EP0876463A1 - Bleaching and washing agents with enzyme bleaching system - Google Patents

Bleaching and washing agents with enzyme bleaching system

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Publication number
EP0876463A1
EP0876463A1 EP96941618A EP96941618A EP0876463A1 EP 0876463 A1 EP0876463 A1 EP 0876463A1 EP 96941618 A EP96941618 A EP 96941618A EP 96941618 A EP96941618 A EP 96941618A EP 0876463 A1 EP0876463 A1 EP 0876463A1
Authority
EP
European Patent Office
Prior art keywords
enzyme
bleaching
weight
substrate
composition according
Prior art date
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Granted
Application number
EP96941618A
Other languages
German (de)
French (fr)
Other versions
EP0876463B1 (en
Inventor
Albrecht Weiss
Marita Grothus
Achim Richert
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
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Henkel AG and Co KGaA
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Publication of EP0876463A1 publication Critical patent/EP0876463A1/en
Application granted granted Critical
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Classifications

    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase

Definitions

  • the invention relates to a bleaching or washing agent which, in addition to the ingredients customary for such agents, contains a bleaching system comprising an amino alcohol or D-amino acid oxidase and a substrate for this oxidase.
  • bleaching agents usually contain an oxidizing agent based on oxygen, in particular a peracid, a peracid salt, hydrogen peroxide or a substance which supplies hydrogen peroxide under aqueous conditions of use. Since the bleaching effect of hydrogen peroxide alone is often perceived as inadequate, bleaching systems consisting of a per-compound which supplies hydrogen peroxide in water and a bleach activator which generates a peracid under perhydrolysis conditions are generally used. The most prominent example of such a bleaching system is the widely used combination of alkali perborate and N, N, N ', N'-tetraacetylethylenediamine.
  • Oxidases are redox enzymes with the classification EC 1 (according to the classification of the Enzy ⁇ me Commission), which are generally flavin-dependent and whose oxidized form is capable. to oxidize a substrate. The resulting reduced form of the enzyme is reoxidized by molecular oxygen in aqueous systems, with hydrogen peroxide being formed as a further product.
  • Examples of such enzymes and their sub- strates that emerge from the name of the enzyme are phenol oxidase, amino acid oxidase, xanthine oxidase, urate oxidase, alcohol oxidase, cholesterol oxidase and glucose oxidase.
  • German published patent application DT 19 18 729 discloses washing and cleaning agents which, in addition to surfactants, contain 0.5% by weight to 10% by weight of glucose oxidase and 5% by weight to 30% by weight of glucose or starch. In the latter case, 0.5% to 10% by weight of amyloglucosidase should also be present.
  • the German published patent application DT 19 18 729 discloses washing and cleaning agents which, in addition to surfactants, contain 0.5% by weight to 10% by weight of glucose oxidase and 5% by weight to 30% by weight of glucose or starch. In the latter case, 0.5% to 10% by weight of amyloglucosidase should also be present.
  • the German published patent application DT 19 18 729 discloses washing and cleaning agents which, in addition to surfactants, contain 0.5% by weight to 10% by weight of glucose oxidase and 5% by weight to 30% by weight of glucose or starch. In the latter case, 0.5% to 10% by weight of amyloglucosidase should also be present.
  • German Offenlegungsschrift DT 20 64 146 discloses washing and cleaning agents which contain 1% by weight to 50% by weight of water-soluble surfactant and 0.01% by weight to 2% by weight of lipoxidase. Polyunsaturated fatty acids are preferred as substrates for the
  • European patent EP 0 072 098 relates to liquid bleaches which contain a C M alcohol oxidase and a C, 4 alcohol.
  • European patent application EP 0 603 931 it is proposed that
  • Bleaches which have an enzymatic system for producing
  • the international patent application WO 94/25574 discloses an L-amino acid oxidase from a particular strain of the microorganism Trichoderma harzianum and detergents which contain such an oxidase. The applicant had set itself the goal of developing a bleaching agent with improved effectiveness of the enzymatically produced hydrogen peroxide under washing and cleaning conditions.
  • the invention therefore relates to a bleaching, washing or cleaning agent containing an enzymatic bleaching system which, under the conditions of use of the agent, is capable of producing hydrogen peroxide, and optionally synthetic surfactant, organic and / or inorganic builder and other customary bleaching agents -, Detergent or cleaning agent components, which is characterized in that the bleaching system consists of an amino alcohol or D-amino acid oxidase activity having an enzyme and a substrate for this enzyme.
  • a second subject of the invention is the use of a bleaching system consisting of an enzyme having amino alcohol or D-amino acid oxidase activity and a substrate for this enzyme for bleaching textile soils under washing conditions.
  • Another object of the invention is the use of a system of an enzyme having amino alcohol or D-amino acid oxidase activity and a substrate for this enzyme for reducing the color transfer from dyed textiles to undyed or differently colored textiles when these are washed or rinsed ⁇ conditions come together.
  • Amino alcohol oxidases catalyze the oxidation of primary alcohol functions of amino alcohols to the corresponding acid function by oxygen with the formation of Hydrogen peroxide. When used, it is essential that an amino alcohol with a primary alcohol function is present as a substrate for the amino alcohol oxidase.
  • Preferred amino alcohol oxidase in the context of the present invention is choline oxidase (EC 1.1.3.17), which is used together with its substrate choline, which is preferably present as a halide.
  • D-amino acid oxidases (EC 1.4.3.3) catalyze the reaction
  • Preferred substrates for D-amino acid oxidases according to the invention are, alone or in a mixture, glycine.
  • D-glutamic acid, D-histidine, D-isoleucine, D-leucine, D-lysine, D-methionine, D-phenylalanine, D-proline, D-serine, D-threonine, D-tryptophan, D-tyrosine and D- Valine which can be used enantiomerically pure or in a mixture with its L-enantiomer.
  • the use of D-alanine is particularly preferred.
  • the oxidases which can be used in agents according to the invention are enzymes which can be obtained from microorganisms or organs of higher animals and which have a pH optimum, preferably in the almost neutral to weakly alkaline range from about pH 6 to pH 9.5.
  • the activity of enzymes is usually expressed in U / g, the unit corresponding to the amount of enzyme which converts 1 ⁇ mol of its substrate at pH 7 and 25 ° C. in 1 minute. 1 U corresponds to 1/60 ⁇ catal.
  • Choline oxidase such as is produced, for example, by Alcaligenes species or Arthrobacter globiformis, is preferably used as the amino alcohol oxidase.
  • D-amino acid oxidase of standardized activity for example obtained from pig kidneys, is commercially available and, like choline oxidase, is offered, for example, by Sigma.
  • Said oxidase is preferably used in the agent according to the invention in amounts such that the entire agent has an oxidase activity of 30 U / g to 20,000 U / g, in particular of 60 U / g to 15,000 U / g.
  • Agents with oxidase activities in the areas mentioned have a rapid enough hydrogen peroxide release for conventional European machine washing processes.
  • the Enzymes used according to the invention with amino alcohol oxidase or D-amino acid oxidase activity have a significantly higher activity under washing or cleaning conditions than glucose oxidase.
  • the amount of the substrate for the oxidase contained in the washing or bleaching agent according to the invention depends on the amount of hydrogen peroxide required to achieve the desired bleaching result.
  • an agent according to the invention can be made up in any form, for example as an aqueous or non-aqueous liquid agent, more or less viscous, aqueous or non-aqueous paste product, granular powder or in stick, piece or ingot form, for the preparation such means can be used on known methods of the relevant prior art.
  • it lies as a free-flowing particulate product, for example as a powder, with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l.
  • the oxidase is preferably used in an adsorbed form which is inert, that is to say not a substrate for the enzyme, embedded in coating substances or in the form of conventional granules with inorganic and / or organic carrier materials.
  • Such enzyme granules can be produced by methods known with other enzymes, such as, for example, in German patent specification DE 16 17 232, German Offenlegungs ⁇ documents DT 20 32 766 or DE 40 41 752 or European patent applications EP 0 168 526, EP 0 170 360 , EP 0 270 608 or EP 0 304 331.
  • oxidase in addition to oxidase, other conventional detergent or cleaning agent enzymes, in particular proteases, lipases, cutinases, amylases, pullulanases, hemicellulases and cellulases, these can be contained in separate particles or in the form of a multi-enzyme granulate, for example in German patent applications DE 44 22 433 or DE 44 22 609 or in the international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein can be used together with oxidase.
  • Liquid to paste-like compositions according to the invention for use in household washing machines are preferably packaged in portioned form, for example in the form of a bag, the container material surrounding a detergent according to the invention, for example film-shaped polyvinyl alcohol, being selected so that it dissolves under the conditions of use, that is to say only in the washing machine during the washing process and releases the detergent so that the bleaching system contained in the detergent only then meets the oxygen contained in the air and forms hydrogen peroxide.
  • the enzyme which has the oxidase activity and / or the substrate for this enzyme is impermeable to the enzyme and / or its substrate at room temperature or in the absence of water
  • Substance enveloped which becomes permeable to the enzyme and / or its substrate under the conditions of use of the agent.
  • composition of the detergents, bleaches or cleaning agents can otherwise be chosen practically as desired in the context of known formulations.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, water-miscible organic solvents, further enzymes, sequestering agents, electrolytes, pH regulators, additional peroxygen bleaching agents and other plasticizers, such as optical brighteners, graying inhibitors, foam regulators, bleach activators, dye - And fragrances and, if desired, additional color transfer inhibitors.
  • bleach activators that is to say compounds which may be present under perhydrolysis conditions
  • Substituted perbenzoic acid and / or aliphatic peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms can be used.
  • the usual bleach activators are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), are preferred.
  • acylated glycolurils in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated phenolsulfonates, in particular nonanoyl- or isononanoyloxy-benzene-sulfonated polyols , in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetyiated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactosamine and acetylated glucose, and optionally
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N analogue compounds known from German patent application DE 196 20 267, which are known from 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 nitrogenous 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 complexes known from European patent application EP
  • 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 customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight .-% to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • the agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof.
  • 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, which correspond to the long-chain alcohol derivatives mentioned with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can also be used.
  • 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 include the salts of Sulfuric acid half-esters of fatty alcohols with 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 which can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part and alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters, which are formed in the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are contained in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while the bleaching agents according to the invention can also be free of surfactants and preferably contain 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of surfactants.
  • 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 aminopolycarboxylic acids. in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methyienphosphonic acid) and l-flydroxyethane-l, l-diphosphonic acid, polycarboxylic acids, in particular citric acid and sugar acids, and also carboxylic acids, in particular, through polymeric (poly) Oxidation of polysaccharides accessible polycarboxylates of international patent application WO 93/161 10, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the relative molecular mass 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 which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C r C 4 carboxylic acids, with vinyl alcohol are particularly preferred.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt can also be a derivative of an allysulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ] -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is substituted.
  • Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallyl sulfonic acid or methallyl sulfonate and as a third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate .
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides are preferred. Sucrose is particularly preferred.
  • terpolymers can be prepared 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 between 1,000 and 200,000, preferably between 200 and 50 000 and in particular between 3,000 and 10,000.
  • 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.
  • organic builder substances of this type can be present in the inventive agents in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents according to the invention.
  • Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
  • 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.
  • the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X are preferred. Amounts close to the above upper limit 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 of less than 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 metal silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 0: Si0 2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 0 5 y H 2 O
  • ⁇ -sodium disilicate being able to be obtained, 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.
  • 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.
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances is preferably 4: 1 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 washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the bleaching agents according to the invention are preferably free from only those Components of the builder substances which complex water hardness are and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of heavy-complexing substances, preferably from the group comprising aminopolycarbonic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.
  • Enzymes which can be used in the compositions in addition to the enzymatic bleaching system are those from the class of proteases, lipases, cutinases, amylases, pullulanases, and cellulases and mixtures thereof. 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.
  • Detected enzymes and the oxidase to be used according to the invention can, as described for example in international patent applications WO 92/11347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation.
  • the additional enzymes mentioned are contained in the agents 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 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 derived from the compound classes mentioned.
  • Such water-miscible solvents are preferably not present in the agents according to the invention in excess of 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or Adipic acid, but also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali metal 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.
  • the preparation of the solid agents according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, the enzymatic bleaching system and optionally other thermally sensitive substances being added later.
  • agents according to the invention with increased bulk density in particular in the range from 650 g / 1 to 950 g / 1, a method known from European Patent EP 486 592 and having an extrusion step is preferred.
  • Washing, cleaning or bleaching according to the invention solutions in the form of aqueous or other customary solvents are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A bleaching detergent composition comprising an enzyme having amino alcohol oxidase activity, a substrate for said enzyme, and a bleach catalyst or activator, a method of bleaching fabric stains with an enzymatic bleaching system comprising an enzyme having amino alcohol oxidase activity and a substrate for said enzyme, and a method of reducing dye transfer in a wash liquor by providing the liquor with an effective amount of an enzymatic bleaching system comprising an enzyme having amino alcohol oxidase activity and a substrate for said enzyme.

Description

Rleich- und Waschmittel mit enzvmatischem Bleichsvstem Bleach and detergent with an envmatic bleaching system
Die Erfindung betrifft ein Bleich- oder Waschmittel, das neben für derartige Mittel üblichen Inhaltsstoffen ein Bleichsystem aus einer Aminoalkohol- oder D-Aminosäure- Oxidase und einem Substrat für diese Oxidase enthält.The invention relates to a bleaching or washing agent which, in addition to the ingredients customary for such agents, contains a bleaching system comprising an amino alcohol or D-amino acid oxidase and a substrate for this oxidase.
Moderne Universalwaschmittel und bleichende Waschhilfsmittel, sogenannte Bleichmittel, enthalten üblicherweise ein Oxidationsmittel auf Sauerstoffbasis, insbesondere eine Persäure, ein Persäuresalz, Wasserstoffperoxid oder eine unter wäßrigen Anwendungsbedingungen Wasserstoffperoxid liefernde Substanz. Da die bleichende Wirkung von Wasserstoffperoxid allein oft als unzureichend empfunden wird, werden in der Regel Bleichsysteme aus einer Perverbindung, die in Wasser Wasserstoffperoxid liefert, und einem Bleichaktivator, der unter Perhydrolysebedingungen eine Persäure generiert, eingesetzt. Prominentestes Beispiel für ein derartiges Bleichsystem ist die weit verbreitet eingesetzte Kombination aus Alkaliperborat und N,N,N',N'-Tetraacetylethylendiamin. Es hat nicht an Versuchen gefehlt, dieses Bleichsystem modifizierend zu verbesssern. So wird zum Beispiel in der internationalen Patentanmeldung WO 89/09813 vorgeschlagen, ein Peroxidase-Enzym, das heißt ein Enzym, welches die Reaktion von Wasserstoffperoxid mit organischen oder anorganischen Substanzen katalysien, als Bleichaktivator zu verwenden.Modern universal detergents and bleaching detergents, so-called bleaching agents, usually contain an oxidizing agent based on oxygen, in particular a peracid, a peracid salt, hydrogen peroxide or a substance which supplies hydrogen peroxide under aqueous conditions of use. Since the bleaching effect of hydrogen peroxide alone is often perceived as inadequate, bleaching systems consisting of a per-compound which supplies hydrogen peroxide in water and a bleach activator which generates a peracid under perhydrolysis conditions are generally used. The most prominent example of such a bleaching system is the widely used combination of alkali perborate and N, N, N ', N'-tetraacetylethylenediamine. There has been no lack of attempts to improve this bleaching system by modifying it. For example, in international patent application WO 89/09813 it is proposed to use a peroxidase enzyme, ie an enzyme which catalyzes the reaction of hydrogen peroxide with organic or inorganic substances, as a bleach activator.
Neben anorganischen Wasserstoffperoxid-vorläufern, wie zum Beispiel Perborat, Percar¬ bonat. Perphosphat und Persilikat, ist auch schon verschiedentlich vorgeschlagen worden, enzymatische Systeme einzusetzten, welche in der Lage sind, aus Sauerstoff, beispiels¬ weise aus Luftsauerstoff, Wasserstoffperoxid zu erzeugen. Derartige Enzyme werden üblicherweise als Oxidasen bezeichnet und je nach ihrem Substrat näher klassifiziert. Oxidasen sind Redox-Enzyme der Klassifizierung EC 1 (gemäß der Einteilung der Enzy¬ me Commission), die in der Regel flavinabhängig sind und deren oxidierte Form in der Lage ist. ein Substrat zu oxidieren. Die dadurch entstehende reduzierte Form des Enzyms wird in wäßrigen Systemen durch molekularen Sauerstoff reoxidiert, wobei sich als weite¬ res Produkt Wasserstoffperoxid ausbildet. Beispiele für derartige Enzyme und ihre Sub- strate, die aus der Bezeichnung des Enzyms hervorgehen, sind Phenol-Oxidase, Amino- säure-Oxidase, Xanthin-Oxidase, Urat-Oxidase, Alkohol-Oxidase, Cholesterol-Oxidase und Glucose-Oxidase.In addition to inorganic hydrogen peroxide precursors, such as perborate, percarbonate. Perphosphate and persilicate has also been proposed on various occasions to use enzymatic systems which are capable of producing hydrogen peroxide from oxygen, for example from atmospheric oxygen. Such enzymes are usually referred to as oxidases and are classified in more detail depending on their substrate. Oxidases are redox enzymes with the classification EC 1 (according to the classification of the Enzy¬ me Commission), which are generally flavin-dependent and whose oxidized form is capable. to oxidize a substrate. The resulting reduced form of the enzyme is reoxidized by molecular oxygen in aqueous systems, with hydrogen peroxide being formed as a further product. Examples of such enzymes and their sub- strates that emerge from the name of the enzyme are phenol oxidase, amino acid oxidase, xanthine oxidase, urate oxidase, alcohol oxidase, cholesterol oxidase and glucose oxidase.
Aus der deutschen Offenlegungsschrift DT 19 18 729 sind Wasch- und Reinigungsmittel bekannt, die neben Tensiden 0,5 Gew.-% bis 10 Gew.-% Glukoseoxidase und 5 Gew.-% bis 30 Gew.-% Glukose beziehungsweise Stärke enthalten. Im letztgenannten Fall sollen zusätzlich 0,5 Gew. -% bis 10 Gew.-% Amyloglucosidase anwesend sein. Die deutscheThe German published patent application DT 19 18 729 discloses washing and cleaning agents which, in addition to surfactants, contain 0.5% by weight to 10% by weight of glucose oxidase and 5% by weight to 30% by weight of glucose or starch. In the latter case, 0.5% to 10% by weight of amyloglucosidase should also be present. The German
Offenlegungsschrift DT 20 64 146 offenbart Wasch- und Reinigungsmittel, die 1 Gew.-% bis 50 Gew.-% wasserlösliches Tensid und 0,01 Gew.-% bis 2 Gew.-% Lipoxidase enthalten. Vorzugsweise sind mehrfach ungesättigte Fettsäuren als Substrate für dieGerman Offenlegungsschrift DT 20 64 146 discloses washing and cleaning agents which contain 1% by weight to 50% by weight of water-soluble surfactant and 0.01% by weight to 2% by weight of lipoxidase. Polyunsaturated fatty acids are preferred as substrates for the
Lipoxidase anwesend. Aus der deutschen Offenlegungsschrift DT 25 57 623 sind Wasch- und Reinigungsmittel bekannt, die neben Tensiden und Buildersubstanzen 0,3 Gew.-% bis 10 Gew.-% Uratoxidase, Galactoseoxidase beziehungsweise CμrAlkoholoxidase undLipoxidase present. From the German patent application DT 25 57 623, detergents and cleaning agents are known which, in addition to surfactants and builder substances, contain 0.3% by weight to 10% by weight of urate oxidase, galactose oxidase or C μr alcohol oxidase and
3 und/oder entsprechende Ketoalkohole enthalten. Die europäische Patentschrift EP 0 072 098 betrifft flüssige Bleichmittel, die eine CM-Alkoholoxidase und einen C,_4-Alkohol enthalten. In der europäischen Patentanmeldung EP 0 603 931 wird vorgeschlagen, das3 and / or corresponding keto alcohols. The European patent EP 0 072 098 relates to liquid bleaches which contain a C M alcohol oxidase and a C, 4 alcohol. In European patent application EP 0 603 931 it is proposed that
System Glukoseoxidase/Glukose in flüssigen Waschmitteln durch den Zusatz von Cu +- und/oder Ag4 -Ionen zu stabilisieren und durch die Anwesenheit von Bleichkatalysatoren, insbesondere Metal lporphinen, Metallporphyrinen, Metallphthalocyaninen und/oderStabilize system glucose oxidase / glucose in liquid detergents by adding Cu + and / or Ag 4 ions and by the presence of bleaching catalysts, in particular metal porphins, metal porphyrins, metal phthalocyanines and / or
Hämin, die Bleichwirkung des enzymatisch erzeugten Wasserstoffperoxids zu steigern. In die gleiche Richtung zielt auch die internationale Patentanmeldung WO 95/07972. aus derHemin to increase the bleaching effect of the enzymatically generated hydrogen peroxide. International patent application WO 95/07972 also aims in the same direction. from the
Bleichmittel bekannt sind, die ein enzymatisches System zur Erzeugung vonBleaches are known which have an enzymatic system for producing
Wasserstoffperoxid und einen bleichkatalysierenden Koordinationskomplex von Mn oderHydrogen peroxide and a bleach-catalyzing coordination complex of Mn or
Fe enthalten. Die internationale Patentanmeldung WO 94/25574 offenbart eine L-Amino- säureoxidase aus einem bestimmten Stamm des Mikroorganismusses Trichoderma harzianum sowie Waschmittel, welche eine deratige Oxidase enthalten. Die Anmelderin hatte sich zum Ziel gesetzt, ein bleichendes Mittel mit verbesserter Wirk¬ samkeit des enzymatisch erzeugten Wasserstoffperoxids unter Wasch- und Reinigungsbe¬ dingungen zu entwickeln.Fe included. The international patent application WO 94/25574 discloses an L-amino acid oxidase from a particular strain of the microorganism Trichoderma harzianum and detergents which contain such an oxidase. The applicant had set itself the goal of developing a bleaching agent with improved effectiveness of the enzymatically produced hydrogen peroxide under washing and cleaning conditions.
Überraschenderweise wurde nun gefunden, daß die Bleichwirkung von Wasserstoffper¬ oxid, welches auf enzymatischem Weg in üblichen Wasch, Bleich- und Reinigungsflotten erzeugt wird, sogar in Abwesenheit üblicher Aktivatoren deutlich gesteigert werden kann, wenn man das Wasserstoffperoxid in situ durch den Einsatz von Aminoalkohol- oder D- Aminosäure-Oxidase erzeugen läßt.Surprisingly, it has now been found that the bleaching effect of hydrogen peroxide, which is produced enzymatically in conventional washing, bleaching and cleaning liquors, can be significantly increased even in the absence of customary activators, if the hydrogen peroxide is used in situ through the use of amino alcohol. or can produce D-amino acid oxidase.
Gegenstand der Erfindung ist daher ein Bleich-, Wasch- oder Reinigungsmittel, ent¬ haltend ein enzymatisches Bleichsystem, das unter Anwendungsbedingungen des Mittels in der Lage ist, Wasserstoffperoxid zu erzeugen, und gegebenenfalls synthetisches Tensid, organischen und/oder anorganischen Builder sowie sonstige übliche Bleich-, Wasch oder Reinigungsmittelbestandteile, welches dadurch gekennzeichnet ist, daß das Bleichsystem aus einem Aminoalkohol- oder D-Aminosäure-Oxidase-Akti vität aufweisenden Enzym und einem Substrat für dieses Enzym besteht.The invention therefore relates to a bleaching, washing or cleaning agent containing an enzymatic bleaching system which, under the conditions of use of the agent, is capable of producing hydrogen peroxide, and optionally synthetic surfactant, organic and / or inorganic builder and other customary bleaching agents -, Detergent or cleaning agent components, which is characterized in that the bleaching system consists of an amino alcohol or D-amino acid oxidase activity having an enzyme and a substrate for this enzyme.
Ein zweiter Gegenstand der Erfindung ist die Verwendung eines Bleichsystems aus einem Aminoalkohol- oder D-Aminosäure-Oxidase-Aktivität aufweisenden Enzym und einem Substrat für dieses Enzym zum Bleichen von Textilanschmutzungen unter Waschbeding¬ ungen.A second subject of the invention is the use of a bleaching system consisting of an enzyme having amino alcohol or D-amino acid oxidase activity and a substrate for this enzyme for bleaching textile soils under washing conditions.
Ein weiterer Gegenstand der Erfindung ist die Verwendung eines Systems aus einem Aminoalkohol- oder D-Aminosäure-Oxidase-Aktivität aufweisenden Enzym und einem Substrat für dieses Enzym zur Verringerung der Farbübertragung von gefärbten Textilien auf ungefärbte oder andersfarbige Textilien, wenn diese unter Wasch- oder Nachspülbe¬ dingungen zusammenkommen.Another object of the invention is the use of a system of an enzyme having amino alcohol or D-amino acid oxidase activity and a substrate for this enzyme for reducing the color transfer from dyed textiles to undyed or differently colored textiles when these are washed or rinsed ¬ conditions come together.
Aminoalkohol-Oxidasen katalysieren die Oxidation primärer Alkoholfunktionen von Aminoalkoholen zur entsprechenden Säurefunktion durch Sauerstoff unter Bildung von Wasserstoffperoxid. Bei ihrem Einsatz ist wesentlich, daß ein Aminoalkohol mit primärer Alkoholfunktion als Substrat für die Aminoalkohol-Oxidase anwesend ist. Bevorzugte Aminoalkohol-Oxidase im Rahmen der vorliegenden Erfindung ist Cholin-Oxidase (EC 1.1.3.17), welche zusammen mit ihrem Substrat Cholin, welches bevorzugt als Halogenid vorliegt, eingesetzt wird. D-Aminosäure-Oxidasen (EC 1.4.3.3) katalysieren die ReaktionAmino alcohol oxidases catalyze the oxidation of primary alcohol functions of amino alcohols to the corresponding acid function by oxygen with the formation of Hydrogen peroxide. When used, it is essential that an amino alcohol with a primary alcohol function is present as a substrate for the amino alcohol oxidase. Preferred amino alcohol oxidase in the context of the present invention is choline oxidase (EC 1.1.3.17), which is used together with its substrate choline, which is preferably present as a halide. D-amino acid oxidases (EC 1.4.3.3) catalyze the reaction
D-Aminosäure + H20 + 02 -> alpha-Ketosäure + NH3 + H202 D-amino acid + H 2 0 + 0 2 -> alpha-keto acid + NH 3 + H 2 0 2
Erfindungsgemäß bevorzugte Substrate für D-Aminosäure-Oxidasen sind, allein oder im Gemisch, Glycin. D-Alanin, D-Arginin, D-Asparagin, D-Asparaginsäure, D-Cystein, D- Glutamin. D-Glutaminsäure, D-Histidin, D-Isoleucin, D-Leucin, D-Lysin, D-Methionin, D-Phenylalanin, D-Prolin, D-Serin, D-Threonin, D-Tryptophan, D-Tyrosin und D-Valin, welche enatiomerenrein oder in Abmischung mit ihrem L-Enatiomeren eingesetzt werden können. Erfindungsgemäß besonders bevorzugt ist der Einsatz von D-Alanin.Preferred substrates for D-amino acid oxidases according to the invention are, alone or in a mixture, glycine. D-alanine, D-arginine, D-asparagine, D-aspartic acid, D-cysteine, D-glutamine. D-glutamic acid, D-histidine, D-isoleucine, D-leucine, D-lysine, D-methionine, D-phenylalanine, D-proline, D-serine, D-threonine, D-tryptophan, D-tyrosine and D- Valine, which can be used enantiomerically pure or in a mixture with its L-enantiomer. According to the invention, the use of D-alanine is particularly preferred.
Die in erfindungsgemäßen Mitteln einsetzbaren Oxidasen sind aus Mikroorganismen oder Organen höherer Tiere gewinnbare Enzyme, welche ein pH-Optimum vorzugsweise im fast neutralen bis schwach alkalischen Bereich von etwa pH 6 bis pH 9,5 aufweisen. Die Aktivität von Enzymen wird üblicherweise in U/g ausgedrückt, wobei die Einheit ("Unit") 1 U der Aktivität derjenigen Enzymmenge entspricht, die 1 μmol ihres Substrats bei pH 7 und 25 °C in 1 Minute umsetzt. 1 U entspricht damit 1/60 μkatal. Vorzugsweise wird als Aminoalkohol-Oxidase Cholin-Oxidase eingesetzt, wie sie zum Beispiel von Alcaligenes Spezies oder Arthrobacter globiformis produziert wird. D-Aminosäure-Oxidase standardi¬ sierter Aktivität, zum Beispiel aus Schweinenieren gewonnen, ist im Handel erhältlich und wird ebenso wie Cholin-Oxidase beispielsweise von der Firma Sigma angeboten. Eine genannte Oxidase wird im erfindungsgemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das gesamte Mittel eine Oxidase-Aktivität von 30 U/g bis 20 000 U/g, insbesondere von 60 U/g bis 15 000 U/g, aufweist. Mittel mit Oxidase-Aktivitäten in den genannten Bereichen weisen eine für übliche europäische maschinelle Waschverfahren ausreichend rasche Wasserstoffperoxidfreisetzung auf. Die erfindungsgemäß eingesetzten Enzyme mit Aminoalkohol-Oxidase- oder D-Aminosäure- Oxidase-Aktivität weisen unter Wasch- beziehungsweise Reinigungsbedingungen eine deutlich höhere Aktivität auf als Glukose-Oxidase.The oxidases which can be used in agents according to the invention are enzymes which can be obtained from microorganisms or organs of higher animals and which have a pH optimum, preferably in the almost neutral to weakly alkaline range from about pH 6 to pH 9.5. The activity of enzymes is usually expressed in U / g, the unit corresponding to the amount of enzyme which converts 1 μmol of its substrate at pH 7 and 25 ° C. in 1 minute. 1 U corresponds to 1/60 μcatal. Choline oxidase, such as is produced, for example, by Alcaligenes species or Arthrobacter globiformis, is preferably used as the amino alcohol oxidase. D-amino acid oxidase of standardized activity, for example obtained from pig kidneys, is commercially available and, like choline oxidase, is offered, for example, by Sigma. Said oxidase is preferably used in the agent according to the invention in amounts such that the entire agent has an oxidase activity of 30 U / g to 20,000 U / g, in particular of 60 U / g to 15,000 U / g. Agents with oxidase activities in the areas mentioned have a rapid enough hydrogen peroxide release for conventional European machine washing processes. The Enzymes used according to the invention with amino alcohol oxidase or D-amino acid oxidase activity have a significantly higher activity under washing or cleaning conditions than glucose oxidase.
Die Menge des im erfindungsgemäßen Wasch- beziehungsweiseBleichmittel enthaltenen Substrats für die Oxidase richtet sich nach der zum Erzielen des gewüschten Bleichergeb¬ nisses erforderlichen Wasserstoffperoxidmenge. Hier kann als Anhaltspunkt dienen, daß bei Enzym-Substrat-Systemen, die pro Mol umgesetztem Substrat ein Mol Wasserstoff¬ peroxid freisetzen, die Anwesenheit von etwa 0,05 Gew.-% bis 0,6 Gew.-% des Substrats in der Wasch-, Bleich- oder Reinigungsflotte in der Regel zur Erzielung eines guten Bleichergebnisses ausreicht.The amount of the substrate for the oxidase contained in the washing or bleaching agent according to the invention depends on the amount of hydrogen peroxide required to achieve the desired bleaching result. Here it can serve as a point of reference that in the case of enzyme-substrate systems which release one mole of hydrogen peroxide per mole of substrate converted, the presence of about 0.05% by weight to 0.6% by weight of the substrate in the wash -, bleaching or cleaning liquor is usually sufficient to achieve a good bleaching result.
Abweichend zum in WO 89/09813 beschriebenen Befund, daß Wasserstoffperoxid in Ge¬ genwart von diese Verbindung abbauenden Enzymen eine erhöhte Bleichwirkung an ver¬ schmutzten Textilien aufweise, wurde von uns gefunden, daß die gleichzeitige Anwesen¬ heit von Peroxidasen oder Katalasen und dem Bleichsystem aus einem Oxidase-Aktivität aufweisenden Enzym und einem Substrat für dieses Enzym in den erfindungsgemäßen Mitteln der Bleichwirkung des enzymatisch erzeugten Wasserstoffperoxids abträglich ist. Falls daher, beispielsweise aus Kostengründen, Enzympräparate eingesetzt werden sollen, die neben Oxidase auch - oft mit dieser zusammen aus dem produzierenden Mikro¬ organismus isolierte - Katalase und/oder Peroxidase enthalten, wird dem erfindungs¬ gemäßen Mittel vorzugsweise ein Inhibitor für derartige Wasserstoffperoxid-zerstörende Enzyme zugesetzt. Als sehr wirksam sind in diesem Zusammenhang insbesondere Hy- droxylammoniumsalze, beispielsweise Hydroxylammoniumsulfat, gefunden worden.In contrast to the finding described in WO 89/09813 that hydrogen peroxide has an increased bleaching action on soiled textiles in the presence of enzymes which break down this compound, we have found that the simultaneous presence of peroxidases or catalases and the bleaching system results from an enzyme having oxidase activity and a substrate for this enzyme in the agents according to the invention is detrimental to the bleaching action of the enzymatically generated hydrogen peroxide. If enzyme preparations are therefore to be used, for example for reasons of cost, which in addition to oxidase also contain catalase and / or peroxidase — often isolated together with this from the producing microorganism — the agent according to the invention is preferably an inhibitor for such hydrogen peroxide-destroying agents Enzymes added. In this connection, hydroxylammonium salts, for example hydroxylammonium sulfate, have been found to be very effective.
Ein erfindungsgemäßes Mittel kann im Prinzip in jeder beliebigen Form, beispielsweise als wäßriges oder nicht-wäßriges flüssiges Mittel, mehr oder weniger viskoses, wäßriges oder nichtwäßriges Pastenprodukt, granuläres Pulver oder in Stift-, Stück- beziehungswei¬ se Barrenform konfektioniert werden, wobei zur Herstellung derartiger Mittel auf bekannte Verfahren des einschlägigen Standes der Technik zurückgegriffen werden kann. In einer bevorzugten Ausführungsform liegt es als rieselfähiges teilchenförmiges Produkt, beispielsweise als Pulver, mit einem Schüttgewicht von 300 g/I bis 1200 g/1, insbesondere 500 g/1 bis 900 g/1, vor. In derartigen teilchenförmigen Produkten wird die Oxidase bevor¬ zugt in an inertes, das heißt kein Substrat für das Enzym darstellendes Trägermaterial ad¬ sorbierter Form, in Hüllsubstanzen eingebettet oder in Form üblicher Granulate mit anor¬ ganischen und/oder organischen Trägermaterialien, eingesetzt. Solche Enzymgranulate können durch mit anderen Enzymen bekannte Verfahren hergestellt werden, wie beispielsweise in der deutschen Patentschrift DE 16 17 232, den deutschen Offenlegungs¬ schriften DT 20 32 766 oder DE 40 41 752 oder den europäischen Patentanmeldungen EP 0 168 526, EP 0 170 360, EP 0 270 608 oder EP 0 304 331 beschrieben. Falls zusätzlich zu Oxidase weitere übliche Wasch- oder Reinigungsmittelenzyme, zu denen insbesondere Proteasen, Lipasen, Cutinasen, Amylasen, Pullulanasen, Hemicellulasen und Cellulasen zu rechnen sind, können diese in getrennten Partikeln enthalten sein oder in Form eines Mehrenzym-Granulats, wie beispielsweise in den deutschen Patentanmeldungen DE 44 22 433 oder DE 44 22 609 oder in den internationalen Patent¬ anmeldungen WO 90/09440 oder WO 90/09428 sowie dem dort zitierten Stand der Technik beschrieben, zusammen mit Oxidase eingesetzt werden.In principle, an agent according to the invention can be made up in any form, for example as an aqueous or non-aqueous liquid agent, more or less viscous, aqueous or non-aqueous paste product, granular powder or in stick, piece or ingot form, for the preparation such means can be used on known methods of the relevant prior art. In a preferred embodiment, it lies as a free-flowing particulate product, for example as a powder, with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l. In such particulate products, the oxidase is preferably used in an adsorbed form which is inert, that is to say not a substrate for the enzyme, embedded in coating substances or in the form of conventional granules with inorganic and / or organic carrier materials. Such enzyme granules can be produced by methods known with other enzymes, such as, for example, in German patent specification DE 16 17 232, German Offenlegungs¬ documents DT 20 32 766 or DE 40 41 752 or European patent applications EP 0 168 526, EP 0 170 360 , EP 0 270 608 or EP 0 304 331. If, in addition to oxidase, other conventional detergent or cleaning agent enzymes, in particular proteases, lipases, cutinases, amylases, pullulanases, hemicellulases and cellulases, are to be counted, these can be contained in separate particles or in the form of a multi-enzyme granulate, for example in German patent applications DE 44 22 433 or DE 44 22 609 or in the international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein can be used together with oxidase.
Bei puiverförmigen Mitteln im Sinne der Erfindung wie auch bei nicht-wäßrigen flüssigen oder pastenförmigen Mitteln tritt normalerweise bei der Lagerung keine merkliche Zer¬ setzung des Oxidase-Substrats durch die Aminoalkohol- und/oder D-Aminosäure-Oxidase auf. In flüssigen oder pastenförmigen Mitteln, die Wasser enthalten, kann die enzyma- tische Zersetzung des Substrates bei der Lagerung zum Problem werden, das allerdings durch die Vermeidung von Sauerstoffzutritt zum erfindungsgemaßen Mittel gelöst werden kann. Wasserhaltige, das heißt mehr als etwa 3 Gew.-% Wasser enthaltende, flüssige oder pastenförmige erfindungsgemäße Mittel werden daher vorzugsweise in luftundurchläs¬ sigen Behältnissen verpackt gelagert, aus denen sie erst möglichst kurz vor ihrer Anwen¬ dung entnommen werden. Bei maschinellen gewerblichen Waschverfahren kann dies in einfacher Weise durch die automatische Dosierung des erfindungsgemäßen Waschmittels direkt aus dem Transportbehälter, wie zum Beispiel in der europäischen Patentschrift EP 0 295 525 beschrieben, erfolgen. Erfindungsgemäße flüssige bis pastenförmige Mittel für den Gebrauch in Haushaltswaschmaschinen werden vorzugsweise in portionierter Form, beispielsweise in Beutelform, konfektioniert, wobei das ein erfindungsgemäßes Waschmittel umgebende Behältnismaterial, beispielsweise folienfbrmiger Polyvinylakohol, so ausgewählt wird, daß es sich unter den Anwendungsbedingungen, das heißt erst in der Waschmaschine während des Waschvorgangs löst und das Waschmittel freisetzt, so daß das im Waschmittel enthaltene Bleichsystem erst dann mit dem in der Luft enthaltenen Sauerstoff zusammentritt und Wasserstoffperoxid bildet.In the case of powdery agents in the sense of the invention, and also in the case of non-aqueous liquid or pasty agents, there is normally no appreciable decomposition of the oxidase substrate by the amino alcohol and / or D-amino acid oxidase during storage. In liquid or pasty compositions which contain water, the enzymatic decomposition of the substrate can become a problem during storage, which, however, can be solved by avoiding oxygen access to the composition according to the invention. Water-containing, ie more than about 3% by weight water-containing, liquid or pasty compositions according to the invention are therefore preferably stored packaged in air-impermeable containers, from which they are removed as shortly as possible before their use. In mechanical industrial washing processes, this can be done in a simple manner by automatically metering the detergent according to the invention directly from the transport container, as described, for example, in European Patent EP 0 295 525. Liquid to paste-like compositions according to the invention for use in household washing machines are preferably packaged in portioned form, for example in the form of a bag, the container material surrounding a detergent according to the invention, for example film-shaped polyvinyl alcohol, being selected so that it dissolves under the conditions of use, that is to say only in the washing machine during the washing process and releases the detergent so that the bleaching system contained in the detergent only then meets the oxygen contained in the air and forms hydrogen peroxide.
in einer weiteren Ausführungsform des erfindungsgemäßen Mittels ist, ebenfalls zur Er¬ höhung der Lagerstabilität, das die Oxidase-Aktivität aufweisende Enzym und/oder das Substrat für dieses Enzym mit einer bei Raumtemperatur oder bei Abwesenheit von Wasser für das Enzym und/oder dessen Substrat undurchlässigen Substanz umhüllt, welche unter Λnwendungsbedingungen des Mittels durchlässig für das Enzym und/oder dessen Substrat wird. Zu diesem Zweck brauchbar sind bei Temperaturen oberhalb Raum¬ temperatur, insbesondere im Bereich von 35 °C bis 75 °C schmelzende organische Sub¬ stanzen, beispielsweise Fettalkohole, Polyglykole, Paraffinwachse oder Fettsäureester. Auch unter Anwendungsbedingungen der Mittel nicht schmelzende, aber wasserlösliche beziehungsweise wasserdispergierbare Stoffe, beispielsweise feinteiliges Alkalialumo- silikat, Schichtsilikat, Ton oder Bentonit, sind geeignet.In a further embodiment of the agent according to the invention, also to increase the storage stability, the enzyme which has the oxidase activity and / or the substrate for this enzyme is impermeable to the enzyme and / or its substrate at room temperature or in the absence of water Substance enveloped which becomes permeable to the enzyme and / or its substrate under the conditions of use of the agent. Organic substances which melt at temperatures above room temperature, in particular in the range from 35 ° C. to 75 ° C., for example fatty alcohols, polyglycols, paraffin waxes or fatty acid esters, can be used for this purpose. Substances which do not melt under the conditions of use of the compositions but are water-soluble or water-dispersible, for example finely divided alkali aluminosilicate, layered silicate, clay or bentonite, are also suitable.
Die Zusammensetzung der Wasch-, Bleich oder Reinigungsmittel kann ansonsten im Rahmen bekannter Rezepturen praktisch beliebig gewählt werden. Die erfindungs¬ gemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, wassermischbare organische Lösungsmittel, weitere Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren, zusätzliche Persauerstoff-Bleichmittel und sonstige Flilfs- stoffe, wie optische Aufheller, Vergrauungsinhibitoren, Schaumregulatoren, Bleichaktiva¬ toren, Färb- und Duftstoffe sowie gewünschtenfalls zusätzliche Farbübertragungsinhibito- ren enthalten.The composition of the detergents, bleaches or cleaning agents can otherwise be chosen practically as desired in the context of known formulations. The agents according to the invention can in particular builder substances, surface-active surfactants, water-miscible organic solvents, further enzymes, sequestering agents, electrolytes, pH regulators, additional peroxygen bleaching agents and other plasticizers, such as optical brighteners, graying inhibitors, foam regulators, bleach activators, dye - And fragrances and, if desired, additional color transfer inhibitors.
Zusätzlich zu dem erfindungswesentlichen Bleichsystem können konventionelle Bleich¬ aktivatoren, das heißt Verbindungen, die unter Perhydrolysebedingungen gegebenenfalls substituierte Perbenzoesäure und/oder aliphatische Peroxocarbonsäuren mit 1 bis 10 C- Atomen, insbesondere 2 bis 4 C-Atomen ergeben, eingesetzt werden. Geeignet sind die üblichen Bleichaktivatoren, 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 Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), acylierte Triazinderivate, insbe¬ sondere l,5-Diacetyl-2,4-dioxohexahydro-l,3,5-triazin (DADHT), acylierte Phenolsulfonate, insbesondere Nonanoyl- oder Isononanoyloxybenzolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy- 2,5-dihydrofuran sowie acetyiiertes Sorbit und Mannit, und acylierte Zuckerderivate, ins¬ besondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactosc sowie acetyiiertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton. Auch die aus der deutschen Patentanmeldung DE 44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren sind normalerweise in Mengen von 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 5 Gew.-% enthalten. Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren oder an deren Stelle können auch die aus den europäischen Patentschriften EP 0 446 982 und EP 0 453 003 bekannten Sullbnimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetall¬ komplexe 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 und/oder die in der europäischen Patentschrift EP 0 443 651 oder den europäischen Patentanmeldungen EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 und EP 0 544 519 be¬ schriebenen Mangan-Komplexe. Kombinationen aus Bleichaktivatoren und Übergangs- metall-Bleichkatalysatoren sind beispielsweise aus der deutschen Patentanmeldung DE 196 13 103 und der internationalen Patentanmeldung WO 95/27775 bekannt. Bleich¬ verstärkende 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 bleaching system which is essential to the invention, conventional bleach activators, that is to say compounds which may be present under perhydrolysis conditions Substituted perbenzoic acid and / or aliphatic peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, can be used. The usual bleach activators are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), are preferred. acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated phenolsulfonates, in particular nonanoyl- or isononanoyloxy-benzene-sulfonated polyols , in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetyiated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactosamine and acetylated glucose, and optionally acetylated glucose, as well as acetylated gluconate and acetylated gluconate, as well as acetylated gluconate and acetylated gluconate, and optionally acylated gluconate and acetylated gluconate, as well as acetylated gluconate and acetylated gluconate, and optionally acylated gluconate and acetylated glucose, as well as acylated glucone and optionally acetylated gluconate, . The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Such bleach activators are normally contained in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 5% by weight. In addition to the conventional bleach activators listed above or in their place, the sulfimimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N analogue compounds known from German patent application DE 196 20 267, which are known from 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 nitrogenous 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 complexes known from European patent application EP 0 693 550, the manganese, iron and cobalt known from European patent EP 0 392 592 and copper complexes and / or those described in European patent EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 ¬ written manganese complexes. 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 customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight .-% to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
Die erfindungsgemaßen Mittel können ein oder mehrere Tenside enthalten, wobei insbe¬ sondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxy- lierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder ver¬ zweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten lang¬ kettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomem im Alkylrest brauchbar.The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof. 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, which correspond to the long-chain alcohol derivatives mentioned with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can also be used.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sul- fonat-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 Sulfa- tierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxylierungs- grad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkylbenzolsul- fonate mit 9 bis 14 C-Atomen im Alkylteil, Alkansulfonate mit 12 bis 18 C-Atomen, sowie Olefinsulfonate 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 include the salts of Sulfuric acid half-esters of fatty alcohols with 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 which can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part and alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters, which are formed in the sulfonation of fatty acid methyl or ethyl esters.
Derartige Tenside sind in den erfindungsgemäßen Reinigungs- oder Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten, während die erfindungsgemäßen Bleichmittel auch tensidfrei sein können und vorzugsweise 0, 1 Gew.-% bis 20 Gew.-%, insbesondere 0.2 Gew.-% bis 5 Gew.-% Tenside enthalten.Such surfactants are contained in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while the bleaching agents according to the invention can also be free of surfactants and preferably contain 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of surfactants.
Ein erfindungsgemäßes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den was¬ serlöslichen organischen Buildersubstanzen gehören Aminopolycarbonsäuren. ins¬ besondere Nitrilotriessigsäure und Ethylendiamintetraessigsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamintetrakis(methyienphos- phonsäure) und l-Flydroxyethan-l ,l -diphosphonsäure, Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden zugänglichen Polycarboxylate der internationalen Patentanmeldung WO 93/161 10, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekül - masse 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 Acryl- säure-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 Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpo¬ lymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/ oder ein Vinylalkohol-Derivat 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-C4-Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure besonders bevorzugt ist. Die dritte monomere Einheit wird in diesem Fall von Vinylalkohol und/oder vorzugsweise einem veresterten Vinylalkohol gebildet. Insbesondere sind Vinylalkohol-Derivate bevorzugt, welche einen Ester aus kurzkettigen Carbonsäuren, beispielsweise von CrC4-Carbonsäuren, mit Vinylalkohol darstellen. Bevorzugte Terpolymere enthalten dabei 60 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 90 Gew.-% (Meth)acrylsäure bzw. (Meth)acrylat, besonders bevorzugt Acrylsäure bzw. Acrylat, und Maleinsäure bzw. Maleat sowie 5 Gew.-% bis 40 Gew.-%, vorzugsweise 10 Gew.-% bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat. Ganz besonders bevorzugt sind dabei Terpolymere, in denen das Gewichtsverhältnis von (Meth)acrylsäure beziehungsweise (Meth)acrylat zu Maleinsäure beziehungsweise Maleat zwischen 1 : 1 und 4: 1 , vorzugsweise zwischen 2: 1 und 3: 1 und insbesondere 2: 1 und 2,5: 1 liegt. Dabei sind sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren be¬ zogen. Das zweite saure Monomer beziehungsweise dessen Salz kann auch ein Derivat einer Allyisulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem C]-C4-Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol-Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 Gew.-% bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure beziehungsweise (Meth)acrylat, besonders bevorzugt Acrylsäure beziehungsweise Acrylat, 10 Gew.-% bis 30 Gew.-%, vorzugsweise 15 Gew.-% bis 25 Gew.-% Methallyl- sulfonsäure bzw. Methallylsulfonat und als drittes Monomer 15 Gew.-% bis 40 Gew.-%, vorzugsweise 20 Gew.-% bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann dabei beispielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligosaccharide bevorzugt sind. Besonders bevorzugt ist Saccharose. Durch den Einsatz des dritten Monomers werden vermutlich Sollbruchstellen in das Polymer einge¬ baut, die für die gute biologische Abbaubarkeit des Polymers verantwortlich sind. Diese Terpolymere lassen sich insbesondere nach Verfahren herstellen, die in der deutschen Pa¬ tentschrift 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, vorzugsweise zwischen 200 und 50 000 und insbesondere zwischen 3 000 und 10 000 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/Acrylsäuresalze 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 aminopolycarboxylic acids. in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methyienphosphonic acid) and l-flydroxyethane-l, l-diphosphonic acid, polycarboxylic acids, in particular citric acid and sugar acids, and also carboxylic acids, in particular, through polymeric (poly) Oxidation of polysaccharides accessible polycarboxylates of international patent application WO 93/161 10, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative molecular mass 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 which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C r C 4 carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 are very particularly preferred , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allysulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ] -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallyl sulfonic acid or methallyl sulfonate and as a third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate . This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides are preferred. Sucrose is particularly preferred. By using the third monomer, predetermined breaking points are presumably built into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers can be prepared 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 between 1,000 and 200,000, preferably between 200 and 50 000 and in particular between 3,000 and 10,000. 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.
Gewünschtenfalls können derartige organische Buildersubstanzen in erfindungsgemäßen Mitteln 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 wer¬ den vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, erfin¬ dungsgemäßen Mitteln eingesetzt.If desired, organic builder substances of this type can be present in the inventive agents in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents according to the invention.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Polyphos- phate, vorzugsweise Natriumtriphosphat, in Betracht. Als wasserunlösliche, wasserdisper- gierbare 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, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosi- likate 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.Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. 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. Among these, the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, are preferred. Amounts close to the above upper limit 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 of less than 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 Alkalisi¬ likate 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. Be¬ vorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsili¬ kate, mit einem molaren Verhältnis Na20:Si02 von 1 :2 bis 1 :2.8. Derartige amorphe Alkalisilikate sind beispielsweise unter dem Namen Portil® im Handel erhältlich. Solche mit einem molaren Verhältnis Na20:Si02 von 1 : 1,9 bis 1 :2,8 können nach dem Verfahren der europäischen Patentanmeldung EP 0 425 427 hergestellt werden. Sie werden im Rahmen der Herstellung erfindungsgemäßer Mittel bevorzugt als Feststoff und nicht in Form einer Lösung zugegeben. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsiiikate der allgemeinen Formel Na2Six02x+ y H20 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 für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden bei¬ spielsweise 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 (Na2Si205 y H2O) bevorzugt, wobei ß-Natriumdisilikat 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 0 452 428 beschrieben, können in erfindungsgemäßen 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 ein¬ gesetzt. Falls als zusätzliche Buildersubstanz auch Alkalialumosilikat, insbesondere Zeolith. vorhanden ist, beträgt das Gewichtsverhältnis Alumosilikat zu Silikat, jeweils be¬ zogen auf wasserfreie Aktivsubstanzen, vorzugsweise 4: 1 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 insbe¬ sondere 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 metal silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 0: Si0 2 molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar Na 2 0: Si0 2 ratio of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427. They are preferably added as a solid and not in the form of a solution in the preparation of agents according to the invention. Crystalline layered silicates of the general formula Na 2 Si x 0 2x + y H 2 0, in which x, the so-called modulus, a number from 1.9 to 4, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates 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 assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicate (Na 2 Si 2 0 5 y H 2 O) are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the general formula mentioned above, in which x is a number of 1, 9 to 2.1 means producible as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 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, as an additional builder, also alkali alumosilicate, in particular zeolite. is present, the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is preferably 4: 1 to 10: 1. In compositions 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 Wasch- oder Reinigungsmitteln vor¬ zugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 5 Gcw.-% bis 40 Gew.-%, ent¬ halten, während die erfindungsgemäßen Bleichmittel vorzugsweise frei von den lediglich die Komponenten der Wasserhärte komplexierenden Buildersubstanzen sind und bevor¬ zugt nicht über 20 Gew.-%, insbesondere von 0, 1 Gew.-% bis 5 Gew.-%, an schwerme- talikomplexiercnden Stoffen, vorzugsweise aus der Gruppe umfassend Aminopolycarbon- säuren, Aminopolyphosphonsäuren und Hydroxypolyphosphonsäuren und deren wasser¬ lösliche Salze sowie deren Gemische, enthalten.Builder substances are contained in the washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the bleaching agents according to the invention are preferably free from only those Components of the builder substances which complex water hardness are and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of heavy-complexing substances, preferably from the group comprising aminopolycarbonic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.
Als in den Mitteln zusätzlich zum enzymatischen Bleichsystem verwendbare Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Cutinasen, Amylasen, Pullulanasen, und Cellulasen sowie deren Gemische in Frage. 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 gegebenenfalls verwen- deten Enzyme und die erfindungsgemäß einzusetzende Oxidase können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/11347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Die genannten zusätzlichen Enzyme sind in den er¬ findungsgemäßen Mitteln 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 enzymatic bleaching system are those from the class of proteases, lipases, cutinases, amylases, pullulanases, and cellulases and mixtures thereof. 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. If necessary, use Detected enzymes and the oxidase to be used according to the invention can, as described for example in international patent applications WO 92/11347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation. The additional enzymes mentioned are contained in the agents 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 pastö- ser Form vorliegen, 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 Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Mitteln vorzugsweise 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, 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 derived from the compound classes mentioned. Such water-miscible solvents are preferably not present in the agents according to the invention in excess of 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, Äpfel¬ säure, 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 erfindungsge¬ mäßen 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 system 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, but also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali metal 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.
Die Herstellung der erfindungsgemäßen festen Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei das enzymatische Bleichsystem und gegebenenfalls sonstige thermisch empfindliche Substanzen später 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 auf¬ weisendes Verfahren bevorzugt. Erfindungsgemaße Wasch-, Reinigungs- oder Bleich- mittcl in Form wäßriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.The preparation of the solid agents according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, the enzymatic bleaching system and optionally other thermally sensitive substances being added later. For the preparation of agents according to the invention with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1, a method known from European Patent EP 486 592 and having an extrusion step is preferred. Washing, cleaning or bleaching according to the invention solutions in the form of aqueous or other customary solvents are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
BeispieleExamples
Die Bildung von Waserstoffperoxid mit Hilfe verschiedener Oxidasen wurde im Puffersystem (Davies-Puffer) und in Gegenwart eines enzym-, bleichmittel- und bleichaktivatorfreien Waschmittels (Konzentration 5 g/1) bei pH 10 und 30 °C untersucht. Die Bestimmung der H2O2-Konzentration erfolgte photometrisch unter Anwendung des Lambcrt-Beer' sehen Gesetzes über die peroxidasekatalysierte Farbstoffbildung aus 4- Aminophenazon und Chromotropsäure. Die Konzentration des jeweiligen Oxidase- Substrats (D-Alanin, Cholin-Chlorid beziehungsweise Glukose) betrug 25 mmol/l. Die Oxidasen wurden in Aktivitäten von jeweils 1 U/ml eingesetzt. Bei den Versuchen mit D- Aminosäure-Oxidase war wie auch bei dem vergleichenden Versuchen mit Glukose¬ oxidase zusätzlich Hydroxylammoniumsulfat (Konzentration 1 mmol/l) anwesend. In der nachfolgenden Tabelle 1 sind die nach 30 Minuten und 45 Minuten erzielten Wasserstoff¬ peroxid-Konzentrationen angegeben.The formation of hydrogen peroxide with the aid of various oxidases was investigated in the buffer system (Davies buffer) and in the presence of an enzyme, bleach and bleach activator-free detergent (concentration 5 g / 1) at pH 10 and 30 ° C. The determination of H 2 O 2 concentration was determined photometrically using the Lambcrt-Beer see 'Law on the peroxidase-catalyzed dye formation from 4- aminophenazon and chromotropic. The concentration of the respective oxidase substrate (D-alanine, choline chloride or glucose) was 25 mmol / l. The oxidases were used in activities of 1 U / ml each. In the experiments with D-amino acid oxidase, as in the comparative experiments with glucose oxidase, hydroxylammonium sulfate (concentration 1 mmol / l) was also present. Table 1 below shows the hydrogen peroxide concentrations achieved after 30 minutes and 45 minutes.
Tabelle 1 : Wasserstoffperoxid-Konzentration [mmol/l]Table 1: Hydrogen peroxide concentration [mmol / l]
a) aus Schweinenieren b) aus Alcaligenes c) aus Aspergillus niger Unter den für die Verwendung in Waschmitteln typischen Bedingungen war bei Einsatz des Systems Glukose-Oxidase/Glukose im Gegensatz zu den Systemen gemäß der Erfin¬ dung nur eine geringe Wasserstoffperoxidentwicklung meßbar. a) from pig kidneys b) from Alcaligenes c) from Aspergillus niger Under the conditions typical for use in detergents, when the system glucose oxidase / glucose was used, in contrast to the systems according to the invention, only a slight development of hydrogen peroxide was measurable.

Claims

Patentansprüche claims
1. Bleich-, Wasch- oder Reinigungsmittel, enthaltend ein enzymatisches Bleichsystem, das unter Anwendungsbedingungen des Mittels in der Lage ist, Wasserstoffperoxid zu erzeugen, und gegebenenfalls synthetisches Tensid, organischen und/oder anorga¬ nischen Builder sowie sonstige übliche Bleich-, Wasch oder Reinigungsmittelbe¬ standteile, dadurch gekennzeichnet, daß das Bleichsystem aus einem Aminoalkohol- oder D-Aminosäure-Oxidase-Aktivität aufweisenden Enzym und einem Substrat für dieses Enzym besteht.1. Bleaching, washing or cleaning agent containing an enzymatic bleaching system which, under the conditions of use of the agent, is capable of producing hydrogen peroxide, and optionally synthetic surfactant, organic and / or inorganic builder and other customary bleaching, washing or Cleaning agent constituents, characterized in that the bleaching system consists of an enzyme having amino alcohol or D-amino acid oxidase activity and a substrate for this enzyme.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, daß das Bleichsystem Cholin- Oxidase und Cholin enthält.2. Composition according to claim 1, characterized in that the bleaching system contains choline oxidase and choline.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Bleichsystem D- Aminosäure-Oxidase und Glycin. D-Alanin, D-Arginin, D-Asparagin, D-Asparagin- säure, D-Cystein, D-Glutamin, D-Glutaminsäure, D-Histidin, D-Isoleucin, D-Leucin, D-Lysin, D-Methionin, D-Phenylalanin, D-Prolin, D-Serin, D-Threonin, D- Tryptophan, D-Tyrosin und/oder D-Valin, welche enatiomerenrein oder in Abmischung mit ihrem L-Enatiomeren eingesetzt werden können, enthält.3. Composition according to claim 1 or 2, characterized in that the bleaching system D-amino acid oxidase and glycine. D-alanine, D-arginine, D-asparagine, D-aspartic acid, D-cysteine, D-glutamine, D-glutamic acid, D-histidine, D-isoleucine, D-leucine, D-lysine, D-methionine, Contains D-phenylalanine, D-proline, D-serine, D-threonine, D-tryptophan, D-tyrosine and / or D-valine, which can be used enantiomerically pure or in a mixture with their L-enantiomer.
4. Mittel nach einem der Anspruch 1 bis 3, dadurch gekennzeichnet, daß es eine Oxidase-Aktivität von 30 U/g bis 20 000 U/g aufweist.4. Composition according to one of claims 1 to 3, characterized in that it has an oxidase activity of 30 U / g to 20,000 U / g.
5. Mittel nach einem der Anspruch 1 bis 4, dadurch gekennzeichnet, daß es zusätzlich Bleichaktivator und/oder Bleichkatalysator enthält.5. Composition according to one of claims 1 to 4, characterized in that it additionally contains bleach activator and / or bleach catalyst.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es in rie¬ selfähiger Teilchenform mit einem Schüttgewicht von 300 g/1 bis 1200 g/1, insbeson¬ dere 500 g/1 bis 900 g/1, vorliegt. 6. Composition according to one of claims 1 to 5, characterized in that it is in rie¬ selbaren particle form with a bulk density of 300 g / 1 to 1200 g / 1, in particular 500 g / 1 to 900 g / 1, is present.
7. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es in Form eines pastenförmigen oder flüssigen Wasch- oder Reinigungsmittels vorliegt.7. Composition according to one of claims 1 to 5, characterized in that it is in the form of a pasty or liquid washing or cleaning agent.
8. Mittel nach Anspruch 7, dadurch gekennzeichnet, daß es in Form eines nicht¬ wäßrigen Flüssigkeit oder einer nicht-wäßrigen Paste vorliegt.8. Composition according to claim 7, characterized in that it is in the form of a non-aqueous liquid or a non-aqueous paste.
9. Mittel nach Anspruch 7, dadurch gekennzeichnet, daß es in Form eines wäßrigen Flüssigkeit oder einer wasserhaltigen Paste vorliegt und in einem luftundurchlässigen Behältnis verpackt ist, aus dem es kurz vor Gebrauch oder während des Waschvor¬ gangs freigesetzt wird.9. Composition according to claim 7, characterized in that it is in the form of an aqueous liquid or a water-containing paste and is packaged in an air-impermeable container from which it is released shortly before use or during the washing operation.
10. Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das die Oxida¬ se-Aktivität aufweisende Enzym und/oder das Substrat für dieses Enzym mit einer bei Raumtemperatur oder bei Abwesenheit von Wasser für das Enzym und/oder dessen Substrat undurchlässigen Substanz umhüllt ist, welche unter Anwendungsbe¬ dingungen des Mittels durchlässig für das Enzym und/oder dessen Substrat wird.10. Composition according to one of claims 1 to 9, characterized in that the enzyme having the Oxida¬ se activity and / or the substrate for this enzyme with an impermeable at room temperature or in the absence of water for the enzyme and / or its substrate Substance is enveloped which becomes permeable to the enzyme and / or its substrate under the conditions of use of the agent.
1 1. Verwendung eines Bleichsystems aus einem Aminoalkohol- oder D-Aminosäure- Oxidase-Aktivität aufweisenden Enzym und einem Substrat für dieses Enzym zum Bleichen von Textilanschmutzungen unter Waschbedingungen.1 1. Use of a bleaching system of an enzyme having amino alcohol or D-amino acid oxidase activity and a substrate for this enzyme for bleaching textile soils under washing conditions.
12. Verwendung eines Systems aus einem Aminoalkohol- oder D-Aminosäure-Oxidase- Aktivität aufweisenden Enzym und einem Substrat für dieses Enzym zur Verringerung der Farbübertragung von gefärbten Textilien auf ungefärbte oder andersfarbige Textilien, wenn diese unter Wasch- oder Nachspülbedingungen zusammenkommen. 12. Use of a system of an enzyme having amino alcohol or D-amino acid oxidase activity and a substrate for this enzyme to reduce the color transfer from dyed textiles to undyed or differently colored textiles when these come together under washing or rinsing conditions.
EP96941618A 1995-12-08 1996-11-29 Bleaching and washing agents with enzyme bleaching system Expired - Lifetime EP0876463B1 (en)

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EP0876463B1 (en) 2006-04-19
DE59611339D1 (en) 2006-05-24
DE19545729A1 (en) 1997-06-12
ES2262160T3 (en) 2006-11-16
US6409770B1 (en) 2002-06-25
ATE323752T1 (en) 2006-05-15
WO1997021796A1 (en) 1997-06-19
JP2000501758A (en) 2000-02-15
JP4044138B2 (en) 2008-02-06

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