EP0964911A1 - Protease and amylase-containing detergent - Google Patents

Protease and amylase-containing detergent

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Publication number
EP0964911A1
EP0964911A1 EP97954439A EP97954439A EP0964911A1 EP 0964911 A1 EP0964911 A1 EP 0964911A1 EP 97954439 A EP97954439 A EP 97954439A EP 97954439 A EP97954439 A EP 97954439A EP 0964911 A1 EP0964911 A1 EP 0964911A1
Authority
EP
European Patent Office
Prior art keywords
weight
protease
amylase
amino acid
mutant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP97954439A
Other languages
German (de)
French (fr)
Inventor
Beatrix Kottwitz
Horst Upadek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0964911A1 publication Critical patent/EP0964911A1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405—Glucanases
    • C12N9/2408—Glucanases acting on alpha -1,4-glucosidic bonds
    • C12N9/2411—Amylases
    • C12N9/2414—Alpha-amylase (3.2.1.1.)
    • C12N9/2417—Alpha-amylase (3.2.1.1.) from microbiological source
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/48—Hydrolases (3) acting on peptide bonds (3.4)
    • C12N9/50—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25)
    • C12N9/52—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea
    • C12N9/54—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea bacteria being Bacillus

Definitions

  • the present invention relates to enzyme-containing detergents which, in addition to the usual constituents, contain a certain protease and a certain amylase.
  • Enzymes are used extensively in washing, auxiliary washing and cleaning agents.
  • proteases from the subtilisin family are used. 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, RD Schmidt, Biotec j_, 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 so-called protein engineering in the form of targeted mutagenesis (Kraut, Ann. Rev. Biochem.
  • 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 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).
  • 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. Among these are protease enzymes, which in particular with multiple washing treatment of Textiles made of proteinogenic fibers, for example textile fabrics made of natural silk or wool, lead to particularly low substance damage or destruction of the fiber dressings without loss of cleaning performance.
  • Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and have also been used for a long time in dishwashing detergents, but also in detergents. It has been observed that the performance of amylases, which correspond to the enzymes found in nature, is relatively severely impaired by bleaching agents usually contained in such agents. In addition to increasing their performance, the genetic modification of amylases essentially aims to increase the stability against attack by oxidants.
  • the invention therefore relates to a protease- and amylase-containing textile detergent which, in addition to the usual ingredients compatible with such enzymes, is a mutant protease in which, at position 211 (BLAP count), the amino acid leucine present at this point in the wild-type protease is replaced by aspartic acid or glutamic acid and an amylase mutant in which at least one methionine, tryptophan, cysteine or tyrosine present in the wild-type amylase is removed or through another amino acid is exchanged, which in particular is not cysteine or methionine.
  • the agent preferably has a proteolytic activity in the range from about 100 PE / g to about 7500 PE / g, in particular 500 PE / g to 5000 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 3 ) is heated to 70 ° C., the pH is adjusted to 8 by adding 0.1 N NaOH, 5 set at 50 ° C.
  • 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.
  • the agent preferably has an amylolytic activity of 50 NU / g to 1000 NU / g, in particular 75 NU / g to 750 NU / g ("Novo units" per gram according to the Novo standard method, 1 kilo Novo unit is the amount of enzyme that breaks down 5.26 g of starch at pH 5.6 and 37 ° C., based on that from P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, page 149 described method).
  • proteases which can be used according to the invention include genetically modified proteases of the abovementioned BLAP type, in which, in position 21 1 (BLAP count), the amino acid leucine (L in the customary one-letter code) present in the wild-type protease at this point against aspartic acid (D) or glutamic acid (E) is exchanged (L211D or L211E). These can be produced as described in international patent application WO 95/23221.
  • other changes to the original Bacillus lentus protease such as at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I, may have been made.
  • Particularly preferred is the variant listed as F49 in the international patent application mentioned, in which the amino acid exchanges
  • amylases which can be used according to the invention include, in particular, genetically modified amylases which, by replacing the methionine in position 197 with another amino acid, in particular leucine, threonine, alanine, glycine, serine, isoleucine, asparagine or aspartic acid, are derived from the ⁇ - found in Bacillus licheniformis Derive amylase (wild-type amylase). Analogous to the nomenclature described above for proteases, these amylases are designated as M197L, M197T, M197A, M197G, M197S, Ml 971, M197N and M197D.
  • Wild-type amylases from other microorganisms such as Bacillus amyloliquefaciens or Bacillus stearothermophilus, whose amino acid sequence homology to Bacillus licheniformis amylase is known from international patent application WO 94/18314, can be used according to the invention.
  • Commercial genetically modified amylases in the sense of the invention are, for example, Duramyl® from Novo Nordisk and Purafect® OxAm from Genencor International.
  • the combination of genetically modified protease and genetically modified amylase which is essential to the invention, can be achieved by incorporating the two separate or, in a known manner, separately assembled enzymes or by means of protease and amylase made up together in a granulate, as for example from international patent applications WO 96/00772 or WO 96 / Known 00773 can be used in detergents according to the invention.
  • the detergents 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 compositions.
  • the agents according to the invention can in particular 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 further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, Contain dyes and fragrances.
  • the agents according to the invention can contain surfactants, anionic surfactants, nonionic surfactants and mixtures thereof being particularly suitable.
  • 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-alkylamines, vicinal diols, fatty acid esters and fatty acid amides are the in terms of the alkyl part correspond to the long-chain alcohol derivatives mentioned, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the surfactants of the sulfate type which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are used in the reaction of corresponding monoolefins with sulfur trioxide arise, as well as alpha-sulfofatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.
  • Surfactants are present in the 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.
  • 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 (methylene-phosphinophenonic acid), ethylenediamine (1) ethylenediamine (1) 1 -diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 or international patent application WO 92/18542 or European patent EP 0232 202, which are accessible by oxidation of polysaccharides or dextrins.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • 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.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
  • 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 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C -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.
  • 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 above upper limit are preferably in paste-like or liquid, in particular water-containing agents according to the invention.
  • Alkali silicates and polyphosphates are particularly suitable as water-soluble inorganic builder materials.
  • 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.
  • the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X are preferred. Amounts 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 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • 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 molar ratio Na O: SiO 2 of 1: 2 to 1: 2.8.
  • crystalline silicates which may be present alone or in a mixture with amorphous silicates
  • crystalline sheet silicates of the general formula Na 2 Si x O 2x + ⁇ y HO are preferably used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 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 in the general formula mentioned assumes the values .2 or 3.
  • ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 y H 2 0
  • ⁇ -sodium disilicate being obtainable, for example, by the method described in international patent application WO 91/08171.
  • ⁇ -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 described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0452 428 , can be used in 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 are used in a further preferred embodiment of agents according to the invention.
  • alkali aluminum silicate, in particular zeolite is also present as an additional builder substance
  • the weight ratio aluminum silicate to silicate, in each case based on anhydrous active substances is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Builder substances are contained in the detergents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • Suitable peroxygen compounds 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, such as perborate, percarbonate and / or persilicate.
  • 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, such as perborate, percarbonate and / or persilicate.
  • solid peroxygen compounds can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide is particularly preferred Form of aqueous solutions containing 3 wt .-% to 10 wt .-% hydrogen peroxide used.
  • a detergent 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.
  • 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.
  • 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
  • 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 known from the German patent application DE 4443 177 combinations of conventional bleach activators can be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • the sulfonimines known from European patents EP 0446 982 and EP 0 453 003 and or bleach-enhancing transition metal salts or transition metal complexes can also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 41 1, the manganese described in German patent application DE 44 16 438 , Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese com.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in conventional amounts, preferably in one Amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.
  • Enzymes which can be used in the compositions in addition to the protease / amylase combination which is essential to the invention are those from the class of the lipases, cutinases, PuUulanases, hemicellulases, cellulases, oxidases and peroxidases and mixtures thereof. If necessary, proteases and / or amylases other than those of 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 or Pseudomonas cepacia are particularly suitable.
  • the enzymes which are essential to the invention and, if appropriate, additionally used 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 detergents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 2% 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 with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned.
  • Such water-miscible solvents are preferably present in the detergents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention can contain systemic and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and or adipic acid also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides.
  • systemic and environmentally compatible acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and or adipic acid also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides.
  • pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • the agents can contain further constituents customary in washing and cleaning agents.
  • These optional components include, in particular, enzyme stabilizers, additional graying inhibitors such as carboxymethyl cellulose, color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyridine-N-oxide, foam inhibitors, for example organopolysiloxanes and / or paraffins, and optical brighteners, for example stilbene disulfonic acid derivatives.
  • the preparation of solid agents according to the invention presents no difficulties 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.
  • agents according to the invention with increased bulk density in particular in the range from 650 g / 1 to 950 g / 1, a process known from European patent EP 486 592 and having an extrusion step is preferred.
  • 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.
  • Table 1 below shows the washing results (in dE initial value minus dE after washing, measuring device Minolta® CR 310) for a detergent V2 which contains 0.6% by weight amylase granules (Termamyl® 60T) and 1.2% not according to the invention .-% of a protease granules (activity 200,000 PE / g) with the genetically modified protease F 49 according to WO 95/23221, for one Detergent VI, which was otherwise of the same composition, but contained BLAP in amounts of protein activity equal to BLAP instead of F 49, a detergent V3 which was otherwise composed of VI and which, instead of Termamyl®, contained the same amount of protein activity as the genetically modified amylase Duramyl®, an otherwise detergent V4 which was composed of VI instead of Termamyl®, the amount of the genetically modified Amylase Purafect® OxAm containing the same protein activity and for detergents Ml or M2 according to the invention, which were otherwise composed
  • Soiling A oatmeal / cocoa
  • B chocolate pudding
  • C milk / cocoa

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Abstract

The combination of a protease mutant, in which the amino acid leucine present in position 211 (BLAP (bacillus lentus alkaline protease) counting method) in the wild-type protease is exchanged at this location for an aspartic acid or glutamic acid, and of an amylase mutant, in which at least one methionine, tryptophane, cysteine or tyrosine present in the wild-type amylase is removed or exchanged for another amino acid which is in particular not cysteine or methionine, results in unexpected synergistic improvements in performance in textile detergents.

Description

Protease- und amylasehaltiges Waschmittel Protease and amylase detergent
Die vorliegende Erfindung betrifft enzymhaltige Waschmittel, die neben üblichen Bestandteilen eine bestimmte Protease und eine bestimmte Amylase enthalten.The present invention relates to enzyme-containing detergents which, in addition to the usual constituents, contain a certain protease and a certain amylase.
Enzyme, insbesondere proteolytische Enzyme, finden ausgedehnte Verwendung in Wasch-, Waschhilfs- und Reinigungsmitteln. Derzeit werden ausschließlich Proteasen aus der Subtilisinfamilie eingesetzt. Dabei handelt es sich um extrazelluläre Proteine mit einem Molekulargewicht im Bereich von etwa 20 000 bis 45 000. Subtilisine sind relativ unspezifische Enzyme, die neben der hydrolytischen Wirkung auf Peptidbindungen auch esterolytische Eigenschaften aufweisen (M. Bahn, R.D. Schmidt, Biotec j_, 119, 1987). Viele Vertreter der Subtilisine sind physikalisch und chemisch genau charakterisiert. Ihre räumliche Struktur ist durch Röntgenstrukturanalyse oft im Detail bekannt. Hierdurch sind die Voraussetzungen für molekulares Modelling und sogenanntes Protein Engineering in Form gezielter Mutagenese gegeben (Kraut, Ann. Rev. Biochem. 46, 331- 358, 1977). Gentechnische Modifikationen von Proteasen sind vielfach beschrieben; so waren im Juni 1991 bereits 219 durch Protein Engineering erhaltene Proteinvarianten der Subtilisine bekannt (A. Recktenwald et al., J.Biotechnol. 28, 1-23, 1993). Die meisten dieser Varianten wurden erzeugt, um die Stabilität der Proteasen zu verbessern.Enzymes, especially proteolytic enzymes, are used extensively in washing, auxiliary washing and cleaning agents. Currently, only proteases from the subtilisin family are used. 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, RD Schmidt, Biotec j_, 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 so-called 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.
Eine unter stark alkalischen Bedingungen stabile und aktive Protease aus der Subtilisinfamilie kann wie in der internationalen Patentanmeldung WO 91/02792 beschrieben in Bacillus lentus (DSM 5483) produziert werden. Diese Bacillus lentus alkalische Protease (BLAP) kann durch Fermentation von Bacillus licheniformis produziert werden, der mit einem Expressionsplasmid transformiert wurde, welches das Gen für BLAP unter der Kontrolle des Promotors aus Bacillus licheniformis ATCC 53926 trägt. Die Zusammensetzung wie auch die räumliche Struktur von BLAP ist bekannt (D.W. Godette et al. J.Mol.Biol. 228, 580-595,1992). Diese Protease ist durch die in der zitierten Literatur beschriebene Sequenz aus 269 Aminosäuren, ein rechnerisches Molekulargewicht von 26 823 Dalton und einen theoretischen isoelektrischen Punkt von 9,7 charakterisiert. Durch Mutation zugängliche Varianten dieser Bacillus lentus DSM 5483 Protease sind in der US-amerikanischen Patentschrift US 5 340 735 beschrieben. Unter diesen sind Proteaseenzyme, die bei insbesondere mehrfacher Waschbehandlung von Textilien aus proteinogenen Fasern, beispielsweise textilen Flächengebilden aus Naturseide oder Wolle, ohne Verlust an Reinigungsleistung zu besonders geringen Substanzschädigungen beziehungsweise Zerstörungen der Faserverbände fuhren.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 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. Among these are protease enzymes, which in particular with multiple washing treatment of Textiles made of proteinogenic fibers, for example textile fabrics made of natural silk or wool, lead to particularly low substance damage or destruction of the fiber dressings without loss of cleaning performance.
Amylasen haben die Aufgabe, die Entfernung stärkehaltiger Anschmutzungen durch die katalytische Hydrolyse des Stärke-Polysaccharids zu erleichtern und werden zu diesem Zweck ebenfalls seit längerer Zeit in Reinigungsmitteln für Geschirr, aber auch in Waschmitteln eingesetzt. Dabei ist beobachtet worden, daß die Leistung von Amylasen, die den in der Natur vorkommenden Enzymen entsprechen, durch in solchen Mitteln üblicherweise enthaltene Bleichmittel relativ stark beeinträchtigt wird. Neben der Erhöhung ihrer Leistungsfähigkeit hat die gentechnische Modifikation von Amylasen daher im wesentlichen die Stabilitätserhöhung gegen den Angriff von Oxdationsmitteln zum Ziel. Ein Ansatz zur Erreichung dieses Ziels, der in der internationalen Patentanmeldung WO 94/18314 vorgeschlagen wurde, besteht in der Entfernung besonders oxidationsanfälliger Aminosäuren, wie Methionin, Tryptophan, Cystein oder Tyrosin, aus der Aminosäuresequenz der Amylase, oder deren Austausch durch andere, oxidationsstabilere Aminosäuren. Ein ähnliches Vorgehen wird auch in der internationalen Patentanmeldung WO 95/21247 vorgeschlagen, die empfiehlt, in der Amylase- Aminosäuresequenz mindestens ein Methionin durch eine Aminosäure, die weder Methionin noch Cystein ist, auszutauschen.Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and have also been used for a long time in dishwashing detergents, but also in detergents. It has been observed that the performance of amylases, which correspond to the enzymes found in nature, is relatively severely impaired by bleaching agents usually contained in such agents. In addition to increasing their performance, the genetic modification of amylases essentially aims to increase the stability against attack by oxidants. 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 to replace them with other amino acids which are more stable to oxidation . 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.
Überraschenderweise wurde nun gefunden, daß die Kombination aus einer oben beschriebenen gentechnisch veränderten Protease und einer obengenannten gentechnisch veränderten Amylase zu unerwartetet synergistischen Leistungsverbesserungen führt, wenn man sie in Waschmitteln einsetzt.Surprisingly, it has now been found that the combination of an above-described genetically modified protease and an above-mentioned genetically modified amylase leads to unexpected synergistic performance improvements when used in detergents.
Gegenstand der Erfindung ist daher ein protease- und amylasehaltiges Textilwaschmittel, das neben üblichen mit derartigen Enzymen verträglichen Inhaltsstoffen eine Proteasemutante, bei der in Position 211 (BLAP-Zählung) die an dieser Stelle in der Wildtyp-Protease vorhandene Aminosäure Leucin gegen Asparaginsäure oder Glutaminsäure ausgetauscht ist, und eine Amylasemutante, bei der mindestens ein in der Wildtyp- Amylase vorhandenes Methionin, Tryptophan, Cystein oder Tyrosin entfernt oder durch eine andere Aminosäure ausgetauscht ist, die insbesondere nicht Cystein oder Methionin ist, enthält.The invention therefore relates to a protease- and amylase-containing textile detergent which, in addition to the usual ingredients compatible with such enzymes, is a mutant protease in which, at position 211 (BLAP count), the amino acid leucine present at this point in the wild-type protease is replaced by aspartic acid or glutamic acid and an amylase mutant in which at least one methionine, tryptophan, cysteine or tyrosine present in the wild-type amylase is removed or through another amino acid is exchanged, which in particular is not cysteine or methionine.
Vorzugsweise weist das Mittel eine proteolytische Aktivität im Bereich von etwa lOO PE/g bis etwa 7500 PE/g, insbesondere 500 PE/g bis 5000 PE/g auf. Die Proteaseaktivität wird gemäß dem nachfolgend beschriebenen standardisierten Verfahren, wie in Tenside 7 (1970), 125 beschrieben, bestimmt: Eine Lösung, die 12 g/1 Casein und 30 mM Natriumtripolyphosphat in Wasser des Härtegrades 15 °dH (enthaltend 0,058 Gew.-% CaCl2 2 H2O, 0,028 Gew.-% MgCl2 6 H2O und 0,042 Gew.-% NaHCO3) wird auf 70 °C erwärmt, der pH- Wert wird durch Zugabe von 0,1 N NaOH auf 8,5 bei 50 °C eingestellt. Zu 600 ml der Substratlösung werden 200 ml einer Lösung des zu testenden Enzyms in 2 gewichtsprozentiger Natriumtripolyphosphat-Pufferlösung (pH 8,5) gegeben. Die Reaktionsmischung wird bei 50 °C für 15 Minuten inkubiert. Die Reaktion wird danach durch Zugabe von 500 ml TCA-Lösung (0,44 M Trichloressigsäure und 0,22 M Natriumacetat in 3 volumenprozentiger Essigsäure) und Abkühlen (Eisbad bei 0 °C, 15 Minuten) gestoppt. Das TCA-unlösliche Protein wird durch Zentrifugation entfernt, 900 ml des Überstandes werden mit 300 ml 2 N NaOH verdünnt. Die Absorption dieser Lösung bei 290 nm wird mit Hilfe eines Absorptionsspektrometers bestimmt, wobei der Absorptionsnullwert durch das Messen einer zentrifugierten Lösung, die durch Mischen von 600 ml der obengenannten TCA-Lösung mit 600 ml der obengenannten Substratlösung und anschließender Zugabe der Enzymlösung hergestellt wird, zu bestimmen ist. Die proteolytische Aktivität einer Proteaselösung, die unter den angegebenen Meßbedingungen eine Absorption von 0,500 OD bewirkt, wird zu 10 PE (Protease- Einheiten) pro ml definiert.The agent preferably has a proteolytic activity in the range from about 100 PE / g to about 7500 PE / g, in particular 500 PE / g to 5000 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 3 ) 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.
Das Mittel weist vorzugsweise eine amylolytische Aktivität von 50 NU/g bis 1000 NU/g, insbesondere 75 NU/g bis 750 NU/g, auf ("Novo-Units" pro Gramm gemäß der Standard-Methode der Firma Novo, wobei 1 Kilo-Novo-Unit die Enzymmenge ist, die 5,26 g Stärke bei pH 5,6 und 37 °C abbaut, basierend auf der von P. Bernfeld in S.P. Colowick und N.D. Kaplan, Methods in Enzymology, Band 1, 1955, Seite 149 beschriebenen Methode). Zu den erfindungsgemäß brauchbaren Proteasen zählen gentechnisch veränderte Proteasen des obengenannten BLAP-Typs, bei denen in Position 21 1 (BLAP -Zählung) die an dieser Stelle in der Wildtyp-Protease vorhandene Aminosäure Leucin (L im gebräuchlichen Ein-Buchstaben-Code) gegen Asparaginsäure (D) beziehungsweise Glutaminsäure (E) ausgetauscht ist (L211D beziehungsweise L211E). Diese können wie in der internationalen Patentanmeldung WO 95/23221 beschrieben hergestellt werden. Zusätzlich können weitere Veränderungen gegenüber der ursprünglichen Bacillus lentus- Protease, wie beispielsweise mindestens einer der Aminosäureaustausche S3T, V4I, R99G, R99A, R99S, A188P, V193M und/oder V199I, vorgenommen worden sein. Besonders bevorzugt ist die in der genannten internationalen Patentanmeldung als F49 aufgeführte Variante, bei welcher die AminosäureaustauscheThe agent preferably has an amylolytic activity of 50 NU / g to 1000 NU / g, in particular 75 NU / g to 750 NU / g ("Novo units" per gram according to the Novo standard method, 1 kilo Novo unit is the amount of enzyme that breaks down 5.26 g of starch at pH 5.6 and 37 ° C., based on that from P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, page 149 described method). The proteases which can be used according to the invention include genetically modified proteases of the abovementioned BLAP type, in which, in position 21 1 (BLAP count), the amino acid leucine (L in the customary one-letter code) present in the wild-type protease at this point against aspartic acid (D) or glutamic acid (E) is exchanged (L211D or L211E). These can be produced as described in international patent application WO 95/23221. In addition, other changes to the original Bacillus lentus protease, such as at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I, may have been made. Particularly preferred is the variant listed as F49 in the international patent application mentioned, in which the amino acid exchanges
S3T + V4I + A188P + V193M + V199I + L211D vorgenommen wurden. Bei der vorstehend beschriebenen Proteasenomenklatur über den Austausch einzelner Aminosäuren ist zu beachten, daß die Numerierung der Aminosäurepositionen in BLAP sich von der häufig anzutreffenden des Subtilisin BPN' unterscheidet. Die Numerierung der Positionen 1 bis 35 ist identisch in Subtilisin BPN' und BLAP; aufgrund fehlender korrespondierender Aminosäuren entsprechen die Positionen 36 bis 54 in BLAP den Positionen 37 bis 55 in BPN', ebenso die Positionen 55 bis 160 in BLAP den Positionen 57 bis 162 in BPN' und die Positionen 161 bis 269 denen von 167 bis 275 in BPN'.S3T + V4I + A188P + V193M + V199I + L211D. 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 '.
Zu den erfindungsgemäß brauchbaren Amylasen gehören insbesondere gentechnisch veränderte Amylasen, die sich durch Austausch des Methionins in Position 197 durch eine andere Aminosäure, insbesondere Leucin, Threonin, Alanin, Glycin, Serin, Isoleucin, Asparagin oder Asparaginsäure, von der in Bacillus licheniformis vorkommenden α- Amylase (Wildtyp-Amylase) ableiten. Analog der oben für Proteasen beschriebenen Nomenklatur werden diese Amylasen als M197L, M197T, M197A, M197G, M197S, Ml 971, M197N und M197D bezeichnet. Die Entfernung sonstiger Aminosäuren, insbesondere an den Positionen 1 und/oder 2 (mit (1-2)* bezeichnet), und/oder weitere Aminosäureaustausche wie L3V, M15T, M15L, R23K, S29A, A30E, Y31H, A33S, E34D, H68Q, W138F, W138Y, R242P, H35I, E255P, T341P, Q374P, E458D, P459T, V461K, N463G und/oder E465D etc., die aus den obengenannten internationalen Patentanmeldungen bekannt sind, können vorgenommen werden. Auch entsprechend veränderte Wildtyp-Amylasen aus anderen Mikroorganismen, wie Bacillus amyloliquefaciens oder Bacillus stearothermophilus, deren Aminosäuresequenz-Homologie zur Amylase aus Bacillus licheniformis aus der internationalen Patentanmeldung WO 94/18314 bekannt ist, können erfindungsgemäß eingesetzt werden. Handelsübliche gentechnisch verändertere Amylasen im Sinne der Erfindung sind zum Beispiel Duramyl® von Novo Nordisk und Purafect® OxAm von Genencor International.The amylases which can be used according to the invention include, in particular, genetically modified amylases which, by replacing the methionine in position 197 with another amino acid, in particular leucine, threonine, alanine, glycine, serine, isoleucine, asparagine or aspartic acid, are derived from the α- found in Bacillus licheniformis Derive amylase (wild-type amylase). Analogous to the nomenclature described above for proteases, these amylases are designated as M197L, M197T, M197A, M197G, M197S, Ml 971, M197N and M197D. The removal of other amino acids, in particular at positions 1 and / or 2 (denoted by (1-2) *), and / or further amino acid exchanges such as L3V, M15T, M15L, R23K, S29A, A30E, Y31H, A33S, E34D, H68Q , W138F, W138Y, R242P, H35I, E255P, T341P, Q374P, E458D, P459T, V461K, N463G and / or E465D etc. known from the above-mentioned international patent applications can be made. Also changed accordingly Wild-type amylases from other microorganisms, such as Bacillus amyloliquefaciens or Bacillus stearothermophilus, whose amino acid sequence homology to Bacillus licheniformis amylase is known from international patent application WO 94/18314, can be used according to the invention. Commercial genetically modified amylases in the sense of the invention are, for example, Duramyl® from Novo Nordisk and Purafect® OxAm from Genencor International.
Die erfϊndungswesentliche Kombination aus gentechnisch veränderter Protease und gentechnisch veränderter Amylase kann durch Einarbeitung der zwei separaten beziehungsweise in bekannter Weise separat konfektionierten Enzyme oder durch gemeinsam in einem Granulat konfektionierte Protease und Amylase, wie zum Beispiel aus den internationalen Patentanmeldungen WO 96/00772 oder WO 96/00773 bekannt, in erfindungsgemäßen Waschmitteln eingesetzt werden.The combination of genetically modified protease and genetically modified amylase, which is essential to the invention, can be achieved by incorporating the two separate or, in a known manner, separately assembled enzymes or by means of protease and amylase made up together in a granulate, as for example from international patent applications WO 96/00772 or WO 96 / Known 00773 can be used in detergents according to the invention.
Die erfindungsgemäßen Waschmittel, die als insbesondere pulverformige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder Suspensionen vorliegen können, können außer der erfϊndungsgemäß eingesetzten Enzymkombination im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Bleichmittel auf Basis organischer und/oder anorganischer Persauerstoffverbindungen, Bleichaktivatoren, wassermischbare organische Lösungsmittel, zusätzliche Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Schaumregulatoren, Färb- und Duftstoffe enthalten.In addition to the enzyme combination used according to the invention, the detergents 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 compositions. The agents according to the invention can in particular 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 further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, Contain dyes and fragrances.
Die erfindungsgemäßen Mittel können Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxy- lierungsprodukte von Alkylglykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylether- gruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungs- produkte von N-Alkylaminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomem im Alkylrest brauchbar.The agents according to the invention can contain surfactants, anionic surfactants, nonionic surfactants and mixtures thereof being particularly suitable. 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. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides are the in terms of the alkyl part correspond to the long-chain alcohol derivatives mentioned, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat-Gruppen mit bevorzugt Alkaliionen als Kationen enthalten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat-Typs gehören die Salze der Schwefelsäurehalbester von Fettalkoholen mit 12 bis 18 C-Atomen und die Sulfatierungs- produkte der genannten nichtionischen Tenside mit niedrigem Ethoxylierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkylbenzolsulfonate mit 9 bis 14 C-Atomen im Alkylteil, Alkansulfonate mit 12 bis 18 C-Atomen, sowie Olefin- sulfonate mit 12 bis 18 C-Atomen, die bei der Umsetzung entsprechender Monoolefine mit Schwefeltrioxid entstehen, sowie alpha-Sulfofettsäureester, die bei der Sulfonierung von Fettsäuremethyl- oder -ethylestern entstehen.Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The surfactants of the sulfate type which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are used in the reaction of corresponding monoolefins with sulfur trioxide arise, as well as alpha-sulfofatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.
Tenside sind in den erfindungsgemäßen Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten.Surfactants are present in the 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.
Ein erfindungsgemäßes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, insbesondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessig- säure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylen- phosphonsäure), Ethylendiamintetrakis(methylenphosphonsäure) und 1-Hydroxyethan- 1 , 1 -diphosphonsäure, polymere Hydroxy Verbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden beziehungsweise Dextrinen zugänglichen Polycarboxylate der internationalen Patentanmeldung WO 93/16110 beziehungsweise der internationalen Patentanmeldung WO 92/18542 oder der europäischen Patentschrift EP 0232 202, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 5 000 und 200 000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 50 000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50 000 bis 100 000 auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinyl- ethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Builder- substanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder einem veresterten Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8-Carbonsäure und vorzugsweise von einer C3-C -Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C -C8-Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Alkyl- oder Arylrest substituiert ist, sein. Derartige Polymere lassen sich insbesondere nach Verfahren herstellen, die in der deutschen Patentschrift DE 42 21 381 und der deutschen Patentanmeldung DE 43 00 772 beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäure- salze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt.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 (methylene-phosphinophenonic acid), ethylenediamine (1) ethylenediamine (1) 1 -diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 or international patent application WO 92/18542 or European patent EP 0232 202, which are accessible by oxidation of polysaccharides or dextrins. polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also have small proportions polymerizable substances without carboxylic acid functionality in copolymerized form. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. 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 which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer. 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 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C -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.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.- % enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenformigen oder flüssigen, insbesondere wasserhaltigen, erfϊndungsgemäßen Mitteln eingesetzt.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 above upper limit are preferably in paste-like or liquid, in particular water-containing agents according to the invention.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkalisilikate und Polyphosphate, vorzugsweise Natriumtripolyphosphat, in Betracht. Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenformigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm.Alkali silicates and polyphosphates, preferably sodium tripolyphosphate, are particularly suitable as water-soluble inorganic builder materials. 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 detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, are preferred. Amounts 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.
Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den erfindungsgemäßen Mitteln als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu Si02 unter 0,95, insbesondere von 1 :1,1 bis 1 :12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na O:SiO2 von 1:2 bis 1 :2,8. Solche mit einem molaren Verhältnis Na2O:SiO2 von 1 :1,9 bis 1 :2,8 können nach dem Verfahren der europäischen Patentanmeldung EP 0 425 427 hergestellt werden. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+ι y H O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte ftir x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte .2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si2O5 y H20) bevorzugt, wobei ß-Natriumdi- silikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO 91/08171 beschrieben ist. δ-Natriumsilikate mit einem Modul zwischen 1,9 und 3,2 können gemäß den japanischen Patentanmeldungen JP 04/238 809 oder JP 04/260 610 hergestellt werden. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, herstellbar wie in den europäischen Patentanmeldungen EP 0 548 599, EP 0 502 325 und EP 0452 428 beschrieben, können in erfϊndungsgemäßen Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es nach dem Verfahren der europäischen Patentanmeldung EP 0 436 835 aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5, wie sie nach den Verfahren der europäischen Patentschriften EP 0 164 552 und/oder EP 0 293 753 erhältlich sind, werden in einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel eingesetzt. Falls als zusätzliche Buildersubstanz auch Alkali- alumosilikat, insbesondere Zeolith, vorhanden ist, beträgt das Gewichtsverhältnis Alumo- silikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, vorzugsweise 1 : 10 bis 10: 1. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amorphem Alkalisilikat zu kristallinem Alkalisilikat vorzugsweise 1 :2 bis 2:1 und insbesondere 1 :1 bis 2:1.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 molar ratio Na O: SiO 2 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. As crystalline silicates, which may be present alone or in a mixture with amorphous silicates, crystalline sheet silicates of the general formula Na 2 Si x O 2x + ι y HO are preferably used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 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 in the general formula mentioned assumes the values .2 or 3. In particular are Both β- and δ-sodium disilicate (Na 2 Si 2 O 5 y H 2 0) are preferred, with β-sodium disilicate being obtainable, 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 described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0452 428 , 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 0 293 753, are used in a further preferred embodiment of agents according to the invention. If alkali aluminum silicate, in particular zeolite, is also present as an additional builder substance, the weight ratio aluminum silicate to silicate, in each case based on anhydrous active substances, is preferably 1:10 to 10: 1. In agents which contain both amorphous and crystalline alkali silicates , the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
Buildersubstanzen sind in den erfindungsgemäßen Waschmitteln vorzugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-%, enthalten.Builder substances are contained in the detergents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
Als geeignete Persauerstoffverbindungen kommen insbesondere organische Persäuren beziehungsweise persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Per- benzoesäure oder Salze der Diperdodecandisäure, Wasserstoffperoxid und unter den Waschbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, in Betracht. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Besonders bevorzugt wird Alkalipercarbonat, Alkaliperborat-Monohydrat oder Wasserstoffperoxid in Form wäßriger Lösungen, die 3 Gew.-% bis 10 Gew.-% Wasserstoffperoxid enthalten, eingesetzt. Falls ein erfindungsgemäßes Waschmittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-%, vorhanden. Der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat kann zweckdienlich sein.Suitable peroxygen compounds 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, such as perborate, percarbonate and / or persilicate. 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. Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide is particularly preferred Form of aqueous solutions containing 3 wt .-% to 10 wt .-% hydrogen peroxide used. If a detergent 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.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl- 2,4-dioxohexahydro-l,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und die aus den deutschen Patentanmeldungen DE 196 16 693 und DE 196 16 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren in der europäischen Patentanmeldung EP 0 525 239 beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den internationalen Patentanmeldungen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 und WO 95/17498 bekannt sind. Die aus der deutschen Patentanmeldung DE 196 16 769 bekannten hydrophil substituierten Acylacetale und die in der deutschen Patentanmeldung DE 196 16 770 sowie der internationalen Patentanmeldung WO 95/14075 beschriebenen Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch die aus der deutschen Patentanmeldung DE 4443 177 bekannten Kom- binationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren sind im üblichen Mengenbereich, vorzugsweise in Mengen von 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten.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 known from the German patent application DE 4443 177 combinations of conventional bleach activators can be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren oder an deren Stelle können auch die aus den europäischen Patentschriften EP 0446 982 und EP 0 453 003 bekannten Sulfonimine und oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren enthalten sein. Zu den in Frage kommenden Übergangsmetallverbindungen gehören insbesondere die aus der deutschen Patentanmeldung DE 195 29 905 bekannten Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Salenkomplexe und deren aus der deutschen Patentanmeldung DE 196 20 267 bekannte N- Analogverbindungen, die aus der deutschen Patentanmeldung DE 195 36 082 bekannten Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Carbonylkomplexe, die in der deutschen Patentanmeldung DE 196 05 688 beschriebenen Mangan-, Eisen-, Cobalt-, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden, die aus der deutschen Patentanmeldung DE 196 20 41 1 bekannten Cobalt-, Eisen-, Kupfer- und Ruthenium- Amminkomplexe, die in der deutschen Patentanmeldung DE 44 16 438 beschriebenen Mangan-, Kupfer- und Cobalt-Komplexe, die in der europäischen Patentanmeldung EP 0 272 030 beschriebenen Cobalt-Komplexe, die aus der europäischen Patentanmeldung EP 0 693 550 bekannten Mangan-Komplexe, die aus der europäischen Patentschrift EP 0 392 592 bekannten Mangan-, Eisen-, Cobalt- und Kupfer-Komplexe, die aus den internationalen Patentanmeldungen WO 96/23859, WO 96/23860 und WO 96/23861 bekannten Cobalt-Komplexe und/oder die in der europäischen Patentschrift EP 0 443 651 oder den europäischen Patentanmeldungen EP 0458 397, EP 0458 398, EP 0 549 271, EP 0 549272, EP 0 544490 und EP 0 544 519 beschriebenen Mangan- Komplexe. Kombinationen aus Bleichaktivatoren und Übergangsmetall- Bleichkatalysatoren sind beispielsweise aus der deutschen Patentanmeldung DE 196 13 103 und der internationalen Patentanmeldung WO 95/27775 bekannt. Bleichverstärkende Übergangsmetallkomplexe, insbesondere mit den Zentralatomen Mn, Fe, Co, Cu, Mo, V, Ti und/oder Ru, werden in üblichen Mengen, vorzugsweise in einer Menge bis zu 1 Gew.-%, insbesondere von 0,0025 Gew.-% bis 0,25 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,1 Gew.-%, jeweils bezogen auf gesamtes Mittel, eingesetzt.In addition to the conventional bleach activators listed above or in their place, the sulfonimines known from European patents EP 0446 982 and EP 0 453 003 and or bleach-enhancing transition metal salts or transition metal complexes can also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 41 1, the manganese described in German patent application DE 44 16 438 , Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese com. Known from European patent application EP 0 693 550 plexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592, the cobalt complexes known from international patent applications WO 96/23859, WO 96/23860 and WO 96/23861 and / or the manganese complexes described in European patent EP 0 443 651 or European patent applications EP 0458 397, EP 0458 398, EP 0 549 271, EP 0 549272, EP 0 544490 and EP 0 544 519. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in conventional amounts, preferably in one Amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.
Als in den Mitteln zusätzlich zur erfϊndungswesentlichen Protease/ Amylase-Kombination verwendbare Enzyme kommen solche aus der Klasse der Lipasen, Cutinasen, PuUulanasen, Hemicellulasen, Cellulasen, Oxidasen und Peroxidasen sowie deren Gemische in Frage. Gegebenenfalls können auch andere als die erfϊndungswesentlichen Proteasen und/oder Amylasen zusätzlich zu diesen vorhanden sein. Besonders geeignet sind aus Pilzen oder Bakterien, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes oder Pseudomonas cepacia gewonnene enzymatische Wirkstoffe. Die erfindungswesentlichen und die gegebenenfalls zusätzlich verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/1 1347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Waschmitteln vorzugsweise in Mengen bis zu 5 Gew.-%, insbesondere von 0,2 Gew.-% bis 2 Gew.-%, enthalten.Enzymes which can be used in the compositions in addition to the protease / amylase combination which is essential to the invention are those from the class of the lipases, cutinases, PuUulanases, hemicellulases, cellulases, oxidases and peroxidases and mixtures thereof. If necessary, proteases and / or amylases other than those of 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 or Pseudomonas cepacia are particularly suitable. The enzymes which are essential to the invention and, if appropriate, additionally used 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 detergents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 2% by weight.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, neben Wasser verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylen- glykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Waschmitteln vorzugsweise in Mengen nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhanden.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 with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned. Such water-miscible solvents are preferably present in the detergents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH- Werts können die erfindungsgemäßen Mittel System- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1,2 Gew. -% bis 17 Gew.-%, enthalten.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 systemic and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and or adipic acid also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.
Zusätzlich können die Mittel weitere in Wasch- und Reinigungsmitteln übliche Bestandteile enthalten. Zu diesen fakultativen Bestandteilen gehören insbesondere Enzymstabilisatoren, zusätzliche Vergrauungsinhibitoren wie Carboxymethylcellulose, Farbübertragungsinhibitoren, beispielsweise Polyvinylpyrrolidon oder Polyvinylpyridin- N-oxid, Schauminhibitoren, beispielsweise Organopolysiloxane und/oder Paraffine, und optische Aufheller, beispielsweise Stilbendisulfonsäurederivate.In addition, the agents can contain further constituents customary in washing and cleaning agents. These optional components include, in particular, enzyme stabilizers, additional graying inhibitors such as carboxymethyl cellulose, color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyridine-N-oxide, foam inhibitors, for example organopolysiloxanes and / or paraffins, and optical brighteners, for example stilbene disulfonic acid derivatives.
Die Herstellung erfϊndungsgemäßer fester Mittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei die Enzyme und eventuelle weitere thermisch empfindliche Inhaltsstoffe wie zum Beispiel Bleichmittel gegebenenfalls später separat zugesetzt werden. Zur Herstellung erfindungsgemäßer Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/1 bis 950 g/1, ist ein aus der europäischen Patentschrift EP 486 592 bekanntes, einen Extrusionschritt aufweisendes Verfahren bevorzugt. Flüssige beziehungsweise pastöse erfindungsgemäße Wasch- oder Reinigungsmittel in Form von übliche Lösungsmittel enthaltenden Lösungen werden in der Regel durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.The preparation of solid agents according to the invention presents no difficulties 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 process known from European patent EP 486 592 and having an extrusion step is preferred. 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.
BeispieleExamples
Zur Bestimmung des Waschvermögens wurden mit standardisierten Testanschmutzungen verunreinigte Baumwollgewebe bei 40°C (Waschmitteldosierung 76 g; Wasserhärte 16 °d; Beladung 3,5 kg, Kurzprogramm) in einer Haushaltswaschmaschine (AEG Öko Lavamat® 694) gewaschen. In der nachfolgenden Tabelle 1 sind die Waschergebnisse (in dE Anfangswert minus dE nach dem Waschen, Meßgerät Minolta® CR 310) für ein Waschmittel V2, das 0,6 Gew.-% nicht erfϊndungsgemäßes Amylasegranulat (Termamyl® 60T) und 1,2 Gew.-% eines Proteasegranulats (Aktivität 200 000 PE/g) mit der gentechnisch veränderten Protease F 49 gemäß WO 95/23221 enthielt, für ein Waschmittel VI, das ansonsten gleich zusammengesetzt war, aber statt F 49 proteinaktivitätsgleiche Mengen BLAP enthielt, ein ansonsten wie VI zusammengesetztes Waschmittel V3, das statt Termamyl® die proteinaktivitätsgleiche Menge der gentechnisch veränderten Amylase Duramyl® enthielt, ein ansonsten wie VI zusammengesetztes Waschmittel V4, das statt Termamyl® die proteinaktivitätsgleiche Menge der gentechnisch veränderten Amylase Purafect® OxAm enthielt, und für erfindungsgemäße Waschmittel Ml beziehungsweise M2, die ansonsten wie V2 zusammengesetzt waren, aber statt Termamyl® die proteinaktivitätsgleiche Menge der gentechnisch veränderten Amylase Duramyl® beziehungsweise der gentechnisch veränderten Amylase Purafect® OxAm als Ergebnis von Doppelbestimmungen angegeben.To determine the washability, contaminated cotton fabrics were washed with standardized test soiling at 40 ° C (detergent dosage 76 g; water hardness 16 ° d; load 3.5 kg, short program) in a household washing machine (AEG Öko Lavamat® 694). Table 1 below shows the washing results (in dE initial value minus dE after washing, measuring device Minolta® CR 310) for a detergent V2 which contains 0.6% by weight amylase granules (Termamyl® 60T) and 1.2% not according to the invention .-% of a protease granules (activity 200,000 PE / g) with the genetically modified protease F 49 according to WO 95/23221, for one Detergent VI, which was otherwise of the same composition, but contained BLAP in amounts of protein activity equal to BLAP instead of F 49, a detergent V3 which was otherwise composed of VI and which, instead of Termamyl®, contained the same amount of protein activity as the genetically modified amylase Duramyl®, an otherwise detergent V4 which was composed of VI instead of Termamyl®, the amount of the genetically modified Amylase Purafect® OxAm containing the same protein activity and for detergents Ml or M2 according to the invention, which were otherwise composed like V2, but instead of Termamyl® the amount of the same activity as the protein activity of the genetically modified Amylase Duramyl® or the genetically modified Amylase Purafect® OxAm stated as the result of duplicate determinations.
Tabelle 1 : Waschergebnisse (dE AW - dE gewaschen)Table 1: Washing results (dE AW - dE washed)
Anschmutzung A: Haferflocken/Kakao B: Schokoladenpudding C: Milch/Kakao Soiling A: oatmeal / cocoa B: chocolate pudding C: milk / cocoa

Claims

Patentansprüche claims
1. Protease- und amylasehaltiges Textilwaschmittel, dadurch gekennzeichnet, daß es neben üblichen mit derartigen Enzymen verträglichen Inhaltsstoffen eine Proteasemutante, bei der in Position 211 (BLAP-Zählung) die an dieser Stelle in der Wildtyp-Protease vorhandene Aminosäure Leucin gegen Asparaginsäure oder Glutaminsäure ausgetauscht ist, und eine Amylasemutante, bei der mindestens ein in der Wildtyp-Amylase vorhandenes Methionin, Tryptophan, Cystein oder Tyrosin entfernt oder durch eine andere Aminosäure ausgetauscht ist, die insbesondere nicht Cystein oder Methionin ist, enthält.1. Protease and amylase-containing textile detergent, characterized in that, in addition to the usual ingredients compatible with such enzymes, a mutant protease in which the amino acid leucine present in the wild-type protease at position 211 (BLAP count) is replaced by aspartic acid or glutamic acid and an amylase mutant in which at least one methionine, tryptophan, cysteine or tyrosine present in the wild-type amylase is removed or replaced by another amino acid which is in particular not cysteine or methionine.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es eine proteolytische Aktivität im Bereich von 100 PE/g bis 7500 PE/g, insbesondere 500 PE/g bis 5000 PE/g aufweist.2. Composition according to claim 1, characterized in that it has a proteolytic activity in the range from 100 PE / g to 7500 PE / g, in particular 500 PE / g to 5000 PE / g.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es eine amylolytische Aktivität im Bereich 50 NU/g bis 1000 NU/g, insbesondere 75 NU/g bis 750 NU/g aufweist.3. Composition according to claim 1 or 2, characterized in that it has an amylolytic activity in the range 50 NU / g to 1000 NU / g, in particular 75 NU / g to 750 NU / g.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß in der Proteasemutante der Aminosäureaustausch L211D oder L211E vorgenommen worden ist.4. Agent according to one of claims 1 to 3, characterized in that the amino acid exchange L211D or L211E has been made in the protease mutant.
5. Mittel nach Anspruch 4, dadurch gekennzeichnet, daß in der Proteasemutante zusätzlich mindestens einer der Aminosäureaustausche S3T, V4I, R99G, R99A, R99S, A188P, V193M und/oder V199I vorgenommen worden ist.5. Composition according to claim 4, characterized in that in the protease mutant at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I has also been carried out.
6. Mittel nach Anspruch 5, dadurch gekennzeichnet, daß in der Proteasemutante die Aminosäureaustausche S3T + V4I + A188P + V193M + V199I + L211D vorgenommen worden sind.6. Composition according to claim 5, characterized in that the amino acid exchanges S3T + V4I + A188P + V193M + V199I + L211D have been made in the protease mutant.
7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß in der Amylasemutante der Aminosäureaustausch M197L, M197T, M197A, M197G, M197S, Ml 971, M197N oder M197D vorgenommen worden ist.7. Composition according to one of claims 1 to 6, characterized in that in the amylase mutant the amino acid exchange M197L, M197T, M197A, M197G, M197S, Ml 971, M197N or M197D has been made.
8. Mittel nach Anspruch 7, dadurch gekennzeichnet, daß in der Amylasemutante die Aminosäuren an den Positionen 1 und/oder 2 entfernt worden sind.8. Composition according to claim 7, characterized in that the amino acids at positions 1 and / or 2 have been removed in the amylase mutant.
9. Mittel nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß in der Amylasemutante zusätzlich mindestens einer der Aminosäureaustausche L3V, M15T, M15L, R23K, S29A, A30E, Y31H, A33S, E34D, H68Q, W138F, W138Y, R242P, H35I, E255P, T341P, Q374P, E458D, P459T, V461K, N463G und/oder E465D vorgenommen worden ist.9. Composition according to claim 7 or 8, characterized in that in the amylase mutant additionally at least one of the amino acid exchanges L3V, M15T, M15L, R23K, S29A, A30E, Y31H, A33S, E34D, H68Q, W138F, W138Y, R242P, H35I, E255P , T341P, Q374P, E458D, P459T, V461K, N463G and / or E465D.
10. Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es 5 Gew.-% bis 50 Gew.-%, insbesondere 8 Gew.-% bis 30 Gew.-% Tenside, bis zu 60 Gew.-%, insbesondere 5 Gew.-% bis 40 Gew.-% Builder, bis zu 50 Gew.-%, insbesondere 5 Gew.-% bis 30 Gew.-% Persauerstoffverbindungen, 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 8 Gew.-% Bleichaktivatoren, bis zu 1 Gew.-%, insbesondere 0,0025 Gew.-% bis 0,25 Gew.-% bleichverstärkende Übergangsmetallkomplexe, bis zu 5 Gew.-%, insbesondere 0,2 Gew.-% bis 2 Gew.-% weitere Enzyme und/oder nicht über 30 Gew.-%, insbesondere 6 Gew.-% bis 20 Gew.-% wassermischbare Lösungsmittel enthält. 10. Composition according to one of claims 1 to 9, characterized in that there are 5 wt .-% to 50 wt .-%, in particular 8 wt .-% to 30 wt .-% surfactants, up to 60 wt .-%, in particular 5% by weight to 40% by weight builder, up to 50% by weight, in particular 5% by weight to 30% by weight peroxygen compounds, 1% by weight to 10% by weight, in particular 2 % By weight to 8% by weight of bleach activators, up to 1% by weight, in particular 0.0025% by weight to 0.25% by weight of bleach-enhancing transition metal complexes, up to 5% by weight, in particular 0, Contains 2% by weight to 2% by weight of further enzymes and / or not more than 30% by weight, in particular 6% by weight to 20% by weight, of water-miscible solvents.
EP97954439A 1997-01-08 1997-12-19 Protease and amylase-containing detergent Ceased EP0964911A1 (en)

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DE1997100327 DE19700327A1 (en) 1997-01-08 1997-01-08 Protease and amylase detergent
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DE19824705A1 (en) * 1998-06-03 1999-12-09 Henkel Kgaa Detergents and cleaning agents containing amylase and protease
DE10007608A1 (en) * 2000-02-18 2001-08-30 Henkel Kgaa Particulate laundry and other detergents contain genetically modified protease of subtilisin type and coated particulate alkali percarbonate
BRPI1010238A2 (en) 2009-04-01 2015-08-25 Danisco Us Inc Compositions and methods comprising alpha-amylase variants with altered properties
DE102011118021A1 (en) * 2011-10-28 2013-05-02 Henkel Ag & Co. Kgaa Performance-enhanced and temperature-stable protease variants
DE102011088751A1 (en) * 2011-12-15 2013-06-20 Henkel Ag & Co. Kgaa Storage stable liquid washing or cleaning agent containing protease and amylase
DE102012201522A1 (en) * 2012-02-02 2013-08-08 Basf Se Storage stable liquid dishwashing detergent containing protease and amylase
DE102013218253A1 (en) 2013-09-12 2015-03-12 Henkel Ag & Co. Kgaa Solid laundry detergent with improved protease performance

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WO1991002792A1 (en) * 1989-08-25 1991-03-07 Henkel Research Corporation Alkaline proteolytic enzyme and method of production
DE4041752A1 (en) * 1990-12-24 1992-06-25 Henkel Kgaa ENZYME PREPARATION FOR WASHING AND CLEANING AGENTS
PL310326A1 (en) * 1993-02-11 1995-12-11 Genencor Int Novel oxidation-stable mutants of alpha-amylase as well as detergent and starch liquefaction compositions containing them
DE4422609A1 (en) * 1994-06-28 1996-01-04 Cognis Bio Umwelt Multi-enzyme granules

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