EP1084217B1 - Detergents contenant une amylase et des derives d'acetonitrile - Google Patents

Detergents contenant une amylase et des derives d'acetonitrile Download PDF

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EP1084217B1
EP1084217B1 EP99925032A EP99925032A EP1084217B1 EP 1084217 B1 EP1084217 B1 EP 1084217B1 EP 99925032 A EP99925032 A EP 99925032A EP 99925032 A EP99925032 A EP 99925032A EP 1084217 B1 EP1084217 B1 EP 1084217B1
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weight
composition
compound
acid
formula
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EP1084217A1 (fr
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Beatrix Kottwitz
Horst-Dieter Speckmann
Karl-Heinz Maurer
Christian Nitsch
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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
    • 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
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • 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 and cleaning agents which, in addition to usual components an amylase from Bacillus amyloliquefaciens and certain contain bleach-activating agents.
  • Detergents contain the ingredients that are essential for the washing process such as surfactants and builder materials, usually other components that can be found under the term washing aids can summarize and the different groups of active ingredients such as foam regulators, graying inhibitors, bleach, Bleach activators and color transfer inhibitors include.
  • active ingredients such as foam regulators, graying inhibitors, bleach, Bleach activators and color transfer inhibitors include.
  • auxiliaries also include substances that affect surfactant performance through enzymatic degradation support from soiling on the textile. The same applies analogously also for cleaning agents for hard surfaces. Besides that comes the Proteases supporting the removal of proteins and the lipases that break down fat Amylases are of particular importance.
  • Amylases have the task of removing Starchy soiling due to the catalytic hydrolysis of the starch polysaccharide to facilitate and have been in for this purpose for a long time Detergents for dishes, but also in detergents for use in the Textile laundry used. To a large extent, this has so far been the case a thermostable amylase from Bacillus licheniformis, for example, under the Termamyl® is commercially available. More recently come in such means Increased genetically modified amylases, that is, compared to natural occurring amylases with the aid of genetic engineering methods modified amino acid sequence, for use. In addition to increasing its performance, the Genetic modification of amylases essentially increases the stability of the Enzyme, especially against the attack of oxidizing agents.
  • the invention therefore relates to an amylase-containing washing or cleaning agent, the ⁇ -amylase from Bacillus amyloliquefaciens and at least one compound of the general formula I, R 1 R 2 R 3 N + CH 2 CN X - in which R 1 , R 2 and R 3 are, independently of one another, an alkyl, alkenyl or aryl group having 1 to 18 C atoms, the groups R 2 and R 3 also being part of a heterocycle which includes the N atom and optionally further hetero atoms and X is a charge-balancing anion, in addition to the usual ingredients compatible with such components.
  • Another object of the invention is the use of a corresponding Combination to increase the cleaning performance of detergents and cleaning agents, especially against starchy and / or colored, in particular tea-based soiling, when used in aqueous washing and cleaning solutions, which contain a peroxygen compound.
  • the cleaning performance compared colored stains are to be understood and encompassed in their broadest meaning both the bleaching of dirt on the textile, the bleaching of dirt in the wash liquor, detached from the textile as well as that oxidative destruction of textile dyes in the wash liquor, which are under detach the washing conditions from textiles before moving onto textiles of different colors can raise.
  • ⁇ -Amylase from Bacillus amyloliquefaciens has long been, for example, from the United States Patent US 1,227,374 known. For example, it is under the Description Amylase BAN® commercially available.
  • An agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of amylolytic protein per gram of the total agent.
  • the protein concentration can be determined using known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).
  • R 1 is preferably an alkyl group with 1 to 3 carbon atoms, in particular a methyl group.
  • 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 , Is sulfate, hydrogen sulfate or methosulfate - preferred is the use of compounds according to formula I in which X is.
  • An acetonitrile derivative according to formula I is preferred in agents according to the invention in amounts from 1% by weight to 10% by weight, in particular from 2% by weight to 7% by weight contain.
  • the detergents and cleaning agents according to the invention which are particularly powdery solids, in densified particle form, as homogeneous solutions or Suspensions can be present in addition to those used according to the invention Active ingredient combination in principle all known ingredients that are common in such agents contain.
  • the agents according to the invention can in particular builder substances, surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, additional bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, Color transfer inhibitors, foam regulators, silver corrosion inhibitors and Dyes and fragrances included.
  • the agents according to the invention can contain one or more surfactants, wherein in particular anionic surfactants, nonionic surfactants and their mixtures, but also cationic, zwitterionic and amphoteric surfactants come into question.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or Propoxylation products of alkyl glycosides or linear or branched Alcohols each with 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 are also 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, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl radical.
  • 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 can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • 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 18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether, each having up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and also end-capped alkyl polyalkylene glycol mixed ethers.
  • C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether each having up to 8 moles of ethylene oxide and butylene oxide units in the molecule
  • end-capped alkyl polyalkylene glycol mixed ethers also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European patent application EP 0 300 305, so-called hydroxy mixed ethers.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (II) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms.
  • R 2 represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] stands for 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) in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 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, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • 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
  • [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 of the kind obtained, for example, from C 12 -C 18 monoolefins having an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are produced by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin at 8 to 20 ° C -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 no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -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 and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • Alk (en) yl sulfates of the chain length mentioned are also preferred. which contain a synthetic, petrochemical-based straight-chain alkyl radical, which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • 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.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols.
  • sulfosuccinates preferably represent fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • 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 also suitable as further anionic surfactants.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. derived soap mixtures.
  • 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 Form of their sodium or potassium salts, especially in the form of the sodium salts.
  • surfactants are preferred in quantitative proportions 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, whereas Agents for cleaning hard surfaces, in particular for machine cleaning of dishes, 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 (methylenephosphonic acid), ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid and ethylenediaminephosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000.
  • Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances can, if desired, in amounts up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight be included. Amounts close to the above upper limit are preferably in paste-like or liquid, in particular water-containing agents according to the invention used.
  • Alkali silicates come as water-soluble inorganic builder materials, Alkali carbonates and alkali phosphates, in the form of their alkaline, neutral or acidic Sodium or potassium salts can be considered.
  • examples for this are Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric Trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, as well as the corresponding potassium salts or mixtures of sodium and Potassium salts.
  • water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in particular in liquid agents from 1% by weight to 5% by weight.
  • crystalline ones 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 S.p.A.), prefers. Amounts close to the above limit are preferably in solid, particulate Funds used.
  • Suitable aluminosilicates in particular have none Particles with a grain size above 30 microns and preferably exist at least 80 wt .-% of particles with a size below 10 microns.
  • Your calcium binding capacity that can be determined according to the information in German patent DE 24 12 837 usually in the range of 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 disilicate 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, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 294 753. are used in a further preferred embodiment of agents according to the invention.
  • Crystalline layered silicates of the formula (I) given above are sold by Clariant GmbH 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 17 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
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 ⁇ -Na 2 Si 2 O 5
  • crystalline layered silicates are given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33 - 38 and in "Soap-oil-fat waxes, 116 year, No. 20/1990" on pages 805 - 808 published articles.
  • Builder substances can optionally be present in amounts in the agents according to the invention up to 90 wt .-% can be included. They are preferably in amounts up to 75% by weight. contain.
  • Detergents according to the invention have builder contents of in particular 5 wt% to 50 wt%.
  • Harder in cleaning agents according to the invention Surfaces, especially for the automatic cleaning of dishes, is the content of builder substances in particular 5% by weight to 88% by weight, with such agents preferably no water-insoluble builder materials are used.
  • means according to the invention for in particular mechanical Cleaning dishes is 20 wt .-% to 40 wt .-% more water-soluble organic Builder, especially alkali citrate, 5 wt .-% to 15 wt .-% alkali carbonate and Contain 20 wt .-% to 40 wt .-% alkali disilicate.
  • peroxygen compounds suitable for use in agents according to the invention come especially organic peracids or peracid salts of organic Acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, Hydrogen peroxide and under the washing conditions hydrogen peroxide releasing inorganic salts, to which perborate, percarbonate, persilicate and / or Persulfate such as caroate should be considered.
  • organic peracids or peracid salts of organic Acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, Hydrogen peroxide and under the washing conditions hydrogen peroxide releasing inorganic salts, to which perborate, percarbonate, persilicate and / or Persulfate such as caroate should be considered.
  • solid peroxygen compounds to be used they can be used in the form of powders or granules that can
  • an inventive Agents containing peroxygen compounds are preferred in amounts of 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 phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as Magnesium sulfate can be useful.
  • bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used.
  • bleach activators Compounds containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or if appropriate carry substituted benzoyl groups.
  • acylates are preferred Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE
  • amylase essential to the invention come from the class of proteases, lipases, cutinases, pullulanases, Hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof in question.
  • amylase other than the invention essential in addition to this.
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus enzymatic substances obtained.
  • the Amylase essential to the invention and the optionally additionally used enzymes can, as for example in the European patent EP 0 564 476 or in the International patent application WO 94/23005 described, adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation protect. They are preferred in the washing or cleaning agents according to the invention in amounts up to 5% by weight, in particular from 0.2% by weight to 4% by weight, contain. If the agent according to the invention contains protease, it preferably has one proteolytic activity in the range from about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g.
  • enzymes in the agents according to the invention can be used by incorporating the two or more separate or separately in a known manner packaged enzymes or by two or more together in one granulate made-up enzymes, such as those from international patent applications WO 96/00772 or WO 96/00773 known.
  • water usable organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and those derived from the compound classes mentioned Ether.
  • Such water-miscible solvents are in the agents according to the invention preferably in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents can be further customary in detergents and cleaning agents Components included.
  • These optional components include in particular Enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners as well as colors and fragrances.
  • Enzyme stabilizers include in particular Enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners as well as colors and fragrances.
  • An inventive Hard surface cleaners can also be abrasive Components, in particular from the group comprising quartz flours, wood flours, Plastic flours, chalks and micro glass balls and their mixtures.
  • Abrasives are preferably not present in the cleaning agents according to the invention 20 wt .-%, in particular from 5 wt .-% to 15 wt .-%, contain.
  • the agents according to the invention cannot be systemic and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, however also mineral acids, especially sulfuric acid, or bases, especially ammonium or Alkali hydroxides included.
  • Such pH regulators are in the invention Agents in amounts of preferably not more than 20% by weight, in particular of 1.2 wt .-% to 17 wt .-%, included.
  • Color transfer inhibitors include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly- (vinylpyridine-N-oxide) and copolymers of Vinyl pyrrolidone with vinyl imidazole.
  • Graying inhibitors are responsible for the dirt detached from the textile fiber to keep suspended in the fleet.
  • water-soluble colloids are usually more organic Suitable in nature, 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, acidic groups containing polyamides are suitable for this purpose.
  • starch derivatives mentioned above for example aldehyde starches.
  • P refers cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • Textile detergents according to the invention can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid are suitable or similarly constructed connections that instead the morpholino group a diethanolamino group, a methylamino group, a Wear anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may be present, for example those 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 be used.
  • 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 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.
  • compositions according to the invention presents no difficulties and can in a known manner, for example by spray drying or granulation, where the enzymes and any other thermally sensitive ingredients such as Example bleach may be added separately later if necessary.
  • Agents with increased bulk density especially in the range of 650 g / l to 950 g / l, is a known from European patent EP 0 486 592, a method having an extrusion step is preferred.
  • Another preferred Production using a granulation process is in the European patent specification EP 0 642 576.
  • agents according to the invention in tablet form which are single-phase or multi-phase, single-color or multi-color and in particular from one layer or from more, especially two layers, can be preferred in such a way that all components - possibly one layer each - in a mixer mixed together and the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably pressed at 60 to 70 kN.
  • a tablet produced in this way preferably has a weight of 10 g to 50 g, in particular from 15 g to 40 g.
  • the shape of the tablets is arbitrary and can be round, oval or angular, with intermediate shapes also possible. Corners and edges are advantageously rounded. Round tablets preferably have one Diameters from 30 mm to 40 mm. In particular the size of angular or cuboid tablets, which are predominantly via the metering device for example, the dishwasher is dependent on the Geometry and volume of this dosing device.
  • Exemplary preferred Embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), especially from 26x36 mm or from 24x38 mm.
  • Liquid or pasty washing or cleaning agents according to the invention in Forms of common solvent-containing solutions are usually simple Mixing the ingredients in bulk or as a solution in an automatic Mixers can be made.
  • a detergent V2 which was otherwise composed the same way, but instead of Termamyl® contained the same amount of protein of the genetically modified amylase Duramyl®, a detergent otherwise composed as V1 V3, which contained instead of Termamyl® the same protein amount of the genetically modified Amylase Purafect® OxAm, a detergent V4 otherwise composed like V1 .
  • agents according to the invention had an agent containing another amylase clearly superior washing performance. Essentially the same applies if you are in agents according to the invention the acetonitrile derivative by the conventional Bleach activator replaced TAED.
  • Detergent ( V5 or V6 ) for the automatic cleaning of dishes containing 55% by weight sodium tripolyphosphate (calculated as anhydrous), 4% by weight amorphous sodium disilicate (calculated as anhydrous), 22% by weight sodium carbonate, 9% by weight.
  • % Sodium perborate, 2% by weight N-methyl-morpholinium acetonitrile methosulfate, 2% by weight nonionic surfactant and 1% by weight or 2% by weight amylase granules (Termamyl® 60T) and 1, 4% by weight of a protease granulate (activity 200,000 PE / g) with the Bacillus lentus protease (remainder to 100% by weight of water, perfume and dye), agents ( V7 or V8 ) which are otherwise like V5 or V6 were composed, but instead of Termamyl®, contained protein-identical amounts of Duramyl®, and agents according to the invention (M3 or M4), which were otherwise composed like V5 or V6 , but instead of Termamyl®, contained protein-identical amounts of amylase from Bacillus amyloliquefaciens, were tested as follows:

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Claims (13)

  1. Produit de lavage ou de nettoyage contenant une amylase,
    caractérisé en ce qu'
    il contient de l'α-amylase de Bacillus amyloliquefaciens et au moins un composé de formule générale I, R1R2R3N+CH2CN X- dans laquelle R1, R2 et R3 représentent, indépendamment les uns des autres, un groupe alkyle, alcényle ou aryle ayant de 1 à 18 atomes de carbone, les groupes R2 et R3 pouvant également faire partie d'un hétérocycle incluant l'atome d'azote et éventuellement d'autres hétéroatomes, et X est un anion équilibrant la charge, en plus de composants usuels, compatibles avec de tels composants.
  2. Produit selon la revendication 1,
    caractérisé en ce qu'
    il contient de l'amylase en quantités de 0,001 mg à 0,5 mg, en particulier de 0,02 mg à 0,3 mg par gramme du produit total.
  3. Produit selon la revendication 1 ou 2,
    caractérisé en ce que
    dans le composé de formule I, R2 et R3 forment, avec incorporation de l'atome d'azote quaternaire, un cycle morpholinium.
  4. Produit la revendication 3,
    caractérisé en ce que
    dans le composé de formule I, R1 est un groupe alkyle ayant de 1 à 3 atomes de carbone, en particulier un groupe méthyle.
  5. Produit selon l'une quelconque des revendications 1 à 4,
    caractérisé en ce que
    dans le composé de formule I, l'anion X- équilibrant la charge est choisie parmi les halogénures tels que chlorure, fluorure, iodure et bromure, le nitrate, l'hydroxyde, l'hexafluorophosphate, le sulfate, l'hydrogénosulfate, le méthosulfate et l'éthosulfate, le chlorate, le perchlorate et les anions d'acides carboxyliques, tels que formiate, acétate, benzoate ou citrate.
  6. Produit selon l'une quelconque des revendications 1 à 5,
    caractérisé en ce que
    dans le composé de formule I, l'anion X- équilibrant la charge est le sulfate, l'hydrogénosulfate ou le méthosulfate.
  7. Produit selon l'une quelconque des revendications 1 à 6,
    caractérisé en ce qu'
    il contient de 1 % en poids à 10 % en poids, en particulier de 2 % en poids à 7 % en poids, d'un composé de formule générale I.
  8. Produit selon l'une quelconque des revendications 1 à 7,
    caractérisé en ce qu'
    il contient de 5 % en poids à 30 % en poids, en particulier de 8 % en poids à 25 % en poids, d'un agent de blanchiment à base d'oxygène.
  9. Produit selon la revendication 8,
    caractérisé en ce qu'
    il contient un composé peroxygéné choisi dans le groupe comprenant des peracides organiques, le peroxyde d'hydrogène, un perborate alcalin et un percarbonate alcalin, ainsi que des mélanges de ceux-ci.
  10. Produit selon l'une quelconque des revendications 1 à 9,
    caractérisé en ce que,
    en plus des composés de formule I, sont présent de 0,5 % en poids à 10 % en poids, en particulier de 1 % en poids à 8 % en poids, de composés libérant des acides peroxocarboxyliques dans les conditions de perhydrolyse.
  11. Produit selon l'une quelconque des revendications 1 à 10,
    caractérisé en ce que,
    en plus du composé de formule I, sont présents des sels ou complexes de métaux de transition catalysant le blanchiment, en particulier en quantités de 0,001 % en poids à 0,5 % en poids.
  12. Utilisation d'une association d'α-amylase de Bacillus amyloliquefaciens et d'un composé de formule I, R1R2R3N+CH2CN X- dans laquelle R1, R2 et R3 représentent indépendamment les uns des autres, un groupe alkyle, alcényle ou aryle ayant de 1 à 18 atomes de carbone, les groupes R2 et R3 pouvant également faire partie d'un hétérocycle incluant l'atome d'azote et éventuellement d'autres hétéroatomes, et X est un anion équilibrant la charge, pour l'augmentation du pouvoir de nettoyage de produits de lavage et de nettoyage dans leur utilisation, en particulier, dans des solutions aqueuses de lavage et de nettoyage qui contiennent un composé peroxygéné.
  13. Utilisation selon la revendication 12,
    caractérisée en ce que
    le pouvoir de nettoyage à l'égard de salissures contenant de l'amidon et/ou colorées, en particulier à base de thé, est accru.
EP99925032A 1998-06-03 1999-05-25 Detergents contenant une amylase et des derives d'acetonitrile Expired - Lifetime EP1084217B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19824687A DE19824687A1 (de) 1998-06-03 1998-06-03 Amylase und Acetonitril-Derivate enthaltende Wasch- und Reinigungsmittel
DE19824687 1998-06-03
PCT/EP1999/003570 WO1999063038A1 (fr) 1998-06-03 1999-05-25 Detergents contenant une amylase et des derives d'acetonitrile

Publications (2)

Publication Number Publication Date
EP1084217A1 EP1084217A1 (fr) 2001-03-21
EP1084217B1 true EP1084217B1 (fr) 2002-09-04

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Country Status (8)

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EP (1) EP1084217B1 (fr)
JP (1) JP2002517553A (fr)
AT (1) ATE223473T1 (fr)
DE (2) DE19824687A1 (fr)
ES (1) ES2183561T3 (fr)
HU (1) HUP0102184A2 (fr)
PL (1) PL344533A1 (fr)
WO (1) WO1999063038A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19914811A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Enzym- und bleichaktivatorhaltige Wasch- und Reinigungsmittel
US6277802B1 (en) * 2000-03-24 2001-08-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Use of cationic nitriles in combination with enzymes in machine dishwashing detergent applications
US6602836B2 (en) 2000-05-11 2003-08-05 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Machine dishwashing compositions containing cationic bleaching agents and water-soluble polymers incorporating cationic groups
EP1280881B1 (fr) * 2000-05-11 2006-09-13 Unilever Plc Compositions detergentes pour lave-vaisselle contenant des agents de blanchiment et des polymeres
DZ3349A1 (fr) 2000-07-28 2002-02-07 Henkel Kgaa Nouvelle enzyme amylolytique issue de bacillus sp. a 7-7 (dsm 12368) ainsi que produits de lavage et nettoyage contenant ledit enzyme amylolytique
WO2002044350A2 (fr) 2000-11-28 2002-06-06 Henkel Kommanditgesellschaft Auf Aktien Nouvelle cyclodextrine-glucanotransferase (cgtase) issue de bacillus agaradherens (dsm 9948) et produits detergents et de nettoyage comprenant cette nouvelle cyclodextrine-glucanotransferase
DE60327248D1 (de) 2002-12-18 2009-05-28 Procter & Gamble Organischer aktivator
DE102004047777B4 (de) 2004-10-01 2018-05-09 Basf Se Alpha-Amylase-Varianten mit erhöhter Lösungsmittelstabilität, Verfahren zu deren Herstellung sowie deren Verwendung
DE102004047776B4 (de) 2004-10-01 2018-05-09 Basf Se Gegen Di- und/oder Multimerisierung stabilisierte Alpha-Amylase-Varianten, Verfahren zu deren Herstellung sowie deren Verwendung
DE102005053529A1 (de) 2005-11-08 2007-06-21 Henkel Kgaa System zur enzymatischen Generierung von Wasserstoffperoxid
BR112012024674B1 (pt) * 2010-04-26 2019-07-02 Novozymes A/S Grânulo, e, composição de detergente granular
DE102012217306B4 (de) * 2012-09-25 2017-01-12 Vacuumschmelze Gmbh & Co. Kg Reinigungsmittel, dessen Verwendung und Verfahren zum Entfernen von ausgehärteten Gießharzen, Klebstoffen, Montageschäumen, Lackfilmen und Lackresten

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6490296A (en) * 1987-09-30 1989-04-06 Kao Corp Detergent composition
GB9012001D0 (en) * 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
ES2126743T5 (es) * 1993-02-11 2010-02-05 Genencor International, Inc. Alfa-amilasa oxidativamente estable.
US5739327A (en) * 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
DE19605526A1 (de) * 1996-02-15 1997-08-21 Hoechst Ag Ammoniumnitrile und deren Verwendung als Bleichaktivatoren
ZA974226B (en) * 1996-05-17 1998-12-28 Procter & Gamble Detergent composition

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PL344533A1 (en) 2001-11-05
JP2002517553A (ja) 2002-06-18
DE19824687A1 (de) 1999-12-09
WO1999063038A1 (fr) 1999-12-09
HUP0102184A2 (hu) 2001-10-28
EP1084217A1 (fr) 2001-03-21
ATE223473T1 (de) 2002-09-15
ES2183561T3 (es) 2003-03-16
DE59902575D1 (de) 2002-10-10

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