EP1165737A2 - Agents de lavage et de nettoyage contenant des enzymes et un activateur de blanchiment - Google Patents

Agents de lavage et de nettoyage contenant des enzymes et un activateur de blanchiment

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Publication number
EP1165737A2
EP1165737A2 EP00920537A EP00920537A EP1165737A2 EP 1165737 A2 EP1165737 A2 EP 1165737A2 EP 00920537 A EP00920537 A EP 00920537A EP 00920537 A EP00920537 A EP 00920537A EP 1165737 A2 EP1165737 A2 EP 1165737A2
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EP
European Patent Office
Prior art keywords
alkyl
weight
composition according
acid
compound
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Granted
Application number
EP00920537A
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German (de)
English (en)
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EP1165737B1 (fr
Inventor
Horst-Dieter Speckmann
Jörg Poethkow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1165737A2 publication Critical patent/EP1165737A2/fr
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to enzyme-containing detergents or cleaning agents which, in addition to the usual constituents, contain a specific bleach activator from the group of the cationic nitriles.
  • detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other constituents, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents and color transfer inhibitors. Such auxiliaries also include substances which support the surfactant performance through the enzymatic degradation of soiling on the textile. The same applies analogously to cleaning agents for hard surfaces.
  • the amylases which have the task of facilitating the removal of starchy soils by the catalytic hydrolysis of the starch polysaccharide, and the cellulases are of particular importance.
  • Cellulases have long been known as aviva agents for cotton fabrics because of their ability to degrade cellulose.
  • laundry softening cellulases preferentially attack and remove microfibrous cellulose, so-called fibrils, which protrudes from the surface of the cotton fiber and hinders the free sliding of the cotton fibers over one another.
  • fibrils which protrudes from the surface of the cotton fiber and hinders the free sliding of the cotton fibers over one another.
  • a side effect of this degradation of fibrils is also the deepening of the optical color impression.
  • Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and Sodium carbonate perhydrate. has long been used as an oxidizing agent for disinfection and bleaching purposes.
  • the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 60 ° C.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- Acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate, and known as pentacellated sugar, acylated aq .
  • bleach activators for which numerous suggestions, especially from the substance classes of the N-
  • detergents and cleaning agents which contain a naturally occurring ⁇ -amylase and a bleach-activating active ingredient of the acetonitrile derivative type.
  • the invention relates to a detergent or cleaning agent containing bleach, which comprises a compound of the general formula I, R 1
  • R 1 for -H, -CH 3 a C 2 . 24 alkyl or alkenyl radical, a substituted C 2.24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a C 1 . 24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C ,.
  • Another object of the invention is the use of a combination of an acetonitrile derivative according to formula (I) and an enzyme, selected from the group comprising protease, amylase, lipase, cellulase and mixtures thereof, to increase the cleaning performance of detergents and cleaning agents, in particular compared proteinaceous, starchy and / or colored, in particular tea-based soiling, when used in, in particular, aqueous washing and cleaning solutions which contain a peroxygen compound.
  • an enzyme selected from the group comprising protease, amylase, lipase, cellulase and mixtures thereof
  • the cleaning performance in relation to colored soiling is to be understood in its broadest meaning and includes both the bleaching of dirt on the textile, the bleaching of dirt in the washing liquor, detached from the textile, and the oxidative destruction of textile colors in the washing liquor that detach from textiles under the washing conditions before they can be drawn onto textiles of a different color. Also when used in cleaning solutions for hard surfaces Both the bleaching of dirt located on the hard surface, in particular tea, and the bleaching of dirt located in the dishwashing liquor and detached from the hard surface are understood by this term.
  • the anions X " include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, hexafluorophosphate, sulfate, hydrogen sulfate, methosulfate and ethosulfate, chlorate, perchlorate, and the anions of carboxylic acids such as formate, acetate, benzoate or Citrate. Preference is given to the use of compounds of the formula I in which X "is chloride, sulfate, hydrogen sulfate or methosulfate.
  • An acetonitrile derivative according to formula I is preferably contained in agents according to the invention in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 7% by weight.
  • a washing or cleaning agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of enzymatically active protein per gram of the total agent.
  • the protein concentration can be determined using known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).
  • proteases which can be used include the enzymes which can be obtained from microorganisms, in particular bacteria or fungi, with a pH optimum in the alkaline range, for example that from international patent applications WO 92/07067. WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.
  • Protease is preferably used in the agent according to the invention in amounts such that the finished agent 100 PE / g to 7 500 PE / g (protease units per gram, determined by the method described in Tenside 7, 125 (1970)), in particular 125 PE / g to 5,000 PE / g and particularly preferably 150 PE / g to 4,500 PE / g.
  • Usable proteases are commercially available, for example under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym®, Everlase®, Maxapem® or Purafect® OxP.
  • amylases which can be used in agents according to the invention and which are preferably used in combination with at least one further enzyme include the enzymes which can be obtained from bacteria or fungi and which have a pH optimum, preferably in the alkaline range up to about pH 10.
  • Usable commercial products are, for example, Termamyl®, Maxamyl®, Duramyl® or Purafect® OxAm.
  • Amylase is preferably used in the agent according to the invention in amounts such that the finished agent 0.01 KNU / g to 2 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme which degrades 5.26 g of starch at pH 5.6 and 37 ° C., based on the method described by P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, page 149), in particular 0.015 KNU / g to 1.8 KNU / g and particularly preferably 0.03 KNU / g to 1.6 KNU / g.
  • the agent according to the invention contains an amylase, this is preferably selected from the genetically modified amylases. Genetically modified amylases are known, for example, from international patent applications WO 94/18314 or WO 95/21247.
  • the lipase optionally contained in the agent according to the invention is an enzyme that can be obtained from microorganisms, in particular bacteria or fungi.
  • microorganisms in particular bacteria or fungi.
  • EP 0 204 208 EP 0 214 761
  • EP 0 258 068 EP 0 385 401
  • EP 0 407 225 EP 0 571 982
  • WO 87/00859 the international national patent applications WO 87/00859 or WO 90/10695 known.
  • Lipase is preferably used in the agent according to the invention in amounts such that the finished agent has a lipolytic activity in the range from 10 LU / g to 100 OOO LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C and pH 7 according to the method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1000 LU / g.
  • Commercial lipases are, for example, Lipolase®, Lipomax®, Lumafast® and Lipozym®.
  • the cellulase which can be used according to the invention belongs to the enzymes which can be obtained from bacteria or fungi and which have a pH optimum, preferably in the almost neutral to weakly alkaline pH range from 6 to 9.5.
  • Such cellulases are known, for example, from German published applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950, European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 or the international patent applications WO 96/34108 and WO 97/34005.
  • the agent according to the invention preferably in amounts such that the finished agent has a cellulolytic activity of 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of sodium Carboxymethyl cellulose at pH 9.0 and 40 ° C., as described in Agric. Biol. Chem. 53, 1275 (1989) by S. Ito et al.), In particular 0.07 IU / g to 1.4 IU / g and particularly preferably 0.1 IU / g to 1.3 IU / g.
  • Suitable commercial products are, for example, Celluzyme® from Novo Nordisk or KAC® from Kao.
  • Suitable peroxygen compounds for use in agents according to the invention are, in particular, hydrogen peroxide and, under the washing conditions, water inorganic salts releasing substance peroxide, including the alkali perborates and percarbonates.
  • - Persilicates and / or persulfates such as caroate belong, but also organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • Peroxygen compounds are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight and particularly preferably from 8% by weight to 25% by weight.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can be expedient.
  • the use according to the invention essentially consists in creating conditions in the presence of a surface contaminated with proteinaceous, starchy and / or colored soils under which a peroxidic oxidizing agent and the combination of acetonitrile derivative and enzyme essential to the invention can react with one another.
  • Such conditions exist especially when all reactants meet in aqueous solution.
  • This can be done by adding the peroxygen compound and the active ingredient combination separately to an optionally detergent-containing solution.
  • a washing or cleaning agent according to the invention which contains the combination of acetonitrile derivative and enzyme and an oxidizing agent containing peroxygen.
  • the detergents and cleaning agents according to the invention which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can, in addition to the active ingredient combination used according to the invention, in principle contain all known ingredients which are customary in such agents.
  • the agents according to the invention can contain builder substances, surface-active surfactants, additional bleaching agents based on organic and or inorganic peroxygen compounds, additional bleach activators, miscible organic solvents, additional enzymes, sequestering agents. Electrolytes, pH regulators and other auxiliary substances such as optical brighteners. Contain graying inhibitors, color transfer inhibitors, foam regulators, silver corrosion inhibitors and colorants and fragrances.
  • the agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable 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.
  • alkyl glycosides and ethoxylation and / or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and also of alkyl phenols with 5 to 12 carbon atoms in the alkyl radical, can be used.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 4 alcohols with 3 EO or 4 EO, C 9 -C ⁇ alcohols with 7 EO, C I3 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C I2 -C 14 alcohol with 3 EO and C 12 -C 18 - alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Extremely low-foaming compounds are usually used in particular in cleaning agents for use in machine dishwashing processes. These preferably include C 12 -C 8 alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • C I2 -C ⁇ 8 -Alkylpolyethy- glycol-polybutylene glycol ethers containing up to 8 moles of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers are also particularly preferred.
  • the hydroxyl-containing alkoxylated alcohols as described in European patent application EP 0 300 305, so-called hydroxy mixed ethers.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (II) in which R'CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are usually separated from one another by a so-called "spacer".
  • This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • the term gemini surfactants is understood not only to mean “dimeric” but also "trimeric” surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061.
  • End group-blocked dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates such as are obtained, for example, from C 12 -C 8 monoolefins with a terminal or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Alkanesulfonates made from C 12 -C 18 alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelhoffreschester C I2 -C 18 fatty alcohols, for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 0 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 6 - alkyl sulfates and C I2 -C] 5 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Surfactants are present in detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, whereas agents for cleaning hard surfaces, in particular for machine cleaning of dishes , have lower surfactant contents of up to 10% by weight, in particular up to 5% by weight and preferably in the range from 0.5% by weight to 3% by weight.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphinephosphonic acid), ethylenediaminethoxy (meth) ethylenediaminethoxy (meth) ethylenediaminethoxy (meth) ethylenediamine (1) 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of European patent EP 0 625 992 or of international patent application WO 92/18542 or of European patent EP 0 232 202,
  • polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality can old.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000.
  • Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • vinyl ethers such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene
  • Terpolymers can also be used as water-soluble organic builder substances, the monomers being two unsaturated acids and / or their salts and also the third monomer vinyl alcohol and / or contain an esterified vinyl alcohol or a carbohydrate.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical, his.
  • Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000.
  • copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents according to the invention.
  • Particularly suitable water-soluble inorganic builder materials are alkali silicates, alkali carbonates and alkali phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric
  • crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. %, used.
  • crystalline sodium aluminosilicates in detergent quality in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA). prefers.
  • Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are -crystalline alkali silicates which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x + 1 y H 2 O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 22, especially 1.9 to 4 and y is a number from 0 to 33 and are preferred values for x 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 y H 2 O
  • ⁇ -sodium disilicate can 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.
  • Crystalline layered silicates of the formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 O 45 xH 2 O, Kenyait), Na-SKS-2 (Na 2 Si 14 O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O I7 xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 xH 2 O, makatite).
  • Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 3H 2 O), Na-SKS-10 (NaHSi 2 O 5 3H 2 O, Kanemit), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ).
  • Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
  • Builder substances can optionally be present in the agents according to the invention in amounts up to 90% by weight. They are preferably contained in amounts of up to 75% by weight. Detergents according to the invention have builder contents of in particular 5% by weight to 50% by weight. In agents according to the invention for cleaning hard surfaces, in particular for machine cleaning of dishes, the builder substance content is in particular 5% by weight to 88% by weight, with such agents preferably not using water-insoluble builder materials. In a preferred embodiment of agents according to the invention for in particular machine cleaning of dishes, 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight of alkali carbonate and 20% by weight to Contain 40 wt .-% alkali disilicate.
  • bleach activators which can be used are, in particular, compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used.
  • Bleach activators of this type can be present in the customary quantitative range, preferably in amounts of 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or known from European patents EP 0 446 982 and EP 0 453 003 can also be used
  • Transition metal complexes can be included 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-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, 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
  • 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% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • Enzymes which can additionally be used in the compositions are those from the class of the cutinases, pullulanases, hemicellulases, oxidases, laccases and peroxidases and mixtures thereof. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus are particularly suitable.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the washing or cleaning agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight.
  • the organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, in addition to water include alcohols 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 those derivable from the compound classes mentioned Ether.
  • Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents can contain further constituents customary in washing and cleaning agents.
  • These optional components include, in particular, enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners as well as colorants and fragrances.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • a cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.
  • 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 contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are present in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • the color transfer inhibitors which are suitable for use in textile detergents according to the invention include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor.
  • water-soluble colloids are usually more organic Naturally suitable, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Starch derivatives other than those mentioned above can also be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixtures such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used .
  • the detergents according to the invention can in particular contain soil release polymers, so-called soil-release polymers, which are generally composed of carboxylic acid units and optionally polymeric diol units and contain, for example, ethylene terephthalate and polyoxyethylene terephthalate groups.
  • soil-release polymers which are generally composed of carboxylic acid units and optionally polymeric diol units and contain, for example, ethylene terephthalate and polyoxyethylene terephthalate groups.
  • Other monomer units for example propylene glycol, polypropylene glycol, alkylene or alkenylene dicarboxylic acids, isophthalic acid, carboxy- or sulfo-substituted phthalic acid isomers can be contained in the soil release polymer.
  • End-capped derivatives that is to say polymers which have neither free hydroxyl groups nor free carboxyl groups, but instead carry, for example, C -alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can also be used.
  • polyesters known from European patent application EP 0 241 985 which, in addition to oxyethylene groups and terephthalic acid units, include 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and Contain glycerol units and are end-capped with C 1 -C 4 -alkyl groups, the soil-release polymers of ethylene terephthalate and polyethylene oxide terephthalate with a molecular weight of 900 to 9000 used in the agents of European patent application EP 0 253 567.
  • polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, which are known from European patent application EP 0 272 033, at least in part by C M - alkyl or Acyl radicals end-capped polyesters with poly-propylene terephthalate and poly-oxyethylene terephthalate units, the sulfoethyl end-capped terephthalate-containing Soil-release polyesters mentioned in European Patent Application EP 0 274 907, the soil-release polyesters with terephthalate, produced by sulfonation of unsaturated end groups, Alkylene glycol and poly-C 1-6 glycol units of the European patent application EP 0 357 280, the cationic soil-release polyesters with amine, ammonium and / or amine oxide groups known from the European patent application EP 0 398 133 and the cationic Soil-release polyesters with eth
  • polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to Polyethylene oxide tere phthalate is 50:50 to 90:10 and its use in detergents is described in German patent DE 28 57 292, and polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, which can be used in detergents according to German patent application DE 33 24 258.
  • Textile detergents according to the invention can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used. In particular when used in machine processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
  • the preparation of solid agents according to the invention is not difficult and can be carried out in a known manner, for example by spray drying or granulation, the enzymes and any further thermally sensitive ingredients, such as bleaching agents, optionally being added separately later.
  • a method known from European Patent EP 0486 592 and having an extrusion step is preferred for producing agents according to the invention with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1.
  • a further preferred production using a granulation process is described in European patent EP 0 642 576.
  • agents according to the invention in tablet form, which can consist of one or more phases, of one color or of more than one color and in particular of one layer or of more than one, in particular of two layers
  • the procedure is preferably such that all constituents - optionally one layer each - are combined in one Mixer mixed together and the mixture is pressed using conventional tablet presses, for example eccentric presses or rotary presses.
  • a tablet produced in this way preferably has a weight of 10 g to 50 g, in particular of 15 g to 40 g.
  • the shape of the tablets is arbitrary and can be round, oval or angular, intermediate forms are also possible. Corners and edges are advantageously rounded.
  • Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of angular or cuboid tablets which are mainly introduced via the metering device, for example the dishwasher, depends on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or of 24x38 mm.
  • Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • agents according to the invention have a significantly improved cleaning performance compared to enzymatically removable soils (A) as well as bleachable soils (B) with the same enzyme content as an agent according to the invention with a higher content of a conventional bleach activator.

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Abstract

L'objectif de l'invention est d'améliorer la capacité de nettoyage d'agents de lavage et de nettoyage contenant un agent de blanchiment, en particulier en ce qui concerne les salissures contenant des protéines et de l'amidon, ainsi que les salissures colorées. Cet objectif est atteint par le fait qu'un tel agent contient, en plus des composants habituels compatibles avec de tels constituants, un composé correspondant à la formule générale (I), dans laquelle: R<1> représente -H, -CH3, un reste alkyle C2-24 ou un reste alcényle, un reste alkyle C2-24 ou un reste alcényle présentant au moins un substituant du groupe -Cl, -Br, -OH, -NH2, -CN, un reste alkyle ou alcénylaryle possédant un groupe alkyle C1-24, ou bien un reste alkyle ou alcénylaryle substitué présentant un groupe C1-24 et au moins un autre substituant sur le cycle aromatique; R<2> et R<3> sont sélectionnés, indépendamment l'un de l'autre, parmi -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH où n = 1, 2, 3, 4, 5 ou 6, et X représente un anion. Cet objectif est également atteint par le fait qu'un tel agent contient une enzyme sélectionnée dans le groupe comprenant la protéase, l'amilase, la lipase, la cellulase et leurs mélanges.
EP00920537A 1999-03-31 2000-03-22 Agents de lavage et de nettoyage contenant des enzymes et un activateur de blanchiment Expired - Lifetime EP1165737B1 (fr)

Applications Claiming Priority (3)

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DE19914811A DE19914811A1 (de) 1999-03-31 1999-03-31 Enzym- und bleichaktivatorhaltige Wasch- und Reinigungsmittel
DE19914811 1999-03-31
PCT/EP2000/002534 WO2000060036A2 (fr) 1999-03-31 2000-03-22 Agents de lavage et de nettoyage contenant des enzymes et un activateur de blanchiment

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EP3011020A1 (fr) 2013-06-17 2016-04-27 Danisco US Inc. Alpha-amylase issue d'un membre de la famille des bacillaceae
US20160160199A1 (en) 2013-10-03 2016-06-09 Danisco Us Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
WO2015050724A1 (fr) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases faisant partie d'un sous-ensemble d'exiguobacterium, et procédés d'utilisation correspondants
MX2016006489A (es) 2013-11-20 2016-08-03 Danisco Us Inc Alfa-amilasas variantes que tienen susceptibilidad reducida a la escision por proteasas y metodos de uso.
WO2017173190A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés
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ES2242613T3 (es) 2005-11-16
AU4107700A (en) 2000-10-23
WO2000060036A3 (fr) 2001-04-26
DE19914811A1 (de) 2000-10-05
JP2002541303A (ja) 2002-12-03
DE50010289D1 (de) 2005-06-16
EP1165737B1 (fr) 2005-05-11
CA2304311A1 (fr) 2000-09-30
US6391838B1 (en) 2002-05-21
WO2000060036A2 (fr) 2000-10-12

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