WO1999063039A1 - Detergents contenant une amylase - Google Patents

Detergents contenant une amylase Download PDF

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Publication number
WO1999063039A1
WO1999063039A1 PCT/EP1999/003571 EP9903571W WO9963039A1 WO 1999063039 A1 WO1999063039 A1 WO 1999063039A1 EP 9903571 W EP9903571 W EP 9903571W WO 9963039 A1 WO9963039 A1 WO 9963039A1
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WIPO (PCT)
Prior art keywords
acid
nonionic surfactant
weight
amylase
cleaning
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PCT/EP1999/003571
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German (de)
English (en)
Inventor
Beatrix Kottwitz
Horst-Dieter Speckmann
Karl-Heinz Maurer
Christian Nitsch
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to HU0102143A priority Critical patent/HUP0102143A2/hu
Priority to PL99344532A priority patent/PL344532A1/xx
Priority to EP99926389A priority patent/EP1084221A1/fr
Priority to JP2000552236A priority patent/JP2002517554A/ja
Publication of WO1999063039A1 publication Critical patent/WO1999063039A1/fr

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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

Definitions

  • the present invention relates to enzyme-containing detergents and cleaning agents which, in addition to the usual constituents, contain an amylase from Bacillus amyloliquefaciens and a specific surfactant system.
  • detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other ingredients, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators 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. In addition to the proteases that support protein removal and the fat-cleaving lipases, amylases are of particular importance.
  • Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and for this purpose have been used for a long time in detergents for dishes, but also in detergents for use in textile washing. For the most part, it was previously a thermostable amylase from Bacillus licheniformis, which is commercially available, for example, under the name Termamyl®. More recently, such agents have increasingly used genetically modified amylases, that is to say with amino acid sequences modified in comparison to naturally occurring amylases with the aid of genetic engineering methods. In addition to increasing their performance, the genetic modification of amylases essentially aims to increase the stability of the enzyme, in particular against the attack of oxidizing agents.
  • the invention therefore relates to an amylase-containing washing or cleaning agent which contains ⁇ -amylase from Bacillus amyloliquefaciens and a system of anionic and nonionic surfactant in which the amount of the nonionic surfactant predominates, in addition to the usual ingredients compatible with such constituents.
  • Another object of the invention is the use of a corresponding combination to increase the cleaning performance of detergents and cleaning agents, especially in relation to starchy soiling, when used in, in particular, aqueous washing and cleaning solutions.
  • ⁇ -Amylase from Bacillus amyloliquefaciens has long been known, for example from US Pat. No. 1,227,374. For example, it is commercially available under the name Amylase BAN®.
  • 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).
  • 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 include, in particular, builder substances, bleaching agents based on organic and / or inorganic peroxygen compounds, 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.
  • the agents according to the invention contain one or more surfactants, and in addition to nonionic surfactants and anionic surfactants, their mixtures with cationic, zwitterionic and / or amphoteric surfactants are also suitable.
  • the proportion of nonionic surfactant in the system of anionic surfactant and nonionic surfactant is preferably more than 75% by weight, in particular 80% by weight to 99% by weight, although the case may also arise that the surfactant system consists entirely of non-ionic surfactant.
  • 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 On average, 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or can contain linear and methyl-branched radicals in the mixture, as is usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • 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.
  • Preferred ethoxylated alcohols include, for example, C 12 -C ⁇ 4 - alcohols with 3 EO or 4 EO, C 1 -C1 9 alcohols containing 7 EO, C 13 - C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C ] 8 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of -C 4 -C 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 18 alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, Ct 2 -C 8 -alkylpolyethylene glycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and also end-capped alkylpolyalkylene-glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols as described in European patent application EP 0 300 305, so-called hydroxymixers.
  • 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.
  • 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
  • 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 - and also the quantity to be determined analytically can take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) 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 (II)
  • 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.
  • non-ionic surfactants that 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 produced 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 generally separated from one another by a so-called “spacer”.
  • This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another.
  • Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • gemini surfactants is understood not only to mean “dimeric” in this way, but also correspondingly “trimeric” surfactants.
  • 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 dimer and trimeric mixed ethers according to German patent application DE 195 13 391 itself i n especially 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, such as those used in the interna- tional patent applications WO 95/19953, WO 95/19954 and WO 95/19955 are described.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • Preferred surfactants of the sulfonate type are C ⁇ > - C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 -C 8 monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 8 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 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 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 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 the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ⁇ -cis fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 oC 20 oxo alcohols and those half esters, are secondary Alcohols of this chain length prefers.
  • 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 1 -C 6 alkyl sulfates and C 12 -C] 5 alkyl sulfates and C 5 d 5 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 -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 ⁇ 2 -C ⁇ 8 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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular 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.
  • 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.
  • the sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.
  • 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • soaps or the known alkenylsuccinic acid salts can also be used 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.
  • the surfactant system essential to the invention is 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.
  • the nonionic surfactant is particularly preferably an ethoxylation and / or propoxylation product of linear or branched alcohols having 12 to 18 carbon atoms in the alkyl part and 3 to 20, in particular 4 to 10, alkyl ether groups, or a mixture of these.
  • the anionic surfactant is particularly preferably alk (en) yl sulfate, alkylbenzenesulfonate, olefin sulfonate, alkane sulfonate, ⁇ -sulfofatty acid, ⁇ -sulfofatty acid alkyl ester, soap or a mixture of these.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylene-phosphinophenonic acid), ethylenediamine (1) ethylenediamine (1) 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of the European patent EP 0 625 992 or the international patent application which are accessible by oxidation of polysaccharides or dextrins WO 92/18542 or European patent EP 0 232 202, polymeric acrylic acids, meth
  • 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, 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.
  • the 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), are preferred .
  • 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, especially the amorphous sodium silicates Kate, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disilicate are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.
  • ⁇ - sodium silicates with a modulus between 1.9 and 3.2 can be prepared 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 ⁇ 4 O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O ⁇ 7 xH 2 O) or Na-SKS-4 (Na 2 Si 4 Oo. XH 2 O, makatite).
  • Na-SKS for example Na-SKS-1 (Na 2 Si 22 O 45 xH 2 O, Kenyait), Na-SKS-2 (Na 2 Si ⁇ 4 O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O ⁇ 7 xH 2 O) or Na-SKS-4 (Na 2 Si 4
  • Na-SKS-5 ⁇ -Na 2 Si O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5 3H
  • Na-SKS-10 NaHSi 2 O 5 3H 2 O, Kanemit
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 ⁇ -Na 2 Si 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.
  • a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the (co) polymeric polycarboxylic acid mentioned above, as described for example in German patent application DE 198 19 187, or of alkali silicate and alkali carbonate is used as described, for example, in international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.
  • Builder substances can optionally be present in the agents according to the invention in amounts of 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 any water-insoluble builder materials.
  • 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.
  • Suitable peroxygen compounds for use in agents according to the invention are, in particular, organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, including perborate, percarbonate, persilicate and or persulfate like Caroat belong.
  • organic peracids or peracidic salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, including perborate, percarbonate, persilicate and or persulfate like Caroat belong.
  • 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
  • an agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight, is present.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be useful.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • 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.
  • Such bleach activators can be in the usual range of amounts, preferably in amounts of 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts.
  • Enzymes which can be used in the compositions in addition to the amylase essential to the invention are those from the class of proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. If appropriate, amylase other than the essential to the invention may also be present in addition to this.
  • 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 amylase essential to the invention and the optionally additionally used enzymes can, as described for example in European patent EP 0 564 476 or in international patent application WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to prevent them from being inactivated prematurely protect.
  • the washing or cleaning agents according to the invention 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 agent according to the invention contains protease, it preferably has a proteolytic activity in the range from about 100 PE / g to about 100 OOO PE / g, in particular 300 PE / g to 8000 PE / g.
  • these enzymes are to be used in the agent according to the invention, this can be done by incorporating the two or more separate or, in a known manner, separately assembled enzymes or by two or more enzymes assembled together in a granulate, as for example from international patent applications WO 96/00772 or WO 96/00773 known.
  • the organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, in addition to water include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned.
  • Such water-miscible solvents are preferably present in the 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, and 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, especially sulfuric acid, or bases, especially ammonium or alkali 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, polyvinyl imidazoles, 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 of mostly organic nature are suitable for this, 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 mixed ethers, 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 .
  • 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-mo holino-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, 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.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 8 -C 4 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.
  • 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 bistearyl ethylene diamine 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.
  • agents according to the invention with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1, a process known from European patent EP 0 486 592 and having an extrusion step is preferred.
  • 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 several, in particular of two layers
  • the procedure is preferably such that all constituents - if appropriate one layer each - are combined in one Mixer mixed together and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN.
  • break-resistant tablets which nevertheless dissolve sufficiently quickly under application conditions, are obtained with breaking and bending strengths of normally 100 to 200 N, but preferably over 150 N.
  • a tablet produced in this way preferably has a weight of 10 g to 50 g, in particular 15 g up 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 one Diameters from 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 26x36 mm or 24x38 mm.
  • Liquid or pasty detergents or cleaning agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • Table 1 below shows the washing results (in dE initial value minus dE after washing, measuring device Minolta® CR 310) for a detergent VI containing 0.25% by weight of amylase granules (Termamyl® 60T) not according to the invention and 0.25% by weight .-% of a protease granulate (activity 200,000 PE / g) with the Bacillus lentus protease contained, for a detergent V2, which was otherwise the same composition, but instead of Termamyl® contained the same amount of protein of the genetically modified amylase Duramyl®, an otherwise as VI compound detergent V3, which contained instead of Termamyl® the protein-identical amount of the genetically modified amylase Purafect® OxAm, an otherwise VI compound detergent V4, which contained the protein-equivalent amount of fungus amylase Fungamyl® instead of Termamyl®, and for a detergent according to the invention Ml, otherwise composed as VI, but instead of Terma
  • Soiling A oatmeal / milk / cocoa
  • B oatmeal / water / cocoa
  • C chocolate pudding
  • the agent according to the invention has a washing performance which is clearly superior to the agents containing another amylase.
  • 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 TAED, 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 granules (activity 200,000 PE / g) with the Bacillus lentus protease (rest on 100 wt .-% water, perfume and dye), agents (V7 or V8), which were otherwise composed like V5 or V6, but instead Termamyl® contained protein-identical amounts of Duramyl®, as well as agents according to the invention (M2 or M3), which are otherwise like V5 or V6 were composed, but instead of Termamyl® containing protein-identical amounts of Bacillus amyloliquefaciens amylase, were tested as follows:
  • agents according to the invention are significantly superior in cleaning performance to agents not according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention vise à améliorer le pouvoir nettoyant des détergents contenants des enzymes, notamment contre les salissures amylacées. A cet effet, le produit contient, outre des substances usuelles compatibles avec des enzymes de ce type, une α-amylase issue de Bacillus amyloliquefaciens et un système constitué d'un tensioactif anionique et d'un tensioactif non ionique, la quantité de ce dernier étant prédominante.
PCT/EP1999/003571 1998-06-03 1999-05-25 Detergents contenant une amylase WO1999063039A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
HU0102143A HUP0102143A2 (hu) 1998-06-03 1999-05-25 Amilázt és tenzidrendszer keverékét tartalmazó mosó- és tisztítószer készítmény és a keverék alkalmazása
PL99344532A PL344532A1 (en) 1998-06-03 1999-05-25 Detergents containing amylase
EP99926389A EP1084221A1 (fr) 1998-06-03 1999-05-25 Detergents contenant une amylase
JP2000552236A JP2002517554A (ja) 1998-06-03 1999-05-25 アミラーゼを含有する洗剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19824686.2 1998-06-03
DE19824686A DE19824686A1 (de) 1998-06-03 1998-06-03 Amylase enthaltende Wasch- und Reinigungsmittel

Publications (1)

Publication Number Publication Date
WO1999063039A1 true WO1999063039A1 (fr) 1999-12-09

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PCT/EP1999/003571 WO1999063039A1 (fr) 1998-06-03 1999-05-25 Detergents contenant une amylase

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EP (1) EP1084221A1 (fr)
JP (1) JP2002517554A (fr)
DE (1) DE19824686A1 (fr)
HU (1) HUP0102143A2 (fr)
PL (1) PL344532A1 (fr)
WO (1) WO1999063039A1 (fr)

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ES2554243T3 (es) * 2011-07-12 2015-12-17 Weylchem Switzerland Ag Empleo de una combinación de sulfonato de parafina secundario y amilasa para el aumento del poder de limpieza de agentes de lavado líquidos

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998011190A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions faiblement moussantes pour lave-vaisselle
EP0861885A1 (fr) * 1997-02-27 1998-09-02 The Procter & Gamble Company Compositions pour trempage
EP0878535A1 (fr) * 1997-05-16 1998-11-18 The Procter & Gamble Company Compositions détergentes douces sous forme liquide ou de gel pour le nettoyage de la vaiselle, qui sont des microémulsions, qui ont des propriétés moussantes et dégraissantes pour les déchets alimentaires

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998011190A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions faiblement moussantes pour lave-vaisselle
EP0861885A1 (fr) * 1997-02-27 1998-09-02 The Procter & Gamble Company Compositions pour trempage
EP0878535A1 (fr) * 1997-05-16 1998-11-18 The Procter & Gamble Company Compositions détergentes douces sous forme liquide ou de gel pour le nettoyage de la vaiselle, qui sont des microémulsions, qui ont des propriétés moussantes et dégraissantes pour les déchets alimentaires

Also Published As

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EP1084221A1 (fr) 2001-03-21
HUP0102143A2 (hu) 2001-10-28
DE19824686A1 (de) 1999-12-09
PL344532A1 (en) 2001-11-05
JP2002517554A (ja) 2002-06-18

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