is essential to the invention are those from the class of the lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. If appropriate, proteases or amylase other than the invention may also be present in addition to these. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus are particularly suitable. The optionally additionally used enzymes can, as described for example in international patent applications WO 92/1 1347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation. They are contained in the washing or cleaning agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight.

The organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, in addition to water include alcohols having 1 to 4 carbon atoms, in particular methanol. Ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the classes of compounds mentioned. Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

In addition, the agents can contain further constituents customary in washing and cleaning agents. These optional components include, in particular, enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners, and colorants and fragrances. In order to provide silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. A cleaning agent for hard surfaces according to the invention can also have an abrasive effect Contain components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.

To set a desired pH value which does not result from the mixture of the other components, the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid. Contain glutaric acid and / or adipic acid, but also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides. Such pH regulators are present in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

The color transfer inhibitors which are suitable for use in textile detergents according to the invention include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor. Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used . Textile detergents according to the invention can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.

In particular when used in machine processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.

The preparation of solid agents according to the invention is not difficult and can be carried out in a known manner, for example by spray drying or granulation, the enzymes and any further thermally sensitive ingredients, such as bleaching agents, optionally being added separately later. For the preparation of agents according to the invention with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1, a method known from European patent EP 0 486 592 is known. a method having an extrusion step is preferred. A further preferred production using a granulation process is described in European patent EP 0 642 576.

For the preparation of agents according to the invention in tablet form, which can consist of one or more phases, of one color or of more than one color and in particular of one layer or of more than one, in particular of two layers, the procedure is preferably such that all constituents - if appropriate one layer each - are combined in one Mixer mixed together and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN. In the case of multi-layer tablets in particular, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at press forces between 5 and 20 kN, in particular at 10 to 15 kN. In this way, break-resistant tablets, which nevertheless dissolve sufficiently quickly under application conditions, are obtained with breaking and bending strengths of normally 100 to 200 N, but preferably over 150 N. A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The shape of the tablets is arbitrary and can be round, oval or angular, intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of angular or cuboid tablets, which are mainly introduced via the metering device, for example the dishwasher, depends on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or of 24x38 mm.

Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. Examples

example 1

To determine the washing ability, cotton fabrics soiled with standardized test soiling were washed at 40 ° C (detergent dosage 76 g; water hardness 16 ° d; load 3.5 kg, short program) in a household washing machine (Miele® W 701). Table 1 below shows the washing results (in dE initial value minus dE after washing, measuring device Minolta® CR 310) for a detergent VI which contains 0.25% by weight of granules not according to the invention (Termamyl® 60T) and 0.25 % By weight of a protease granulate (activity 200,000 PE / g) with the Bacillus lentus protease, for a detergent V2, which was otherwise of the same composition, but instead of Termamyl® contained the same amount of protein of the genetically modified amylase Duramyl®, otherwise detergent V3 composed like VI, which contained the protein-identical amount of the genetically modified amylase Purafect® OxAm instead of Termamyl®, an otherwise detergent V4 composed like VI which contained the protein-equivalent amount of the fungamamase Fungamyl® instead of Termamyl®, and for a detergent Ml according to the invention, which was otherwise composed like VI, but instead of Termamyl® contains the protein-equal amount of the amylase from Bacillus amyloliquefaciens as the result of quadruple determinations.

Table 1: Washing results (dE AW - dE washed)

Soiling A: oatmeal / milk / cocoa B: oatmeal / water / cocoa C: chocolate pudding

It can be seen that the agent according to the invention has a washing performance which is clearly superior to the agents containing another amylase.

Example 2

Detergent (V5 or V6) for the automatic cleaning of dishes, containing 55% by weight sodium tripolyphosphate (calculated as anhydrous), 4% by weight amorphous sodium disilicate (calculated as anhydrous), 22% by weight sodium carbonate, 9% by weight. % Sodium perborate, 2% by weight TAED, 2% by weight nonionic surfactant and 1% by weight or 2% by weight amylase granules (Termamyl® 60T) and 1.4% by weight of a protease granules (activity 200,000 PE / g) with the Bacillus lentus protease (rest on 100 wt .-% water, perfume and dye), agents (V7 or V8), which were otherwise composed like V5 or V6, but instead Termamyl® protein-equal amounts of Duramyl® contained, as well as agents according to the invention (M2 or M3), which were otherwise composed like V5 or V6, but instead of Termamyl® containing protein-equal amounts of Bacillus amyloliquefaciens amylase, were tested as follows:

In a Miele® G 575 dishwasher (doses of 20 g each of the agent to be tested in the universal program, water hardness 14-16 ° dH, operating temperature 55 ° C), 6 plates with standardized starch soiling were washed and the remaining residue of the soiling was determined gravimetrically and in relation to the initial value before rinsing (= 100%). The table below shows the percentage of soiling removed.

Table 2: Cleaning performance [% starch removalj

It can be seen that the agents according to the invention are significantly superior in cleaning performance to agents not according to the invention.

Claims

claims

1. Protease and amylase-containing detergent or cleaning agent, characterized in that it contains, in addition to the usual ingredients compatible with such enzymes, α-amylase from Bacillus amyloliquefaciens and protease from Bacillus lentus, which may have been genetically modified.

2. Composition according to claim 1, characterized in that it contains amylase in amounts of 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, per gram of the total composition.

3. Composition according to claim 1 or 2, characterized in that it has a proteolytic activity in the range from 100 PE / g to 10,000 PE / g, in particular 300 PE / g to 8000 PE / g.

4. Agent according to one of claims 1 to 3, characterized in that it is a mutant protease in which the amino acid leucine present in the wild-type protease at position 21 1 (BL AP count) is replaced by aspartic acid or glutamic acid, contains.

5. Agent according to one of claims 1 to 4, characterized in that it contains a protease mutant in which at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or VI 991 has been carried out.

6. Composition according to claim 5, characterized in that the amino acid exchanges S3T + V4I + V 193M + V 1991 + L211 D have been made in the protease mutant.

7. Use of a combination of α-amylase from Bacillus amyloliquefaciens and protease from Bacillus lentus, which may have been genetically modified, to increase the cleaning performance of detergents and cleaning agents when used in aqueous washing and cleaning solutions. Use according to claim 7, characterized in that the cleaning performance compared to starchy soiling is increased.