JP2002517552A - Detergent containing amylase and percarboxylic acid - Google Patents

Abstract

  (57) [Summary] It is an object of the present invention to provide an enzyme-containing detergent that exhibits improved cleaning performance, especially with respect to starch stains and colored stains. It is an amylase-containing detergent that contains (natural) α-amylase from Bacillus amyloliquefaciens and a percarboxylic acid (and / or a percarboxylic acid alkali metal salt) and is compatible with these components. This is substantially achieved by a detergent characterized by including representative components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention provides, in addition to the representative components, Bacillus amyloliquefaciens (Bacill)
amyloliquefaciens) and an enzyme-containing detergent containing a specific peroxide bleaching agent.

2. Description of the Related Art In general, detergents contain, in addition to components essential to the washing process, such as surfactants and builder substances, components which can be classified into a group of cleaning aids. Auxiliaries include various actives, such as antifoams, anti-redeposition agents, bleaches, bleach activators and dye transfer inhibitors. The above auxiliaries also include substances that assist the performance of the surfactant by enzymatically degrading the soil present on the fabric. With the necessary changes, the same is true for cleaning compositions for hard surfaces. In the above sense, not only proteases that assist in protein removal and lipases that degrade fat, but also amylase are of particular importance. Amylase has the function of promoting the removal of starchy soil by catalytic hydrolysis of starch polysaccharides, and has been used in dishwashing detergents for this purpose, and also in textile washing detergents. . If it contains amylase, most of it will typically be, for example, Te
It comprises a thermostable amylase derived from Bacillus licheniformis sold under the name of rmamyl (registered trademark) or the like. More recently, genetically engineered amylases, i.e., amylases whose amino acid sequence has been modified by genetic engineering methods compared to natural amylase, have been increasingly used in such compositions. The purpose of genetically modifying an amylase is to improve the stability of the enzyme, in particular, the stability against attack by an oxidizing agent, in addition to improving the action ability of the enzyme. As one way to achieve this goal, WO 94/18314 is directed to removing particularly oxidizable amino acids, such as methionine, tryptophan, cysteine or tyrosine, from the amino acid sequence of the amylase, or converting those particularly oxidizable amino acids to A method consisting of substituting with a more stable other amino acid was proposed. WO 95/21247 also proposes a similar method and recommends replacing at least one methionine in the amylase amino acid sequence with an amino acid that is neither methionine nor cysteine.

[0003] Although genetic manipulation as described above can lead to improved amylase stability under certain application conditions, it does increase the contribution of the amylase to the washing or cleaning performance of a composition comprising the amylase. Is useless.

[0004] Surprisingly, it has been found that the use of a combination of a natural α-amylase and a specific peroxide-based oxidizing agent in a detergent results in a surprisingly synergistic improvement in performance.

DISCLOSURE OF THE INVENTION Accordingly, the present invention provides an amylase-containing detergent comprising a (natural) α-amylase from Bacillus amyloliquefaciens and a percarboxylic acid (and / or an alkali metal percarboxylate). It is intended to provide a detergent characterized by containing a representative component compatible with these components.

[0006] The present invention furthermore relates to a combination of a natural amylase from Bacillus amyloliquefaciens with a percarboxylic acid (peroxycarboxylic acid) when used in laundry and washing solutions, in particular aqueous washing and washing solutions. The present invention provides the use of a detergent comprising a substance-based compound for improving the cleaning performance (for starch-based stains and / or colored stains, especially tea-based stains). As used herein, cleaning performance with respect to colored (colored) soils is to be interpreted in the broadest sense and refers to the bleaching of soils present on textiles and the bleaching of soils detached from textiles and present in washing liquors. It also involves oxidatively destroying textile dyes that are detached from the textile under the wash conditions and are present in the wash liquor before the dyes can adhere to different colored fabrics. In addition, with respect to use in hard surface cleaning solutions, the term cleaning performance with respect to colored soil refers to the bleaching of soil (especially tea) present on hard surfaces and the removal of soil present in dishwashing liquids from hard surfaces. Bleaching means both.

Α-Amylase α-amylase from Bacillus amyloliquefaciens is described, for example, in US Pat. No. 1,227.
No. 374, for example. This α-amylase is, for example, Amylase
It is commercially available under a name such as BAN (registered trademark).

[0008] The detergent of the present invention preferably contains 0.001 mg to 0.5 mg, particularly 0.02 mg to 1 g of the whole composition.
Contains 0.3 mg of amylolytic protein. Protein concentration can be determined by known methods, for example, by the bicinchoninic acid method (BCA method, Pierce Chemical Co., Rockford, Ill.) Or by the biuret method (AGGornall, CS Bardawill and
MMDavid, J. Biol. Chem. 177 , 751-766, 1948).

The detergent according to the invention preferably contains 0.5% to 20% by weight, in particular 1% to 15% by weight, of a percarboxylic acid. The term percarboxylic acid refers to the free acid and percarboxylate (
Especially alkali metal salts). Both aliphatic and aromatic percarboxylic acids, such as, for example, perbenzoic acid or perphthalic acid, can be used. The peroxycarboxylic acid is preferably the formula _{(I): HOOOC- (CH 2} ) n -COOOH (I) [wherein, n 8-20, in particular number of 10 to 14. Or amide alkyl percarboxylic acids, especially phthalimidoalkyl percarboxylic acids. In the case of phthalimidoalkyl percarboxylic acids, phthalimidopercaproic acid is particularly preferred. Among the dipercarboxylic acids of the formula (I), 1,12-didodecandioic acid and 1,9-diperazeline acid are particularly preferred.

[0010] Amidoalkylpercarboxylic acids and their preparation are described, for example, in European Patent Application EP 0 349
940 and EP 0 739 880.

The above percarboxylic acids are described, for example, in European Patents EP 0 450 587, EP 0 521 962, EP 06
It can be incorporated in detergents, especially solid detergents according to the invention, if desired in compounded or coated form, as is known, for example, from 95 343 or European Patent Application EP 0 816 418.

The detergent according to the invention, which can be present in particular as a powdered solid, or as post-compacted particles, or as a homogeneous solution or suspension, is a product of the active substances used according to the invention. In addition to the combination, any known ingredients typically found in detergents can in principle be included. In particular, the detergents of the present invention include builders, surfactants, additional bleaching agents of organic and / or inorganic peroxide-based compounds, bleaching activators, water-miscible organic solvents, additional enzymes, sequestering agents, Electrolytes,
pH adjusters and other auxiliaries such as optical brighteners, redeposition inhibitors, dye transfer inhibitors,
Antifoams, silver corrosion inhibitors and dyes and fragrances can be included.

Surfactants The compositions of the present invention can include one surfactant or two or more surfactants. Suitable surfactants are in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants can be used. .

Nonionic surfactants Suitable nonionic surfactants are, in particular, alkylglycosides of straight / branched alcohols and their ethoxylated and / or propoxylated products. The straight-chain / branched alcohols contain in each case 12 to 18 carbon atoms in the alkyl group and 3 to 12, preferably 4 to 10 carbon atoms in the alkyl ether group. Also,
N-alkylamine corresponding to the long-chain alcohol derivative with respect to the alkyl group,
The corresponding ethoxylated and / or propoxylated products of vicinal diols, fatty acid esters and fatty acid amides and alkylphenols containing 5 to 12 carbon atoms in the alkyl group can also be used.

[0015] Suitable nonionic surfactants are alkoxylated (preferably ethoxylated) alcohols, especially primary alcohols. It consists preferably of an alcohol having 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mol of alcohol,
The alcohol residue may be straight-chain or suitably 2-methyl-branched, or may have a mixture of straight-chain and methyl-branched groups as in conventional oxo alcohol residues. However, C _{12 ~ 18} alcohols derived from natural products (
Alcohol ethoxylates having, for example, straight-chain groups of coconut oil fatty alcohol, palm oil fatty alcohol, tallow fatty alcohol or oleyl alcohol) and an average of 2 to 8 EO per mol of alcohol are particularly preferred. Suitable ethoxylated alcohols, e.g., C _{12 ~ 14} alcohol + 3EO or 4 EO, C _{9 ~ 11} alcohol + 7EO, C _{13 ~ 15} alcohol + 3EO, 5 EO, 7 EO or 8EO, C _{12 ~ 18} alcohol + 3EO
, 5 EO or 7 EO, and mixtures thereof (e.g., mixtures of C _{12 ~ 14} alcohol + 3EO, and C _{1 2 ~ 18} alcohol + 7 EO) are exemplified. The degree of ethoxylation is a statistical average, which may be an integer or a fraction for a particular product. Suitable alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to such nonionic surfactants, fatty alcohols having an EO of more than 12 can also be used. Examples of such compounds are (tallow) fatty alcohols + 14EO, 16EO, 20EO, 25EO, 30EO or 40EO.

In general, low foaming compounds are used in detergents used in dishwashers. Preferred compounds of this type are C ₁₂ -C ₁₈ alkyl polyethylene glycol polypropylene glycol ethers (up to 8 mol ethylene oxide units and
Up to 8 mol propylene oxide units). However, other known low-foaming nonionic surfactants may also be used, for example, C ₁₂ -C ₁₈ per alkyl polyethylene glycol polybutylene glycol ethers (one molecule, 8 mol
Up to 8 mol ethylene oxide units and up to 8 mol butylene oxide units. ), Mixed ethers of alkyl polyalkylene glycol with terminal group cap, and the like. Particular preference is given to hydroxy-containing alkoxylated alcohols, referred to as hydroxy mixed ethers (EP-A-0 300 305).

In addition, examples of additional nonionic surfactants include alkyl glycosides represented by the formula: RO (G) _x . Wherein, R, primary, straight-chain or methyl-branched chain (especially, 2-methyl-branched) C ₈ -C _22, and preferably a C ₁₂ -C ₁₈ aliphatic group. G is a glucose unit having 5 or 6 carbon atoms (preferably a glucose unit). The degree of oligomerization x indicates the distribution of monoglycosides and oligoglycosides, is any desired numerical value, is a variable determined by analysis, may be a fraction, preferably a numerical value of 1 to 10, More preferably, it is a numerical value of 1.2 to 1.4.

Another suitable surfactant is of formula (II):

Embedded image Wherein R ¹ CO is a C ₆ -C ₂₂ aliphatic acyl group, R ² is hydrogen or a C ₁ -C ₄ alkyl or hydroxyalkyl group, and
[Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. ] The polyhydroxy fatty acid amide represented by these. The polyhydroxy fatty acid amide is preferably derived from a reducing sugar having 5 to 6 carbon atoms (particularly glucose). The group of polyhydroxy fatty acid amides comprises the formula (III):

Embedded image Wherein R ³ is a C ₇ -C ₁₂ linear or branched alkyl or alkenyl group, R ⁴ is a C ₂ -C ₈ linear, branched or cyclic alkyl or arylene group R ⁵ is a C ₁ -C ₈ linear, branched or cyclic alkyl or aryl or oxyalkyl group (preferably a C ₁ -C ₄ alkyl or phenyl group), and [Z Is a linear polyhydroxyalkyl group in which the alkyl chain is substituted with at least two hydroxyl groups or an alkoxylated (preferably ethoxylated or propoxylated) derivative of said group. ] The compound shown by these is also included. Again, [Z] is preferably glucose,
Obtained by reductive amination of sugars such as fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy-substituted or N-aryloxy-substituted compound is then converted to the desired polyhydroxy fatty acid amide by reaction with a fatty acid methyl ester in the presence of an alkoxide as a catalyst, for example, as taught in WO95 / 07331. can do. Another class of suitably used nonionic surfactants, used alone or in combination with other nonionic surfactants, especially with alkoxylated fatty alcohols and / or alkyl glycosides The activator is an alkoxylated (preferably ethoxylated or ethoxylated and propoxylated) fatty acid alkyl ester, preferably having from 1 to 4 carbon atoms in the alkyl chain, in particular, e.g. Fatty acid methyl esters as described in national patent application JP58 / 217598, and the like, or alkoxylated fatty acid alkyl esters suitably produced by the production method described in WO90 / 13533. Amine oxide type nonionic surfactants (eg, N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide) and fatty acid alkanolamide type nonionic surfactants, It is preferably used. The dose of the nonionic surfactant is suitably less than or equal to the dose of ethoxylated fatty alcohol, in particular less than half the dose of ethoxylated fatty alcohol. Another suitable surfactant includes:
Included are surfactants known as gemini surfactants. The term gemini surfactant is commonly used to describe a compound having two hydrophilic groups per molecule. The two hydrophilic groups are generally separated from each other by a structure called a spacer. The spacer is generally a carbon chain, and the carbon chain must be long enough so that the hydrophilic groups are sufficiently separated and the hydrophilic groups can act independently of one another. Surfactants of this type are generally notable for their exceptionally low critical micelle concentrations and the ability to significantly lower the surface tension of water. However, in exceptional cases, the expression gemini surfactant is used to encompass not only dimeric surfactants, but also similar trimeric surfactants. Examples of suitable gemini surfactants are the sulfated hydroxy mixed ethers of German Patent Application DE 43 21 022 or the alcohol dimer bis- of German Patent Application DE 195 03 061.
And the alcohol trimer Tris-sulfate. German patent application DE-A-195
The end-capped dimer and trimer mixed ethers of 13 391 are notable especially for their bifunctional and polyfunctional nature. Accordingly, the above terminal group-capped surfactant has good wettability and low foaming property, and is particularly suitable for a machine washing or washing process. However, it is also possible to use gemini-type polyhydroxy fatty acid amides or polypolyhydroxy fatty acid amides as described in WO 95/19953, WO 95/19954 and WO 95/19955.

Suitable anionic surfactants are, in particular, soap and sulfate type or sulfonate type anionic surfactants. Suitable surfactants of the sulphonate type are C _9-13 alkyl benzene sulphonates, olefin sulphonates, i.e., for example, after sulfonation with sulfur trioxide gas, the alkaline or acidic nature of the resulting sulfonated product. by hydrolysis, such as obtained from C _{1 2-18} monoolefins having a terminal or internal double bond, mixtures of alkene sulfonates and hydroxyalkane sulfonates and disulfonates. Also suitable are the alkene sulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization, respectively. Also, α-
Esters of sulfo fatty acids (ester sulfonates), for example, 8
Hydrogenated coconut oil, palm kernels, produced by alpha-sulfonating methyl esters of fatty acids of plant and / or animal origin having up to 20 carbon atoms and then neutralizing to obtain a water-soluble monosalt Also suitable are α-sulfonated methyl esters of oils or tallow fatty acids. The α-sulfofatty acid ester is preferably hydrogenated coconut oil,
Α-sulfonated esters of palm oil, palm kernel oil or tallow fatty acids, wherein the sulfonated products of unsaturated fatty acids such as oleic acid are present in small amounts, preferably about 2-3% by weight.
It may be present in the following amounts: Α-sulfofatty acid alkyl ester having an alkyl chain having 4 or less carbon atoms in the ester group, for example, methyl ester, ethyl ester,
Propyl esters and butyl esters and the like are particularly preferred. Methyl esters of α-sulfofatty acids (MES) and saponified methyl salts of α-sulfofatty acids are particularly advantageously used. Other suitable anionic surfactants, such as those obtained from the production by esterifying monoglycerol with 1-3 moles of fatty acids or as obtained by transesterification of triglycerides with 0.3-2 moles of glycerol Glycerol esters of sulfated fatty acids which are monoesters, diesters and triesters and mixtures thereof. Suitable alkyl (or alkenyl) sulfates, C ₁₂ -C ₁₈ fatty alcohols (e.g., coconut oil fatty alcohols, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol) or C ₁₀ -C ₂₀ sulfuric monoesters of oxo alcohols And alkali metal salts of sulfuric acid monoesters of secondary alcohols of the above chain length, especially the sodium salts. Also suitable are petrochemically produced alkyl (or alkenyl) sulphates of the above-mentioned chain length which comprise petrochemically produced synthetic straight-chain alkyl groups having similar degradability to similar compounds based on lipochemical raw materials. Viewed from the surface of the detergent, C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are especially preferred. Further, 2,3-alkyl sulfates, which can be prepared, for example, according to U.S. Patent Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company under the name DAN®, are suitable. Is an anionic surfactant. Linear or branched C _7-21 alcohol ethoxylated with 1-6 moles of ethylene oxide (eg, 2-methyl branched C _9-11 alcohol containing an average of 3.5 moles of ethylene oxide (EO) or C _12-18 acid monoesters of fatty alcohols) containing 4EO also suitable. Suitable anionic surfactants, also referred to as sulfosuccinates or sulfosuccinates, comprise the monoesters and / or diesters of sulfosuccinic acids with alcohols, preferably fatty alcohols, especially ethoxylated fatty alcohols. And salts of alkyl sulfosuccinic acids. Preferred sulfosuccinates comprise _C8-18 fatty alcohol groups or mixtures thereof. Particularly preferred sulfosuccinates contain fatty alcohol groups derived from ethoxylated fatty alcohols corresponding to nonionic surfactants. Also, sulfosuccinates having fatty alcohol groups derived from ethoxylated fatty alcohols having a narrow homolog distribution are particularly preferred. Similarly, it is also possible to use alkyl (or alkenyl) succinic acids or salts thereof, which preferably contain from 8 to 18 carbon atoms in the alkyl (or alkenyl) chain. Other suitable anionic surfactants include fatty acid derivatives of amino acids, such as fatty acid derivatives of N-methyltaurine (tauride) and / or fatty acid derivatives of N-methylglycine (sarcoside). Sarcosides and sarcosinates are particularly preferred according to the invention,
Of the sarcosides and sarcosinates, sarcosinates of higher fatty acids, which may be mono- or polyunsaturated, such as oleyl sarcosinate, are preferred. Another suitable anionic surfactant is, in particular, soap. Suitable soaps include, in particular, saturated fatty acid soaps, for example salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and especially natural fatty acids, such as coconut oil, palm kernel oil or tallow fatty acid And mixtures of soaps derived therefrom. It is also possible to use the known alkenyl succinates with or as substitutes for the above-mentioned soaps.

Anionic surfactants can be present in the form of sodium, potassium or ammonium salts, including soaps, and as soluble salts of organic bases (eg, mono-, di- or tri-ethanolamine). . Anionic surfactants are
Preferably, it takes the form of a sodium or potassium salt, especially the sodium salt.

Surfactant Dosage According to the present invention, the surfactant is present in laundry detergents in an amount of about 5% to 50% by weight, especially 8% by weight.
Hard surface cleaners, especially dishwashing compositions, are present in lower proportions, preferably in amounts of up to 10% by weight, in particular up to 5% by weight, whereas they are present in a proportion of from 30% by weight to 30% by weight. And particularly preferably in an amount of from 0.5% to 3% by weight.

Builders The compositions of the present invention preferably comprise at least one water-soluble and / or water-insoluble organic and / or inorganic builder. Suitable water-soluble organic builder substances include polycarboxylic acids (especially citric and sugar acids), aminopolycarboxylic acids in monomeric and polymeric form (especially methylglycine diacetate, nitrilotriacetic acid and ethylenediaminetetraacetic acid) and polycarboxylic acids. Aspartic acid, polyphosphonic acid (
In particular, polymeric trihydroxy compounds such as aminotris (methylene phosphonic acid), ethylenediamine tetrakis (methylene phosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid), dextrin, and (poly) carboxylic acid polymers, especially polysaccharides or The polycarboxylates of EP 0 625 992 or WO 92/18542 or EP 0 232 202, each of which can be obtained by oxidizing dextrins, are copolymerized with a very small amount of polymerizable substance without carboxylic acid functional groups. Acrylic acid polymers, methacrylic acid polymers, maleic acid polymers and copolymers thereof, which may be included in different forms. Converted to the respective free acids, the relative molecular mass of the unsaturated carboxylic acid homopolymer is generally 3,000 to 200,000.
And the relative molecular mass of the copolymer is 2000-200,000, preferably 30,000-120.
, 000. Particularly preferred acrylic acid-maleic acid copolymers have a relative molecular mass between 30,000 and 100,000. Commercially available products are, for example, Sokalan® CP5 from BASF
, CP10 and PA30. Of these types of compounds, although less preferred, acrylic or methacrylic acid and vinyl ether (vinyl methyl ether)
, Vinyl esters, copolymers with ethylene, propylene or styrene (acid portion at least 50% by weight).

Also, as a suitable water-soluble organic builder substance, a terpolymer containing two unsaturated acids and / or salts thereof as monomers and containing vinyl alcohol and / or esterified vinyl alcohol or carboxylate as a third monomer Can be used. The first acidic monomer or its salt, monoethylenically unsaturated C ₃ -C ₈ carboxylic acid, preferably can be obtained from the C ₃ -C ₄ monocarboxylic acid, in particular (meth) acrylic acid. The second acidic monomer or its salt, C ₄ -C ₈ dicarboxylic acids, preferably may be a derivative of an allyl sulfonic acid derivatives of maleic acid and / or 2-position is substituted by an alkyl or aryl group . Such polymers can in particular be prepared by methods described in the literature (DE 42 21 3
81, DE 43 00 772, see, in general, the relative molecular weights 1,000 to 200,000). Furthermore, suitable copolymers are described in the literature (DE 43 03 320 and DE 44 17 734, preferably containing, as monomers, acrolein and acrylic acid and / or its salts and / or vinyl acetate). In particular, the organic builder substances for the production of liquid compositions can be used in the form of an aqueous solution, preferably in the form of a 30-50% by weight aqueous solution.
All acids can generally be used in the form of their water-soluble salts, in particular the alkali metal salts.

Organic builders of this kind can be used if desired in amounts of up to 40% by weight, in particular in amounts of up to 25% by weight, particularly preferably in amounts of 1 to 8% by weight. Preferably, a paste or liquid composition, particularly a composition containing water, can be used in an amount close to the upper limit.

Suitable water-soluble inorganic builders include, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which are alkali, neutral or acidic sodium or potassium salts thereof. It can exist in a form.
Examples of the alkali metal salt include trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, and oligomeric trisodium phosphate (oligomerization degree 5 to 1,000). , Especially 5-5
0) and the corresponding sodium salts and / or mixtures of sodium and potassium salts. Water-insoluble, water-dispersible inorganic builder substances, in particular crystalline or amorphous alkali metal aluminosilicates, in an amount of up to 50% by weight, preferably of up to 40% by weight, in particular in liquid compositions from 1 to It can be used in an amount of 5% by weight. Among them, preferably, a detergent amount of crystalline sodium aluminosilicate, especially zeolite A, P
And particularly preferably, X alone or a mixture in the form of a co-crystallized product of zeolite X and zeolite A (CONDEA Augusta SpA, trade name VEGOBOND AX) can be used. Suitable aluminosilicates do not particularly comprise any particles having a particle size of more than 30 μm and preferably comprise particles having a particle size of less than 10 μm in an amount of at least 80% by weight. The calcium binding capacity of aluminosilicates (measured according to DE 24 12 837) is generally
CaO is 100 to 200 mg / g.

A complete or partial replacement of the above aluminosilicates is a crystalline silicate alkali metal salt, which exists in a single form or in a mixture with an amorphous silicate. be able to. In the composition of the present invention, the alkali metal silicate that can be used as a builder preferably has a alkali metal oxide / SiO ₂ molar ratio of:
It is less than 0.95, especially 1: 1.1 to 1:12, and can be present in amorphous or crystalline form. Preferred alkali metal silicates include sodium silicate, in particular sodium amorphous silicate, the molar ratio of Na ₂ O / SiO ₂ is 1: 2 to 1: 2.8. Na ₂ O /
Sodium silicate having a molar ratio of SiO ₂ of 1: 1.9 to 1: 2.8 can be produced by the method described in EP 0 425 427. As crystalline silicates which can be present alone or in the form of mixtures with amorphous silicates, preference is given to crystalline phyllosilicates of the formula Na ₂ SiO _{2X + 1} [
x (so-called coefficient) = 1.9 to 22, especially 1.9 to 4, y = 0 to 33, preferably x = 2, 3 or 4]. The crystalline phyllosilicate represented by this formula is, for example, EP 0
164 514. Preferred phyllosilicates are those in which x is 2 or 3. β- and γ-sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O) are particularly preferred. β-Sodium silicate can be produced by the method described in WO 91/08171. Sodium silicate with a coefficient of 1.9 to 3.2 is described in JP 04/238 809 and JP
04/260 610. In addition, a substantially anhydrous crystalline alkali metal silicate represented by the above formula (x = 1.9 to 2.1, EP 0 548 599, EP 0 502 325)
And prepared according to the methods described in EP 0 452 428) can also be used in the compositions according to the invention. According to another preferred embodiment of the present invention, sodium phyllosilicate having a coefficient of 2-3 can be used (made from silica sand and soda by the method described in EP 0 436 835). Crystalline sodium silicate having a coefficient of 1.9 to 3.5 (EP 0 164 552 and / or
Or by the method described in EP 0 294 753) can also be used in a preferred embodiment of the invention.

The crystalline layered silicate of the above formula is commercially available under the trade name Na-SKS (Clariant GmbH, Germany)
It), for example, Na-SKS-1 (Na_TwoSi_{twenty two}O₄₅・ XH_TwoO, Keniyaite), Na-SKS
-2 (Na_TwoSi₁₄O₂₉・ XH_TwoO, Magadiite), Na-SKS-3 (Na_TwoSi₈O₁₇・ XH _Two O), Na-SKS-4 (Na_TwoSi_FourO₉・ XH_TwoO, Makatite)
.

Among these silicates, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ ,
Natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ .H ₂ O), Na-SKS-10 (N
_{aHSi 2 O 5 · 3H 2 O} , kanemite (Kanemite)), Na-SKS -11 (γ-Na 2 Si 2 O 5) and N
a-SKS-13 (NaHSi ₂ O ₅ ) is preferred, and Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) is particularly preferred. An overview of crystalline layered silicates can be found in the following literature:
echst High Chem Magazin 14/1993, pages 33-38 and "Seifen-Oele-Fette-Wa"
schse, Vol. 116, No. 20, 1990, pp. 805-808.

According to a preferred embodiment of the present invention, as the granular compound, crystalline phyllosilicate (layer silicate) and citrate, crystalline phyllosilicate and the (co) polymer polycarboxylic acid ( For example, DE 198 19 187) or an alkali metal silicate and the above-mentioned alkali metal carbonate (for example, those described in WO 95/22592 or commercially available Nabion (
Registered trademark) 15) can be used.

In the composition according to the invention, the builder substance can be used if desired in an amount of up to 90% by weight. Suitably, the builder can be used in amounts up to 75% by weight. The laundry detergent of the present invention has a builder content of 5 to 50% by weight. In compositions of the present invention for cleaning hard surfaces, especially compositions for dishwashers, the amount of builder substance is:
Builder materials, especially 5 to 88% by weight, preferably water insoluble, are not used in such compositions. According to one preferred embodiment of the invention, especially for dishwashers, 20 to 40% by weight of a water-soluble organic builder, in particular alkali metal citrate, 5 to 15% by weight of alkali metal carbonate and 20 to 40% by weight. % By weight of the alkali metal disilicate.

Peroxide-based compounds Suitable peroxide-based compounds for use in the compositions of the present invention include, in particular, organic peracids or organic acid persalts, such as phthalimidopercaproic acid, perbenzoic acid or dibenzoic acid. Salts of perdodecandioic acid, hydrogen peroxide, and inorganic salts that release hydrogen peroxide under washing conditions,
For example, perborate, percarbonate, persilicate and / or caroate
) Are included. If it is necessary to use solid peroxide-based compounds, these solid peroxide-based compounds can be used in the form of powders or granules which may be coated in a manner known in principle. It should be noted that small amounts of known stabilizers can also be used, for example, phosphates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate.

Bleaching activators The bleaching activators which can be used according to the invention are, in particular, preferably C _{1 to} C ₁₀ (particularly C _{2 to} C ₄ ) aliphatic peroxycarboxylic acids under perhydrolysis conditions. Compounds that release acids and / or substituted or unsubstituted perbenzoic acids. Suitable substances are those that carry O-acyl and / or N-acyl groups and / or substituted or unsubstituted benzoyl groups of the above number of carbon atoms. Suitable bleach activators are the following substances: polyacylated alkylenediamines, especially tetraacetylethylenediamine (TA
ED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycoluril, especially tetraacetylglycoluril (TAGU), N -Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonic acids, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,
In particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German Patent Applications DE 196 16 693 and DE 196 16 767, Acetylated sorbitol and mannitol and / or their mixtures (SORMAN) as described in European Patent Application EP 0 525 239, acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose And acetylated (optionally N-alkylated) glucamine and gluconolactone and / or N-acylated lactams, such as WO 94/27970, WO 94/28102, WO 94/28103, WO 95/0
0626, N-benzoylcaprolactam known from WO 95/14759 and WO 95/17498. Acyl acetals substituted with hydrophilic groups known from German Patent Application DE 196 16 769 and acyllactams described in German Patent Applications DE 196 16 770 and WO 95/14075 are also preferably used. Combinations of the usual bleach activators known from DE 44 43 177 can also be used. When the above-mentioned hydrogen peroxide releasing bleaching agent is present, such a bleaching activator is used in a usual amount, preferably from 0.5% to 10% by weight, especially from 1% by weight to 10% by weight, based on the whole composition. It can be included in an amount of 8% by weight. However, when a percarboxylic acid essential for the present invention is used, such a bleach activator is not used.

Bleaching catalyst In addition to or instead of the conventional bleach activators mentioned above, EP 0 446 9
Sulfonimines known from 82 and EP 0 453 003 and / or transition metal salts or complexes having a bleach-enhancing action can be present as so-called bleach catalysts.

Enzymes In addition to the amylase essential for the present invention, enzymes that can be used in the composition include enzymes selected from proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases. And mixtures thereof. Amylases other than the amylase essential for the present invention may be present. Particularly suitable active enzyme substances are Bacillus subtilis, Bacillus licheniformis, Bacillus lentus (Bacillus l.)
entus), Streptomyces griseus, Humicola lanuginosa, Humicola insolens
insolens), Pseudomonas pseudoal
caligenes, Pseudomonas cepacia or Coprinus cinereus. Amylases essential for the invention and enzymes which can additionally be used are used to protect the enzymes from premature inactivation, as described, for example, in EP 0 564 476 or WO 94/23005. Can be adsorbed on a carrier material and / or embedded in a coating material. The detergents according to the invention preferably contain the abovementioned enzymes in amounts of up to 5% by weight, in particular in amounts of 0.2% to 4% by weight. When the composition of the present invention comprises a protease, the protease is preferably at about 100 PU / g.
It has proteolytic activity in the range of up to about 10,000 PU / g, especially 300 PU / g to 8,000 PU / g. If two or more enzymes need to be used in the composition according to the invention, they can be mixed by mixing two or more individual enzymes or enzymes which are conventionally individually compounded, or for example in WO 96/00772 or As is known from WO 96/00773, the above need can be fulfilled by using two or more enzymes compounded together in granules.

Organic solvent Composition of the present invention (particularly when the composition of the present invention is in a liquid or paste form)
In the organic solvent which can be used in addition to water, an alcohol (particularly methanol, ethanol, isopropanol and tert- butanol) C ₁ -C _4, diols C ₂ -C ₄ (in particular ethylene glycol and propylene glycol) and Included are mixtures thereof, as well as ethers that can be derived from the above types of compounds. Such water-miscible solvents are present in the compositions according to the invention preferably in amounts of up to 30% by weight, in particular in amounts of from 6% to 20% by weight.

Other Detergent Ingredients In addition, the present compositions can also include components normally present in detergents. Such optional ingredients include, inter alia, enzyme stabilizers, redeposition inhibitors, dye transfer inhibitors, foam control agents and optical brighteners, and dyes and fragrances. In the dishwashing detergent of the present invention, a silver corrosion inhibitor can be used to prevent silver corrosion. The cleaning composition according to the invention for hard surfaces can further comprise abrasive components, in particular quartz powder, wood powder, polymer powder, chalk and glass microbeads and mixtures thereof. The abrasive is preferably present in the detergent according to the invention in a proportion of up to 20% by weight, in particular from 5% to 15% by weight.

[0037] In order to adjust the pH to the desired level automatically obtained that no by mixing pH adjusting agent other ingredients, the compositions of the present invention is to fit and conform to the system and environment acid,
Especially containing citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, or inorganic acids, especially sulfuric acid, or bases, especially ammonium hydroxide or alkali metal hydroxide. it can. This kind of
The pH adjusting agent is suitably present in the composition according to the invention in an amount of up to 20% by weight, in particular from 1.2% to 17% by weight.

Dye Transfer Inhibitors Suitable dye transfer inhibitors for use in the laundry detergents of the present invention include, in particular, polyvinylpyrrolidone, polyvinylimidazole, poly (vinylpyridine N-oxide) and the like.
N-oxide polymers and copolymers of vinylpyrrolidone and vinylimidazole are included.

Anti -redeposition agent The anti -redeposition agent has a function of keeping the soil detached from the fiber product fibers suspended in the liquid. For the above purposes, water-soluble colloids, usually organic, such as starch, glue, gelatin, starch or cellulose salts of ether carboxylic acids or ether sulfonic acids, or cellulose or salts of acid sulfate esters of starch are suitable. . Water-soluble polyamides containing acidic groups are also suitable for the above purpose.
Furthermore, other starch derivatives, such as aldehyde starch, can also be used. Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, for example in amounts of 0.1 to 5% by weight, based on the composition. , And mixtures thereof are preferred.

Fluorescent Whitening Agent The laundry detergent of the present invention can comprise, as a fluorescent whitening agent, a derivative of diaminostilbene disulfonic acid and / or an alkali metal salt thereof. For example,
4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene
Preference is given to -2,2'-disulfonic acid or salts of compounds of a similar structure which carry a diethanolamino, methylamino, anilino or 2-methoxyethylamino group instead of a morpholino group. Brighteners of the substituted diphenylstyryl type, for example 4,4 '
Alkali metal of -bis (2-sulfostyryl) biphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) biphenyl or 4- (4-chlorostyryl) -4 '-(2-sulfostyryl) biphenyl Salts may be included. Mixtures of the above optical brighteners can also be used.

[0041] Seiawazai Particularly, in the case of a composition for dishwashers, it is advantageous to add a conventional suds control agent to the composition described above. Examples of suitable Seiawa agents, C ₁₈ -C ₂₄ fatty acid content of soap of higher natural or synthetic. Examples of suitable non-surfactant type foam control agents include organopolysiloxanes and mixtures of organopolysiloxanes with ultrafine silica, optionally silanized, and paraffins, waxes, microcrystalline waxes, and silanizations thereof. It is a mixture with silica or bis-fatty acid alkylenediamine. Mixtures of different antifoams, for example mixtures comprising silicones, paraffins or waxes, are also advantageously used. Foaming agents, especially those comprising silicone and / or paraffin, are preferably bound to a particulate water-soluble or water-dispersible carrier material. Mixtures of paraffin and bisstearylethylenediamide are particularly preferred.

Preparation of the Solid Detergent The preparation of the solid detergent according to the invention is not difficult and, according to the customary method, is spray-dried or granulated against any other heat-sensitive ingredients, such as enzymes and bleaches, and If desired, it can be done by individual addition. High bulk density,
In particular, to produce a composition of the invention having a bulk density in the range of 650 g / l to 950 g / l,
Preference is given to the method known from EP 0 486 592 which involves an extrusion step.
Another suitable preparation using a granulation process is described in EP 0 642 576.

Preparation of Tablet Detergents The present invention can have one or more layers, can have one or more colors, and especially a tablet-type composition of the invention consisting of one or two or more layers. To produce a product, all of the ingredients (optionally one by one) are mixed together in a mixer and the resulting mixture is mixed for about 50 minutes using a conventional tablet press (eg an eccentric press or rotary press). Compress with a compression force in the range of 100100 kN, preferably 60-70 kN. Particularly in the case of multilayer tablets, it is advantageous to compress at least one layer in advance. This pre-compression is preferably performed with a compression force of 5 to 20 kN, in particular 10 to 15 kN. By such a method, it is possible to obtain a tablet which has a breaking strength and a bending strength of usually 100 to 200 N (but preferably more than 150 N) and exhibits a breakage resistance while dissolving sufficiently quickly under the use conditions without any problem. Can be Tablets produced in this way are preferably
It has a weight of 10 g to 50 g, especially 15 g to 40 g. The three-dimensional shape of the tablet is arbitrary and can be circular, oval or angular, and intermediate shapes are possible. The corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of a tablet with a square design or a cube-like design that is mainly injected using, for example, a detergent input device of a washing machine,
It depends on the shape and volume of the detergent dosing device. As a preferred embodiment, 20 to
It has a bottom area of 30 mm x 34 to 40 mm, especially 26 x 36 mm or 24 x 38 mm.

Preparation of Liquid / Paste Detergents Liquid / paste detergents in the form of a solution contain ordinary solvents and are generally prepared by mixing each component in the form of a raw powder or a solution by an automatic mixer and simply mixing. Can be.

[0045]

【Example】

Example 1 To check the washing performance, wash a cotton cloth with standardized test dirt
Washed at 40 ° C with a washing machine (Miele (registered trademark) W701) (detergent dose: 76 g, water hardness: 16 ° d)
, 3.5kg cloth, short time program). The laundry test uses the following detergent composition.
I went. 0.25% by weight of known amylase granules (Termamyl® 60T) and Bacill
Protease granules containing Bacillus lentus protease (activity 2
(00,000 PU / g) containing 0.25% by weight as well as 4% by weight of 1,12-perdodocanedioic acidWashing
Agent C1A genetically modified amylase Du of the same protein amount in place of Termamyl®
Contains ramyl®, otherwise identical in composition to C1Detergent C2A genetically modified amylase Pu of the same protein content in place of Termamyl®
Contains rafect (registered trademark) OxAm, and otherwise has the same composition as C1Detergent C3; Termam
fungal amylase Fungamyl (registered trademark) with the same protein content in place of yl (registered trademark)
The composition is the same as C1.Detergent C4A Bacillus amyloliqueur of the same protein amount in place of Termamyl®
Including the amylase from Faciens, other than the same composition of C1 of the present invention Detergent D1 And the same amount of phthalimidopercaproic acid in place of 1,12-perdodecandioic acid, and
Except for this, the composition of the present invention has the same composition as D1.Detergent D2.

The detergent of the present invention was clearly superior in cleaning performance to detergents containing other amylase. The results were generally the same when using a conventional perboric acid / TAED bleach system instead of the above peracids in the detergents of the present invention.

[0047]Example 2 The following detergent compositions were prepared and tested. 55% by weight sodium tripolyphosphate (calculated as anhydrous), 4% by weight amorphous
Sodium disilicate (calculated as anhydrous), 22% by weight sodium carbonate, 11% by weight
% Phthalimidopercaproic acid, 2% by weight nonionic surfactant, and 1% by weight
Or 2% by weight amylase granules (Termamyl® 60T), and batyl
Protease granules containing Bacillus lentus protease (activity 2
(00,000 PU / g) contains 1.4% by weight (the balance up to 100% by weight is water, flavor and pigment)
Dishwashing detergentC5 and C6Containing Duramyl® of the same protein amount in place of Termamyl®
Other than C5 and C6C7 and C8And Bacillus amyloliqueur of the same protein amount in place of Termamyl®
Contains Faciens-derived amylase, otherwise identical in composition to C5 and C6 M3 and M4 of the present invention .

In a Miele® G575 dishwasher, six dishes each washed with standardized starch soil or bleachable soil (detergent dose 20 g, universal program, water hardness 14-16 d) ° dH, temperature 55 ° C). The soil residue was measured by gravimetry, and the ratio to the initial value (100%) before washing was calculated. The detergent of the present invention had considerably better cleaning performance than the detergent of the comparative example. When the usual perborate / TAED bleaching system was used in place of the above peracids in the detergents of the present invention, the results were generally the same.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Horst-Dieter Speckmann Germany-Day 4067 Langenfeld, Eichenfeldstraße 24th (72) Inventor Karl-Heinz Maurer Germany-Day 40406 Erkler D, Dechenstrasse No. 5 (72) Inventor Christian Nich, Germany D-40591 Düsseldorf, Otto-Hahn-Strasse 185 F-term (reference) 4H003 DA01 DA05 DA19 EA09 EA15 EA16 EB10 EB12 EB17 EC01 EC02 EE06 FA42 FA47

Claims (10)

[Claims] 1. An amylase-containing detergent comprising α-amylase derived from Bacillus amyloliquefaciens and a percarboxylic acid, and a representative component compatible with these components. 2. The detergent according to claim 1, wherein said detergent is present in an amount of from 0.001 mg to 0.5 mg per g of detergent.
2. The detergent according to claim 1, comprising amylase in an amount of from 02 mg to 0.3 mg. 3. The detergent according to claim 1, wherein the detergent is 0.5% to 20% by weight, in particular 1% to 15% by weight.
The detergent according to claim 1 or 2, comprising a percarboxylic acid of the formula (1). 4. The percarboxylic acid is of the formula (I): HOOOC- (CH ₂ ) _n —COOOH (I) wherein n is a number from 8 to 20, in particular from 10 to 14. The detergent according to any one of claims 1 to 3, which is a compound represented by the formula: 5. The detergent according to claim 1, wherein the percarboxylic acid is an amide alkyl percarboxylic acid, especially a phthalimidoalkyl percarboxylic acid. 6. The detergent according to claim 5, wherein the percarboxylic acid is phthalimidopercaproic acid. 7. Detergent according to claim 1, wherein the detergent comprises 5% to 50% by weight, in particular 8% to 30% by weight, of a surfactant. 8. Detergent for hard surfaces, in particular detergent for dishwashers, characterized in that said detergent comprises a surfactant in an amount of up to 10% by weight, in particular in an amount of from 0.5% to 3% by weight. The detergent according to any one of claims 1 to 6, wherein 9. Use of a combination of an α-amylase derived from Bacillus amyloliquefaciens and a percarboxylic acid for improving the washing performance of a detergent. 10. Use according to claim 9, characterized in that the cleaning performance is improved against starch-containing stains and / or colored stains.