EP0876463B1 - Agents de blanchiment et de lavage avec systeme de blanchiment enzymatique - Google Patents

Agents de blanchiment et de lavage avec systeme de blanchiment enzymatique Download PDF

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Publication number
EP0876463B1
EP0876463B1 EP96941618A EP96941618A EP0876463B1 EP 0876463 B1 EP0876463 B1 EP 0876463B1 EP 96941618 A EP96941618 A EP 96941618A EP 96941618 A EP96941618 A EP 96941618A EP 0876463 B1 EP0876463 B1 EP 0876463B1
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Prior art keywords
bleaching
oxidase
weight
enzyme
acid
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EP96941618A
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German (de)
English (en)
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EP0876463A1 (fr
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Albrecht Weiss
Marita Grothus
Achim Richert
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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 bleach or detergent which contains, in addition to conventional ingredients for such agents, a conventional bleach activator and a bleaching system of a choline oxidase and the substrate for this oxidase.
  • bleaches Modern universal detergents and bleaching detergents, so-called bleaches, usually contain an oxygen-based oxidant, in particular a peracid, a peracid salt, hydrogen peroxide or a substance which gives hydrogen peroxide under aqueous conditions of use. Since the bleaching effect of hydrogen peroxide alone is often found to be insufficient, bleaching systems are usually used from a per-compound which provides hydrogen peroxide in water and a bleach activator which generates a peracid under perhydrolysis conditions. The most prominent example of such a bleaching system is the widely used combination of alkali metal perborate and N, N, N ', N'-tetraacetylethylenediamine. There has been no lack of attempts to modify this bleaching system by modifying it. For example, International Patent Application WO 89/09813 proposes using a peroxidase enzyme, that is to say an enzyme which catalyzes the reaction of hydrogen peroxide with organic or inorganic substances, as a bleach activator
  • Oxidases are redox enzymes of classification EC 1 (according to the classification of the Enzyme Commission), which are usually Flavintermin, and whose oxidized form is able to oxidize a substrate. The resulting reduced form of the enzyme is reoxidized in aqueous systems by molecular oxygen, which forms hydrogen peroxide as a further product.
  • Examples of such enzymes and their substrates, from the name of the enzyme are phenol oxidase. Amino acid oxidase, xanthine oxidase, urate oxidase, alcohol oxidase. Cholesterol oxidase and glucose oxidase.
  • German Offenlegungsschrift DT 19 18 729 discloses detergents and cleaners 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, an additional 0.5% by weight to 10% by weight of amyloglucosidase should be present.
  • German Offenlegungsschrift DT 20 64 146 discloses detergents and cleaners containing from 1% to 50% by weight of water-soluble surfactant and from 0.01% to 2% by weight of lipoxidase. Preferably, polyunsaturated fatty acids are present as substrates for the lipoxidase.
  • 2,557,623 discloses detergents and cleaners which, in addition to surfactants and builders, contain from 0.3% by weight to 10% by weight of urate oxidase, galactose oxidase or C 1-3 -alcohol oxidase and from 3% by weight to 30% % By weight of uric acid, galactose or C 1-3 -alcohols and / or corresponding ketoalcohols.
  • European Patent EP 0 072 098 relates to liquid bleaches containing a C 1-4 alcohol oxidase and a C 1-4 alcohol.
  • European Patent Application EP 0 603 931 proposes to stabilize the glucose oxidase / glucose system in liquid detergents by the addition of Cu 2+ and / or Ag + ions and by the presence of bleach catalysts, in particular metalloporphines, metalloporphyrins, metallophthalocyanines and or hemin, to increase the bleaching action of the enzymatically generated hydrogen peroxide.
  • bleach catalysts in particular metalloporphines, metalloporphyrins, metallophthalocyanines and or hemin.
  • WO 95/07972 discloses bleaching agents containing an enzymatic system for generating hydrogen peroxide and a bleach-catalyzing coordination complex of Mn or Fe.
  • International Patent Application WO 94/25574 discloses an L-amino acid oxidase from a specific strain of the microorganism Trichoderma harzianum and detergents containing a derate oxidase.
  • the patent application WO 93/15176 A1 discloses methods of preventing color transfer during laundering of textiles and means suitable therefor, characterized by comprising (a) a specific metal-on-metal catalyst (metallo-porphine, metallo-porphyrin or metallo-phthalocyanine or water-soluble or -dispersible derivatives thereof), (b) an amino base catalyst stabilizer for binding to the fifth ligand of the metallocene catalyst, and (c) an enzymatic system capable of generating hydrogen peroxide.
  • a specific metal-on-metal catalyst metallo-porphine, metallo-porphyrin or metallo-phthalocyanine or water-soluble or -dispersible derivatives thereof
  • an amino base catalyst stabilizer for binding to the fifth ligand of the metallocene catalyst
  • an enzymatic system capable of generating hydrogen peroxide.
  • an oxidase is used together with its respective substrate.
  • the choline oxidase is called; Alcohol and aldehyde and glucose oxidase are preferred.
  • Bleach activators are not disclosed in this context; rather, it is said that the funds in question should be free of conventional bleaching agents.
  • the patent application DE 4231767 A1 discloses bleaches and detergents which, in addition to ingredients customary for such compositions, contain a bleach system comprising an enzyme and a substrate for the enzyme, which under use conditions of the composition is capable of producing hydrogen peroxide.
  • suitable enzymes include D-amino acid oxidase, xanthine oxidase, urea oxidase.
  • the aim was to produce in this way the hydrogen peroxide in situ enzymatically in the liquor, so that can be dispensed with to achieve the bleaching effect of conventional bleach activators.
  • the Applicant's aim was to develop a bleaching agent with improved efficacy of the enzymatically generated hydrogen peroxide under washing and cleaning conditions.
  • the invention therefore relates to a bleaching, washing or cleaning agent containing optionally synthetic surfactant, organic and / or inorganic builder and other conventional bleaching, washing or cleaning ingredients, which is characterized in that it is a conventional bleach activator and an enzymatic bleaching system which, under conditions of use of the composition, is capable of producing hydrogen peroxide and which consists of choline oxidase and choline.
  • a second object of the invention is the use of an enzymatic.
  • Bleaching system capable of generating hydrogen peroxide under conditions of use and consisting of choline oxidase and choline for bleaching textile stains under washing conditions, using in addition a conventional bleach activator.
  • Amino alcohol oxidases catalyze the oxidation of primary alcohol functions of amino alcohols to the corresponding acid function by oxygen to form Hydrogen peroxide.
  • an aminoalcohol having primary alcohol function is present as a substrate for the aminoalcohol oxidase.
  • Aminoalcohol oxidase essential to the invention 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.
  • 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 of about pH 6 to pH 9.5.
  • the activity of enzymes is usually expressed in U / g, where the unit corresponds to 1 U of the activity of that 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 ⁇ katal.
  • the aminoalcohol oxidase used is choline oxidase, as produced, for example, by Alcaligenes species or Arthrobacter globifonnis.
  • Choline oxidase is commercially available from Sigma, for example.
  • a said oxidase is preferably used in the agent according to the invention in amounts such that the total agent has an oxidase activity of from 30 U / g to 20,000 U / g, in particular from 60 U / g to 15,000 U / g.
  • Agents with oxidase activities in the stated ranges have sufficiently rapid hydrogen peroxide release for common European machine washing processes.
  • enzymes having amino alcohol oxidase activity used according to the invention have a significantly higher activity 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.
  • it may serve as an indication that in enzyme-substrate systems which release one mole of hydrogen peroxide per mole of reacted substrate, the presence of from about 0.05% to 0.6% by weight of the substrate in the wash, Bleaching or cleaning liquor is usually sufficient to achieve a good bleaching result.
  • an agent according to the invention can be formulated in any desired form, for example as aqueous or nonaqueous liquid agent, more or less viscous, aqueous or nonaqueous paste product, granular powder or in stick, bar or bar form, whereby for the production of such agents recourse can be had to known methods of the relevant state of the art.
  • it is present as a free-flowing particulate product, for example, as a powder having a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l before.
  • the oxidase is preferably used in an adsorbed to inert, that is no substrate for the enzyme-representing carrier material adsorbed form, in coating substances or in the form of conventional granules with inorganic and / or organic carrier materials.
  • Such enzyme granules can be prepared by processes known with other enzymes, as for example in German patent DE 16 17 232, German Offenlegungsschriften 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, further customary detergent or cleaning agent enzymes are added, in particular proteases, lipases, cutinases, amylases, pullulanases, hemicellulases and cellulases, these may be present in separate particles or in the form of a multenzyme granulate, such as in US Pat German patent applications DE 44 22 433 or DE 44 22 609 or in international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein, are used together with oxidase.
  • Inventive liquid to pasty agents for use in household washing machines are preferably in portioned form, for example in bag form, confectioned, wherein a detergent according to the invention surrounding container material, such as sheet Polyvinylakohol is selected so that it dissolves under the conditions of use, that is only in the washing machine during the washing process and releases the detergent so that the bleach system contained in the detergent first meets with the oxygen in the air and forms hydrogen peroxide.
  • container material such as sheet Polyvinylakohol
  • the enzyme comprising the oxidase activity and / or the substrate for this enzyme are enveloped with a substance which is impermeable to the enzyme and / or its substrate at room temperature or in the absence of water which becomes permeable to the enzyme and / or its substrate under conditions of use of the agent.
  • a substance which is impermeable to the enzyme and / or its substrate at room temperature or in the absence of water which becomes permeable to the enzyme and / or its substrate under conditions of use of the agent are at temperatures above room temperature, in particular in the range of 35 ° C to 75 ° C melting organic substances, for example fatty alcohols, polyglycols, Paraffinwachsc or fatty acid esters.
  • water-soluble or water-dispersible substances such as finely divided Alkalialumosilikat, layered silicate, clay or bentonite, are suitable.
  • composition of the washing, bleaching or cleaning agents can be selected virtually as desired within the scope of known formulations.
  • the agents according to the invention may in particular be builders, surface-active surfactants, water-miscible organic solvents, further enzymes, sequestering agents, electrolytes, pH regulators, additional peroxygen bleaching agents and other auxiliaries, such as optical brighteners, grayness inhibitors, foam regulators, bleach activators, dyes and fragrances and, if desired, additional Color transfer inhibitors included.
  • conventional bleach activators that is to say compounds which under perhydrolysis conditions are optionally present substituted perbenzoic acid and / or aliphatic peroxycarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, used.
  • Suitable are the customary bleach activators which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenolsulfonates , in particular nonanoyl or Isononanoyloxybenzolsulfonat, acylated polyhydric alcohols, especially triacctin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, tetra
  • the sulfone imines 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 bleach catalysts.
  • the candidate transition metal compounds include in particular from the German patent application DE 195 29 905 known manganese. Iron-.
  • Bleach-enhancing transition metal complexes in particular having 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 of 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.
  • compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • N-alkyl-amines vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of Sulfuric acid half esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation of said nonionic surfactants with a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Surfactants of this type are contained in the cleaning or washing agents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, while the bleaching agents according to the invention can also be surfactant-free and preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% 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 (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polycarboxylic acids, in particular citric acid and sugar acids, and also polymeric (poly) carboxylic acids , In particular, accessible by oxidation of polysaccharides polycarboxylates of International Patent Application WO 93/16110, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, though 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 wt .-%.
  • 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, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C 1 -C 4 carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% 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 .-% of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
  • This carbohydrate can be for example a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides are preferred. Particularly preferred is sucrose.
  • the use of the third monomer presumably incorporates predetermined breaking points 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 DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1,000 and 200,000, preferably between 200 and 50,000 and especially between 3,000 and 10,000.
  • copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation 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 may be present in compositions according to the invention 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. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and are preferably at least 80 wt .-% of particles having a size less than 10 microns.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O 2x + .yH 2 O used in the x, the so-called module is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O
  • ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • compositions according to the invention can be used in compositions according to the invention.
  • a crystalline sodium layer silicate having a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • alkali metal aluminosilicate in particular zeolite
  • 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 metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • Builders are preferably present in the detergents or cleaners according to the invention 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 those which complex only the components of the water hardness Builders are and preferably not more than 20 wt.%, In particular from 0.1 wt .-% to 5 wt .-%, of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic, Aminopolyphosphonklaren and hydroxypolyphosphonic 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. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • the optionally used Enzymes and the oxidase to be used according to the invention can be adsorbed on carriers and / or embedded in encapsulating substances, as described for example in International Patent Applications WO 92/11347 or WO 94/23005, in order to protect them against premature inactivation.
  • the additional enzymes mentioned are preferably present in the compositions according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 2% by weight.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers.
  • Such water-miscible solvents are preferably present in the compositions according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions 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, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions according to the invention.
  • compositions 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.
  • preparation of compositions according to the invention having an increased bulk density in particular in the range from 650 g / l to 950 g / l, preference is given to a process known from the European patent EP 486 592 which has an extrusion step.
  • Detergents, cleaners or bleaches according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageous by simply mixing the ingredients that can be added in bulk or as a solution in an automatic mixer produced.
  • the formation of hydrogen peroxide by means 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 / l) at pH 10 and 30 ° C.
  • the H 2 O 2 concentration was determined photometrically using Lambert-Beer's law on peroxidase-catalyzed dye formation from 4-aminophenazone and chromotropic acid.
  • the concentration of the respective oxidase substrate D-alanine, choline chloride or glucose
  • the oxidases were used in activities of 1 U / ml.
  • Hydroxylammonium sulfate (concentration 1 mmol / l) was additionally present in the experiments with D-amino acid oxidase as well as in the comparative experiments with glucose oxidase. Table 1 below shows the hydrogen peroxide concentrations obtained after 30 minutes and 45 minutes.

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Claims (7)

  1. Agent de blanchiment, de lavage ou de nettoyage, contenant éventuellement un tensio-actif synthétique, des builders organiques et/ou inorganiques ainsi que divers composants habituels d'agent de blanchiment, de lavage ou de nettoyage, caractérisé en ce qu'il contient un système de blanchiment enzymatique qui, dans les conditions d'application de l'agent, est en mesure de produire du peroxyde d'hydrogène, et qui est constitué de choline oxydase et de choline, et qui contient en sus un activateur de blanchiment classique.
  2. Agent selon la revendication 1, caractérisé en ce qu'il présente une activité d'oxydase de 30 U/g à 20 000 U/g.
  3. Agent selon l'une quelconque des revendications 1 à 2, caractérisé en ce qu'il contient en sus, un catalyseur de blanchiment.
  4. Agent selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il se présente sous une forme particulaire fluide ayant une masse volumique apparente de 300 g/l à 1 200 g/l, en particulier de 500 g/l à 900 g/l.
  5. Agent selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il se présente sous la forme d'un agent de lavage ou de nettoyage pâteux ou liquide.
  6. Agent selon la revendication 5, caractérisé en ce qu'il se présente sous la forme d'un liquide non aqueux ou d'une pâte non aqueuse.
  7. Utilisation d'un système de blanchiment enzymatique qui, dans des conditions d'application, est en mesure de produire du peroxyde d'hydrogène, et qui est constitué de choline oxydase et de choline, pour blanchir des salissures de textile dans des conditions de lavage où, en sus, un activateur de blanchiment classique est mis en oeuvre.
EP96941618A 1995-12-08 1996-11-29 Agents de blanchiment et de lavage avec systeme de blanchiment enzymatique Expired - Lifetime EP0876463B1 (fr)

Applications Claiming Priority (3)

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DE19545729 1995-12-08
DE19545729A DE19545729A1 (de) 1995-12-08 1995-12-08 Bleich- und Waschmittel mit enzymatischem Bleichsystem
PCT/EP1996/005282 WO1997021796A1 (fr) 1995-12-08 1996-11-29 Agents de blanchiment et de lavage avec systeme de blanchiment enzymatique

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EP0876463A1 EP0876463A1 (fr) 1998-11-11
EP0876463B1 true EP0876463B1 (fr) 2006-04-19

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EP (1) EP0876463B1 (fr)
JP (1) JP4044138B2 (fr)
AT (1) ATE323752T1 (fr)
DE (2) DE19545729A1 (fr)
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WO (1) WO1997021796A1 (fr)

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ATE323752T1 (de) 2006-05-15
ES2262160T3 (es) 2006-11-16
DE19545729A1 (de) 1997-06-12
JP4044138B2 (ja) 2008-02-06
DE59611339D1 (de) 2006-05-24
US6409770B1 (en) 2002-06-25
JP2000501758A (ja) 2000-02-15
EP0876463A1 (fr) 1998-11-11
WO1997021796A1 (fr) 1997-06-19

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