JP2003514069A - Enzyme-based redeposition inhibitor - Google Patents

Abstract

  (57) [Summary] The present invention relates to the use of 20K-cellulase obtained from Melanocarpus sp. Or Myriocockum sp. Or a cellulase having more than 80% homology thereto as a redeposition inhibitor in detergents. The cellulase, when combined with an optionally genetically modified protease and / or alkali metal percarbonate, reduces redeposition of soil particles on the washed laundry.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to certain enzyme-based redeposition inhibitors for use in detergent-containing laundry detergents, and, in particular, other enzyme-based redeposition inhibitors in combination with other selected ingredients. Containing detergent.

BACKGROUND ART Fine-grained zeolites, in particular zeolite NaA, are currently added to detergents in order to scavenge hardness sources in laundry liquors and soils, in particular calcium and / or magnesium ions. However, so-called cobuilders or cobuilder systems are used in considerable amounts, especially in laundry detergents, in order to act especially on unwanted deposits.

Such deposits, such as calcium soaps or organic residues, are deposited on the inner wall of the washing machine and especially on the laundry. This deposit adversely affects the feel, appearance, odor and absorptive capacity of the laundry, and the adverse effects are particularly remarkable after repeated washing.

In general, when the soil suspension performance of the washing liquid is unsuitable due to the defect of the detergent and the stains once removed from the laundry are redeposited from the laundry liquid to the laundry, after frequent washing, Discoloration of the laundry also occurs.

The above-mentioned builders or co-builders are added to detergents in order to prevent or minimize deposits and discoloration. It is also known to additionally use complexing agents such as aminocarboxylic acids, eg nitrilotriacetic acid and phosphonic acid derivatives. When the detergent is actually used, this type of co-builder combination prevents the precipitation of poorly soluble calcium salts and the deposits that form on fabrics or other surfaces. In addition, laundry detergents in particular have additional redeposition inhibitors that are specifically intended to prevent soil particles suspended in the wash liquor from redepositing on the washed textile. May be included.

DE-A-3329400 reconstitutes a mixture containing methylcellulose, carboxymethylcellulose and a (meth) acrylic acid-maleic acid copolymer in a ratio of 1: (1.5-4) :( 3-10). It is proposed to be used in zeolite-containing detergents as an anti-deposition additive, the cellulose ether must have a certain degree of substitution.

European patent application EP 054325 prevents redeposition of ternary mixtures of sodium carboxymethyl cellulose, linear polycarbonate and C ₁ -C ₃ alkyl cellulose having a degree of substitution of at least 0.5 and a degree of polymerization of up to 300. Use in detergents to do so. DE-A-4325882 proposes to use cellulase as a redeposition inhibitor in detergents.

(Disclosure of the Invention) (Technical Problem to be Solved by the Invention) Although the methods described in the above documents often give sufficiently satisfactory results,
There is a need to develop more effective redeposition prevention system.

The Solution Surprisingly, it has been found that the use of certain cellulases can particularly effectively reduce the redeposition and discoloration of soil particles on the laundered laundry. The present invention relates to Melanocarpus sp. Or Myriococcum (Myrio).
Coccum) sp. 20K-cellulase as a redeposition inhibitor in detergents. The invention also relates to a similar use as a redeposition inhibitor in detergents containing particulate water-insoluble inorganic builders, especially zeolites.

Further, the present invention provides 2 obtained from Melanocarpus sp. Or Myriococcum sp.
Detergents containing 0K-cellulase together with optionally genetically modified proteases and / or alkali metal percarbonates from Bacillus lentus are also concerned. The use of such a combination further enhances the anti-redeposition effect of the cellulase used according to the present invention.

20K-cellulases obtained from Melanocarpus sp. Or Myriococcum sp. Are known from WO 97/14804. As described in that international publication,
This cellulase has a molecular weight of approximately 20 kDa, exhibits approximately 80% of maximum activity at 50 ° C./pH 4-9, and retains approximately 50% of maximum activity at pH 10.
This cellulase is described in Melanocarpus a, also as described in WO97 / 14804.
Genetically engineered Trichoderma reseei-transf isolated from lbomyces
Manufactured from ormants. Cellulases with greater than 80% homology with 20K-cellulases can also be used for the purposes of the present invention.

Another particular advantage of the cellulase used according to the invention is that, when it is used, it is not inferior to other cellulases in terms of color reproduction and fiber softening effect, even though it is laundered. The reduction in wet tear strength of the resulting textiles is not as great as with other cellulases.

The 20 K-cellulase is preferably used in such an amount that the final detergent has a cellulolytic activity of 1 to 500 NCU / g, preferably 2 to 400 NCU / g, more preferably 6 to 200 NCU / g. The cellulolytic activity was determined by Bailey et al.
Microb. Technol. 3: 153 (1981), it was measured by hydrolyzing 1% by mass of carboxymethylcellulose at 50 ° C. and neutral pH and quantifying the released reducing sugar with dinitrosalicylic acid. can do. The detergent of the present invention may additionally contain other cellulases.

The detergent according to the invention comprises preferably 0.001 to 0.5 mg, in particular 0.02 to 0.3 mg of cellulolytic protein per gram of total detergent. Protein concentrations can be determined by known methods, such as the bicinchoninic 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 protease from Bacillus lentus is stable and active under strongly alkaline conditions. Such proteases are described by Bacill, as described in WO91 / 02792.
Produced in us lentus (DSM5483). This Bacillus lentus alkaline protease (BLAP) transforms Bacillus licheniformis transformed with an expression plasmid carrying the BLAP gene into Bacillus licus
It can be produced by culturing under the control of the promoter from heniformis ATCC 53926. The composition and three-dimensional structure of BLAP is known (DW Godette et al., J. Mol. Bi.
ol. 228, 580-595, 1992). This protease is described in the document 2
The 69 amino acid sequence is characterized by a calculated molecular weight of 26823 Daltons and a theoretical isoelectric point of 9.7. This Bacillus lentus DSM 54 can be obtained by mutation
Variants of 83 protease are described in US Pat. No. 5,340,735. Included therein are protease enzymes that produce minimal material damage and destruction of fiber structure without loss of washability in the washing of proteinaceous fibers, such as silk or wool fibers, especially repeated washing. is there.

In addition to the natural protease from Bacillus lentus, proteases suitable for use in the present invention include natural proteases (position 211 (BLAP count)).
The amino acid leucine (L in the standard one-letter code) is replaced by asvala silver acid (D) or glutamic acid (E) (L211D or L211E), including genetically engineered proteases of the above BLAP species. It Such a protease can be produced by the method described in WO95 / 23221. In addition, the original Bacillus l
Further denaturation of the entus protease is possible, eg at least one conversion of amino acids (S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I).
). Variant S3T + V4I + A188P + V193M + V199 in which at least one amino acid has been exchanged
I + L211D) is particularly preferred. With respect to the nomenclature for the individual amino acid conversions of the above proteases, it is important to note that the numbering of amino acid positions in BLAP is different from that commonly found in subtilisin BPN '. The numbers at positions 1-35 are the same for subtilisin BPN 'and BLAP, but the corresponding absent amino acids at positions 36-54 of BLAP correspond to positions 37-55 of BPN'. Similarly, BLAP 55 to 16
The 0th position corresponds to the 57th to 162nd positions of BPN ', and the 161st to 269th positions of BLAP are 1st of BPN'.
It corresponds to the 67th to 275th positions.

The detergent of the present invention is preferably about 100 to 10000 PU / g, more preferably 30.
It has a proteolytic activity of 0 to 8000 PU / g. Protease activity is Tensid
Measured by the following standard method described in e 7 (1970), 125: Hardness of 15 ° dH (CaCl ₂ · 2H ₂ O 0.058% by mass, MgCl ₂ · 6H ₂ O 0.028% by mass) A solution of 12 g / l casein and 30 mM sodium tripolyphosphate in water with NaHCO _{3 and} 0.042% by weight is heated to 70 ° C. and 0.1 N NaOH is added at 50 ° C. to obtain a pH value of 8. Adjust to 5. 200 ml of the test enzyme solution in 2% by weight sodium tripolyphosphate buffer (pH 8.5) is added to 600 ml of the substrate solution. The reaction mixture is incubated at 50 ° C for 15 minutes. Next, 500 ml of TCA solution (3
Add 0.44 M trichloroacetic acid in volume% acetic acid and 0.22 M sodium acetate) and cool to quench (15 min at 0 ° C. in ice bath). TCA-insoluble protein is removed by centrifugation. 900 ml of the supernatant phase are diluted with 300 ml of 2N NaOH.
The absorption of this solution at 290 nm is measured by an absorption spectrometer. The zero absorption value is determined on a centrifuge solution prepared by mixing 600 ml of the TCA solution with 600 ml of the substrate solution and then adding the enzyme solution. 0.500 under the above measurement conditions
The proteolytic activity of the protease solution resulting in the absorption of OD is defined as 10 PU (protease unit) / ml. The ratio of cellulolytic activity expressed in NCO / g to proteolytic activity expressed in PU / g in the detergent of the invention is preferably 1:
It is 10,000 to 5: 1, and more preferably 1: 1600 to 4: 3.

The enzyme may be adsorbed to a carrier to prevent premature inactivation, especially when used in particulate detergents (eg as described for other enzymes in EP0564476 or WO94 / 23005). Alternatively, and / or it may be encapsulated by a membrane material. The combination according to the invention of a particular cellulase and optionally a genetically modified protease is carried out by combining two individual enzymes or two enzymes prepared separately by known methods, or WO96 / 00772 or WO96 / 007
It can be used in the detergents of the present invention by incorporating cellulases and proteases that have been processed together in the same particles as described in 73.

The detergent of the present invention is preferably up to 50% by mass, more preferably 5 to 30% by mass.
Alkali metal percarbonate, particularly preferably sodium percarbonate. This ingredient is
It can be produced by known methods, especially when used as a granular detergent, for example
WO91 / 15423, WO92 / 17400, WO92 / 17404, WO93 / 04159, WO93 / 04982, WO93 / 20007,
WO94 / 03553, WO94 / 05594, WO94 / 14701, WO94 / 14702, WO94 / 24044, WO95 / 02555,
WO95 / 02672, WO95 / 06615, WO95 / 15291 or WO95 / 15292 or EP0459625, EP048
It is optionally made into granules or stabilized and / or coated, as described in 7256, EP0567140, EP0623553, EP0592969 or EP0748764. For reasons of stability, this component is preferably an alkaline earth metal sulfate, an alkali metal sulfate, an alkali metal silicate, an alkaline earth metal halide, an alkali metal halide, an alkali metal carbonate, an alkali metal hydrogencarbonate, an alkali phosphate. Manufactured or coated with metal, alkali metal borate, alkali metal perborate, boric acid, partially hydrated alumosilicate, carboxylic acid, dicarboxylic acid, unsaturated carboxylic acid and / or dicarboxylic acid polymer, or a mixture thereof. Used in a granular form. In a preferred embodiment, the Morphology Index (MI) of 0.06.
ex) (specified in EP0451893).

In one preferred embodiment, the ratio of cellulase used according to the invention to alkali metal percarbonate is 0 per 1% by weight of alkali metal percarbonate in the detergent.
． The range is 0001 to 0.1 mg, and more preferably 0.001 to 0.01 mg.

The detergent is preferably a perborate-containing detergent or a light detergent, optionally containing a fabric softener used in the rinse cycle after washing. In one preferred embodiment of the present invention, the use of a special cellulase is intended to reduce redeposition during washing of laundry with a laundry detergent comprising a particulate water-insoluble inorganic builder component, especially zeolite NaA. Has an aim.

The cellulase and optionally other enzymes can be used in granular detergents, optionally in the form of a stabilized liquid formulation, but preferably for example DE
1617232, DE-A-2032766 or DE4041752 or EP168526, EP170360, EP270608 or EP304331, adsorbed on a carrier, encapsulated by a membrane material, or with an inorganic and / or organic support material Used as a typical granule. Other enzymes include, in addition to the proteases mentioned above, in particular amylases, lipases, oxidases, peroxidases, cutinases, pullulanases, xylanases and / or hemicellulases, and optionally other cellulases and / or
Alternatively proteases are included and the other enzymes are present in the detergent preferably in an amount of 0.1 to 2% by weight. Enzymes may be included as separate particles or used in the form of multi-enzyme granules as described for example in DE4422433 or DE4422609 or WO90 / 09440 or WO90 / 09428 and references cited therein. May be done.

Besides the combinations used according to the invention, the detergents according to the invention which can be present in particular as powdered solids, as post-compacted particles or as homogeneous solutions or suspensions, are generally It may include any of the known ingredients included. Furthermore, the detergents of the invention are based on builders, surfactants, bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators, organic and / or inorganic peroxygen compounds. Other bleaching agents may be included, as well as other auxiliaries such as optical brighteners, redeposition inhibitors, dye transfer inhibitors, foam control agents, silver corrosion inhibitors and dyes and fragrances.

The detergents of the present invention may comprise one or more surfactants, especially anionic surfactants, nonionic surfactants and mixtures thereof, and also cationic surfactants, zwitterionic surfactants. Agents and amphoteric surfactants may be included.

Suitable anionic surfactants are, in particular, soaps and surfactants containing sulphate or sulphonate groups. Suitable sulphonate-based surfactants are preferably C ₉ -C ₁₃ alkylbenzene sulphonates, olefin sulphonates, such as alkene and hydroxyalkane sulphonate mixtures, such as C ₁₂ -C ₁₈ monoolefins with internal or terminal double bonds in gaseous form. A disulfonate obtained by sulfonating with sulfur trioxide and then subjecting the sulfonated product to alkali or acid hydrolysis. Other suitable sulfonate surfactants are C _{1 2} -C ₁₈ alkane sulfonates obtainable by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization alkanes. Also suitable are esters of α-sulfo fatty acids (ester sulfonates), such as hydrogenated coconut, palm kernels or α-sulfonated methyl esters of tallow fatty acids. These are obtained by α-sulfonating the methyl esters of vegetable and / or animal fatty acids containing 8 to 20 carbon atoms in the fatty acid molecule and then neutralizing them into water-soluble monosalts. Esters of this type are preferably α-sulfonated esters of hydrogenated coconut, palm, palm kernels or tallow fatty acids, but with a small amount of unsaturated fatty acids such as the sulfonated products of oleic acid, preferably about 2-3. It may be present in an amount that does not exceed mass%. Particularly preferred are α-sulfofatty acid alkyl esters having an alkyl chain with not more than 4 carbon atoms in the ester group, such as methyl esters, ethyl esters, propyl esters and butyl esters. The methyl ester of α-sulfofatty acid (MES) and its saponified di-salt can be used particularly advantageously.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters,
For example monoesters, diesters and triesters and mixtures thereof, which are the esterification of monoglycerols with 1 to 3 mol of fatty acids or the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Manufactured by. Preferred alkyl or alkenyl sulphates are C ₁₂ -C ₁₈ fatty alcohols (eg coco fatty alcohols, tallow fatty alcohols, lauryl alcohols, myristyl alcohols, cetyl alcohols or stearyl alcohols) or sulfuric acid semiesters of C ₁₀ -C ₂₀ oxo alcohols. , And the corresponding semi-esters of secondary alcohols having the same chain length, in particular the alkali metal salts, in particular the sodium salt. Other preferred alkyl or alkenyl sulphates are sulphates of the above chain length which contain synthetic linear alkyl chains based on petrochemicals and which show similar decomposition behavior to the corresponding compounds based on oleochemical raw materials. From the viewpoint of washing _performance, C 12 _{-C 16} alkyl _sulfates, the _C 1 2 _{-C 15} alkyl sulfates and _C 14 _{-C 15} alkyl sulfates especially preferred.

Other suitable anionic surfactants are 2,3-alkyl sulphates, which can be prepared, for example, according to US3234258 or US5075041 and are commercially available from Shell Oil Company as DAN®. 1-6 moles of linear or branched _C 7 _{-C 21} alcohol ethoxylated with ethylene oxide (e.g., mean including 3.5 moles of ethylene oxide (EO) 2-methyl-branched _C 9 _{-C 11} alcohol or 1 sulfuric monoesters of _C 12 _{-C 18} alcohol), including a 4EO also preferred. Due to their high foaming capacity, they are used only in relatively small amounts, for example in amounts of 1 to 5% by weight, in laundry detergents.

Other preferred anionic surfactants are salts of alkyl sulfosuccinic acids, also known as sulfosuccinates or sulfosuccinates, sulfosuccinic acid and alcohols, preferably fatty alcohols, more preferably Are monoesters and / or diesters with ethoxylated fatty alcohols.
Preferred sulfosuccinates comprise C ₈ -C ₁₈ fatty alcohol molecule, or a mixture thereof. Particularly preferred sulfosuccinates, when considered alone, contain a fatty alcohol molecule derived from an ethoxylated fatty alcohol which is a nonionic surfactant. Of these sulfosuccinates, those in which the fatty alcohol molecule is derived from a narrow range ethoxylated fatty alcohol are particularly preferred. Alkyl or alkenyl succinic acids or salts thereof, preferably containing 8 to 18 carbon atoms in the alkyl or alkenyl chain, can also be used.

Other suitable anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (tauride) and / or N-methylglycine (sarcoside). Sarcosides or rather sarcosinates, especially sarcosinates of higher fatty acids which may be mono- or polyunsaturated, such as oleyl sarcosinate,
Particularly preferred. Other suitable anionic surfactants are especially soaps. Suitable soaps are derived from saturated fatty acid soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid salts, and especially natural fatty acids such as coconut fatty acid, palm kernel fatty acid or tallow fatty acid. Is a soap mixture. Known alkenyl succinates may be used with or as soap substitutes.

Anionic surfactants, including soaps, can be present 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 surfactant is preferably present in the form of the sodium or potassium salt, more preferably the sodium salt.

Suitable nonionic surfactants are especially alkyl glycosides and alkyl glycosides or linear chains containing 12 to 18 carbon atoms in the alkyl group and 3 to 20, preferably 4 to 10 alkyl ether groups. Or ethoxylated and / or propoxylated products of branched alcohols. Corresponding ethoxylation of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides (which correspond to the long-chain alcohol derivatives mentioned above with respect to the alkyl group) and alkylphenols containing 5 to 12 carbon atoms in the alkyl group. Also suitable are propoxylated products.

[0032]   Preferred nonionic surfactants preferably contain 8 to 18 carbon atoms and
Particularly primary, containing on average 1 to 12 moles of ethylene oxide (EO) per mole of coal
Alkoxylated alcohols, preferably ethoxylates. Where Arco
Group may be linear or branched, preferably 2-methyl branched, typically
Mixing linear and 2-methyl branching groups as present in the oxo alcohol group
May be included. However, natural sources with 12 to 18 carbon atoms
Source alcohol (eg coconut alcohol, palm alcohol, tallow alcohol
(Or oleyl alcohol) and an average of 2 to 1 mole of alcohol and 1 mole of alcohol.
Alcohol ethoxylates containing 8 EO are particularly preferred. Preferred ethoxyl
Alcohols include, for example, C containing 3EO or 4EO.₁₂-C₁₄Alcohol, 7
C including EO₉-C₁₁C containing alcohol, 3EO, 5EO, 7EO or 8EO_Thirteen−
C₁₅C containing alcohol, 3EO, 5EO or 7EO₁₂-C₁₈Alcohol and
And mixtures thereof, eg C containing 3 EO₁₂-C₁₄C containing alcohol and 7EO ₁₂ -C₁₈Mixtures with alcohol are included.   The above degrees of ethoxylation are statistical averages, and for certain products are whole numbers.
Or it can be a fraction. Preferred alcohol ethoxylates have a narrow homolog distribution
With (narrow range ethoxylates, NRE).   Fatty alcohols containing more than 12 EO in addition to these nonionic surfactants
Can also be used. Examples of such fatty alcohols are 14EO, 16EO, 20EO, 2
(Tallow) fatty alcohol containing 5 EO, 30 EO or 40 EO.

[0033]   Very low foaming surfactants are usually used, especially for dishwashing detergents
. Such surfactants preferably contain up to 8 moles of ethylene per molecule.
C containing oxide units and up to 8 moles of propylene oxide units₁₂-C₁₈ Includes alkyl polyethylene glycol polypropylene glycol ether
. However, other known low foaming surfactants, eg 8 moles per molecule
C containing up to 8 ethylene oxide units and up to 8 moles butylene oxide units ₁₂ -C₁₈Alkyl polyethylene glycol Polybutylene glycol ether
, And end-capped alkyl polyalkylene mixed ethers may also be used. EP03
Hydroxy-functional alkoxylated alcohols described in 00305, so-called
Hydroxy mixed esters are also particularly preferred.

Nonionic surfactants are of the formula: RO (G) x, where R is a primary straight-chain or methyl branch containing 8 to 22, preferably 12 to 18 carbon atoms, especially 2- A methyl-branched aliphatic group, G being a glucose having 5 or 6 carbon atoms, preferably glucose). The degree of oligomerization x, which indicates the distribution of mono and oligoglycosides, is a number from 1 to 10 (which may be a fraction if determined by analysis), preferably x is 1.2 to 1.4.
Is.

[0035]   Other suitable nonionic surfactants are of formula (I):

[Chemical 1] (In the formula, R ¹ CO is an aliphatic acyl group containing 6 to 22 carbon atoms, R ² is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms, and [Z ] Is a linear or branched polyhydroxyalkyl group containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.) Is a polyhydroxy fatty acid amide. The polyhydroxy fatty acid amides are preferably derived from reducing sugars containing 5 or 6 carbon atoms, especially glucose. A group of polyhydroxy fatty acid amides has formula (II):

[Chemical 2] (In the formula, R ³ is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, and R ⁴ is a linear, branched or cyclic group containing 2 to 8 carbon atoms. Is an alkylene or arylene group, R ⁵ is a linear, branched or cyclic alkyl, aryl or hydroxyalkyl group containing 1 to 8 carbon atoms, preferably a C ₁ -C ₄ alkyl group or a phenyl group , [Z] is a linear polyhydroxy group in which the alkyl group is substituted by at least two hydroxyl groups, or an alkoxylated, preferably ethoxylated or propoxylated derivative of such a group.). Also includes compounds. Again, [Z] is preferably obtained by reductive amination of sugars such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. Then N-alkoxy or N
The aryloxy-substituted compounds may be converted to the desired polyhydroxy fatty acid amides by reacting with fatty acid methyl esters in the presence of alkoxides as catalysts, eg according to the teaching of WO95 / 07331.

Another class of preferred nonionic surfactants, which can be used alone or in combination with other nonionic surfactants, in particular alkoxylated fatty alcohols and / or alkyl glycosides, is preferably one per alkyl chain. Alkoxylated, preferably ethoxylated or ethoxylated / propoxylated fatty acid alkyl esters containing up to 4 carbon atoms, especially preferred by the process described in JP 58-217598 or WO 90/13533 Is the fatty acid methyl ester produced.

Also suitable are amine oxide type nonionic surfactants such as N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide oxide, and fatty acid alkanolamide type nonionic surfactants. ing.

The amount of these nonionic surfactants used preferably does not exceed the amount of ethoxylated fatty alcohols used, especially not more than half thereof.

Other suitable surfactants are the so-called Gemini (twin) surfactants. Gemini surfactants are generally understood to be compounds containing two hydrophilic groups and two hydrophobic groups in a molecule. These groups are usually separated from each other by so-called "spacers". The spacer is usually a carbon chain having a sufficient length so that the hydrophilic groups have a sufficient spacing so that the hydrophilic groups can act independently of each other. Gemini surfactants are generally characterized by a very low critical micelle concentration and the ability to significantly reduce the surface tension of water. In exceptional cases, Gemini surfactants are not only understood as "dimeric" surfactants, but also as "trimeric" surfactants.
It is also understood as a surfactant. Suitable Gemini surfactants are, for example, DE4321022
And the dimer alcohol bis- and trimer alcohol tris-sulfates and -ether sulphates described in DE 19503061. The end-capped dimeric and trimeric mixed ethers described in DE19513391 are characterized in particular by their difunctionality and polyfunctionality. Therefore, the described end-capped surfactants exhibit good wetting properties and low foaming properties, which makes them particularly suitable for use in machine washing or cleaning processes. However, the gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides described in WO95 / 19953, WO95 / 19954 and WO95 / 19955 can also be used.

Surfactants are present in the laundry detergents according to the invention in an amount of preferably 5 to 50% by weight, more preferably 8 to 30% by weight, while hard surface cleaning detergents, especially dishwashing detergents. Is up to 10% by mass, preferably up to 5% by mass, more preferably 0.5 to
It has a lower surfactant content of 3% by weight.

The detergent of the present invention preferably comprises at least one water-soluble and / or water-insoluble organic and / or inorganic builder. Suitable water-soluble organic builders include polycarboxylic acids, especially citric acid and sugar acids, monomeric or polymeric aminopolycarboxylic acids, especially methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyasparasilic acid, polyphosphonic acid, Especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1
-Hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin, and polymeric (poly) carboxylic acids, especially EP0625992, WO92 / 1854
2 or polycarboxylates obtained by oxidation of polysaccharides or dextrins described in EP 0232202, acrylic acid, methacrylic acid or maleic acid polymers,
Included are copolymers of these with a small amount of polymerizable material that does not have a carboxylic acid functional group in the copolymerized form. The relative molecular weight of homopolymers of unsaturated carboxylic acids is usually 3000-200000 (based on free acid) and the relative molecular weight of copolymers is 200.
It is 0 to 200000, preferably 30,000 to 120,000. A particularly preferred acrylic acid / maleic acid copolymer has a relative molecular weight of 30,000 to 100,000. Commercially available products are, for example, Sokalan® CP5, CP10 and PA30 (manufactured by BASF). Suitable (less preferred) compounds of this type are copolymers of acrylic or methacrylic acid with vinyl ethers (for example vinyl methyl ether), vinyl esters, ethylene, propylene and styrene (where the acid is at least 50).
Account for mass%). Other suitable water-soluble organic builders are terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or esterified vinyl alcohols or carbohydrates as third monomers. First acid monomer or a salt thereof, monoethylenically unsaturated C ₃ -
C ₈ carboxylic acid, preferably _C 3 -C ₄ monocarboxylic acid, more preferably derived from (meth) acrylic acid. The second acid monomer or salt thereof may be a derivative of C ₄ -C ₈ dicarboxylic acid, particularly preferably maleic acid, and / or a derivative of allyl sulfonic acid substituted at the 2-position by an alkyl or aryl group. Such polymers can be prepared, inter alia, by the methods described in DE4221381 and DE4300772 and usually have a relative molecular weight of 1000 to 200,000. Other preferred copolymers are those described in DE4303320 and DE4417734, preferably those containing acrolein and acrylic acid / acrylate or vinyl acetate as monomers.

Advantageously, the organic builders can be used in the form of an aqueous solution, preferably a 30-50% by weight aqueous solution. All of the above acids are usually used in the form of their water-soluble salts, especially their alkali metal salts. If desired, such organic builders may be present in an amount of up to 40% by weight, preferably up to 25% by weight, more preferably 1 to 8% by weight. In the pasty or liquid detergent of the present invention, especially in the water-containing detergent, an amount near the above upper limit is preferable.

Suitable water-soluble inorganic builders are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be present in the form of alkaline, neutral or acidic sodium or potassium salts. Examples of such builders are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, phosphoric acid having an oligomerization degree of 5-1000, more preferably 5-50. Trisodium oligomers and the corresponding potassium salts or mixtures of sodium and potassium salts.

As a water-insoluble inorganic or water-dispersible inorganic builder substance, a crystalline or amorphous alkali metal alumosilicate is used in a liquid detergent in an amount of up to 50% by weight, preferably not exceeding 40% by weight, in particular 1 to Used in an amount of 5% by weight. Among these, detergent-quality crystalline sodium aluminosilicates, in particular zeolites A, P and optionally X, alone or as a mixture, for example in the form of a co-crystallisation of zeolites A and X (Vegobond® AX, Condea Augusta SPA product) preferred. In solid granular detergents, amounts near the above upper limit are preferably used. Suitable aluminosilicates do not contain particles with a size larger than 30 μm, preferably at least 80% by weight consists of particles with a size smaller than 10 μm. These calcium-binding ability can be measured by the method described in DE2412837, and is usually 10
It is 0 to 200 mg CaO / g.

The alumosilicate substitute or partial substitute is a crystalline alkali metal silicate, which may be present alone or as a mixture with an amorphous silicate. Alkali metal silicates suitable as builders in the detergents of the invention are preferably 0.95.
It has a molar ratio of alkali metal oxide to SiO ₂ of less than 1: 1, in particular 1: 1.1 to 1:12, and may be amorphous or crystalline. A preferred alkali metal silicate is sodium silicate, especially amorphous sodium silicate with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Sodium silicate with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be prepared by the method described in EP 0425427. As the crystalline silicate, the formula: Na ₂ Si _x O _{2x + 1} · yH ₂ O (where x (so-called coefficient) is a number of 1.9 to 22, particularly 1.9 to 4, and y is , A number of 0 to 33. The preferable value of x is 2, 3 or 4.) The crystalline layered silicate represented by the formula (3) is preferably used alone or as a mixture with an amorphous silicate. Crystalline layered silicates corresponding to this formula are described, for example, in EP0164514. Preferred crystalline layered silicates are compounds where x in the above formula is 2 or 3. β- and δ
-Sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O) is particularly preferred, and sodium β-disilicate can be produced, for example, by the method described in WO91 / 08171. Δ-sodium disilicate having a coefficient of 1.9 to 3.2 is JP04-238809 or JP04-260610.
Can be manufactured according to. It can be produced from amorphous alkali metal silicates as described in EP0548599, EP0502325 and EP0425428, where x is 1.
A substantially anhydrous crystalline alkali metal silicate corresponding to the above formula of 9 to 2.1 is also
It can be used in the detergents of the invention.

Another preferred embodiment of the detergent according to the invention is characterized by the use of crystalline layered sodium silicate with a modulus of 2 which can be produced from sand and soda by the method described in EP0436835. In another preferred embodiment of the detergent according to the invention, EP016455
2 and / or the coefficient produced by the method described in EP 0294753 is 1.9 to 3
． A crystalline sodium silicate of 5 is used. The crystalline layered silicate represented by the above formula is, for example, a trade name Na-SKS (for example, Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O
, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ · xH ₂ O, Magadiite), Na-
It is commercially available from Clariant GmbH as SKS-3 (including Na ₂ Si ₈ O ₁₇ · xH ₂ O) and Na-SKS-4 (including Na ₂ Si ₄ O ₉ · xH ₂ O, macatite). Among them, Na-SKS-5 (α-
Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , Natrosilite), Na-SKS-7 (NaH
Si ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ / 3H ₂ O, kanemite), Na-SKS-11 (
τ-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ) are preferred, especially Na-SKS-
6 (δ-Na ₂ Si ₂ O ₅ ) is preferred. For an overview of crystalline layered silicates, see, for example, "Hoechst
High Chem Magazin 14/1993 "pp. 33-38 and" Saifen-Oele-Fette-Wachse ",
Vol. 116, No. 20, 1990, pp. 805-808.

Yet another preferred embodiment of the detergents according to the invention is a granular compound of crystalline layered silicates and citrates, such as the crystalline layered silicates described in DE 19819187 and the abovementioned polycarboxylic acids (co). It is characterized by using a granular compound of a polymer or a granular compound of alkali metal silicates and carbonates described, for example, in WO 95/22592 or commercially available, for example as Nabion® 15.

Builders are optionally present in the detergents of the invention up to 90% by weight, preferably 75%.
It may be present in an amount up to% by weight. The laundry detergent of the invention has a builder content of especially 5 to 50% by weight. In the hard surface cleaning compositions of the invention, especially in dishwashing detergents, the builder content is in particular 5 to 88% by weight, such compositions being free of water insoluble builders. Another preferred embodiment of the dishwashing detergent according to the invention comprises a water-soluble organic builder, in particular 20-40% by weight alkali metal citrate, 5-15% by weight alkali metal carbonate, and 20-40% by weight alkali metal disilicate. There is.

In addition to the alkali metal percarbonates already mentioned, suitable peroxygen compounds for use in the detergents according to the invention are in particular organic peracids or peracid salts of organic acids (eg phthalimidopercaproic acid, persulfates). Benzoic acid or salts of diperdodecanedioic acid), hydrogen peroxide and inorganic salts which release hydrogen peroxide under washing conditions (eg perborate, percarbonate, persilicate and / or persulfate, For example caroate). If solid peroxygen compounds are used, they can be used in the form of powders or granules, which can be coated in known manner. If the detergent according to the invention comprises a peroxygen compound, the peroxygen compound may be present preferably in an amount of up to 50% by weight, more preferably 5 to 30% by weight. Small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulphate can be used.

A compound which, under perhydrolysis conditions, produces an aliphatic peroxocarboxylic acid containing preferably 1 to 10, more preferably 2 to 4 carbon atoms and / or an optionally substituted perbenzoic acid, It can be used as a bleach activator. Compounds having O- and / or N-acyl groups of the abovementioned carbon number and / or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT). , Acylated glycoluril, especially tetraacetylglycoluril (TAGU), N-acylimide, especially N-nonanoylsuccinimide (NOSI), acetylated phenolsulfonate, especially n.
-Nonanoyl or isononanoyl-oxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetic acid, 2,5-diacetoxy-2,
5-Dihydrofuran and the enol esters known from DE19616693 and DE19616767, the acetylated sorbitol and mannitol described in EP0525239 and mixtures thereof (SORMAN), acetylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetyl. Xylose and octaacetyllactose, and acetylated, desired N-alkylated glucamine and gluconolactone, and / or N-acetylated lactams, such as N-benzoylcaprolactam (which are WO94 / 27970, WO94 / 28102, WO94 / 281.
03, WO95 / 00626, WO95 / 14759 and WO95 / 17498). Substituted hydrophilic acyl acetals known from DE19616769, and the acyllactams described in DE19616770 and WO95 / 14075 are also preferably used. Combinations of conventional bleach activators known from DE 4443177 can also be used. These bleach activators are preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight based on the effective amount and the total amount of the detergent.
Used in an amount of% by weight.

In addition to or in place of the conventional bleach activators mentioned above, it is also possible to use sulfoimines and / or bleach-assisting (enhancing) transition metal salts or transition metal complexes known from EP0446982 and EP0453003 as so-called bleach catalysts. .

Suitable organic solvents for use in addition to water in the detergents according to the invention, especially when the detergents are liquid or pasty, include C ₁ -C ₄ alcohols, especially methanol, ethanol, isopropanol and tert- butanol - le, C ₂ -C ₄ diol, especially ethylene glycol and propylene glycol, and mixtures thereof, as well as ethers derived from these compounds. Such a water-miscible solvent is preferably contained in the detergent of the present invention in an amount of 30% by mass or less, more preferably 6 to 2%.
It is present in an amount of 0% by weight.

The detergent may further include other typical detergent ingredients. Such desired ingredients include, among others, enzyme stabilizers, anti-redeposition agents, dye transfer inhibitors, suds suppressors, and optional brighteners, as well as dyes and fragrances. To protect silverware from corrosion, the dishwashing detergent of the present invention may include a silver corrosion inhibitor. In addition, the hard surface detergents of the present invention may include abrasive components, especially silica powder, wood powder, polymer powder, chalk and glass particulates, and mixtures thereof. The abrasive is present in the dishwashing detergent according to the invention in an amount of up to 20% by weight, in particular 5 to 15% by weight.

In order to bring the desired pH value which is not spontaneously adjusted by the mixing of the other ingredients, the detergents according to the invention comprise a system-compatible and environmentally compatible acid, in particular citric acid, acetic acid. , Tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, and mineral acids, especially sulfuric acid, or bases, especially ammonium hydroxide and / or alkali metal hydroxides. Such a pH adjusting agent is preferably contained in the detergent of the present invention in an amount of 20% by mass or less, more preferably 1.2 to 17%.
Present in an amount of% by weight.

Dye transfer inhibitors suitable for use in the laundry detergents of the present invention include, among others, polyvinylpyrrolidone, polyvinylimidazole, polymeric N-oxides such as poly- (vinylpyridine-N-oxide), and vinylpyrrolidone. / Vinylimidazole copolymer.

Additional redeposition inhibitors can also be included in the detergents of the present invention. Suitable additional anti-redeposition agents are water-soluble, generally organic colloids such as starch, pastes, gelatin, starch or salts of ethercarboxylic acids or ethersulphonic acids of cellulose, or acid sulfates of starch or cellulose. . Water-soluble polyamides containing acidic groups are also suitable for this purpose. Other starch derivatives than the above, such as aldehyde starches, can also be used. Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl celluloses, mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof also for example from 0.1 to 5 based on the detergent. It is preferably used in an amount of% by weight.

The laundry detergent of the present invention may contain diaminostilbene disulfonic acid or an alkali metal salt thereof as an optical brightening agent. Suitable optical brighteners are, for example, 4
, 4'-bis- (2-amino-4-morpholino-1,3,5-triazinyl-6-amino) -stilbene-2,2'-disulfonic acid salt, or a diethanolamino group instead of the morpholino group, It is a compound having a similar structure containing a methylamino group and an anilino group or a 2-methoxyethylamino group. Substituted diphenylstyryl type brighteners such as 4,4′-bis- (2-sulfostyryl) -diphenyl,
4,4′-bis- (4-chloro-3-sulfostyryl) -diphenyl or 4- (4
An alkali metal salt of -chlorostyryl) -4 '-(2-sulfostyryl) -diphenyl may be present. Mixtures of the above brighteners can also be used.

Particularly when the detergent is used in a washing machine, it is advantageous to add the foam control agents typical of detergents. Suitable foam control agents are, for example, natural or synthetic soap containing C ₁₈ -C ₂₄ fatty acid with a high proportion. Suitable non-surfactant suds suppressors are, for example, organopolysiloxanes, or mixtures thereof with finely divided silica, optionally silanized, and paraffins, waxes, microcrystalline waxes and silanized silica or bisfatty acid alkylenediamides. Is a mixture of. Mixtures of different foam control agents, for example mixtures of silicones, paraffins and waxes, can also be used to advantage. The suds suppressor, in particular the silicone- and / or paraffin-containing suds suppressor, is preferably fixed to a particulate water-soluble or water-dispersible carrier. A mixture of paraffin and bisstearylethylenediamide is particularly preferred.

The production of the solid detergents according to the invention can be carried out without difficulty in a known manner, for example by spray drying or granulation, optionally with enzymes and other heat-sensitive ingredients such as bleaching agents. It will be added separately in a later step. High bulk density, especially 650-950
The detergents according to the invention having a bulk density of g / l can preferably be produced by a process comprising an extrusion step known from EP0486592. Another preferred manufacturing method is EP06.
Granulation method according to 42576.

Containing one or more phases, colored in one or more colors, in particular 1
In the case of a tablet press, for example an eccentric press or a rotary press, in order to produce a detergent according to the invention in the form of a tablet consisting of one or several phases, in particular two phases, all ingredients (optionally for each layer) are mixed in a mixer. Mix and tablet the resulting mixture at a pressure of about 50-100 kN, preferably 60-70 kN, in a conventional manner. Especially in the case of a multi-layer tablet, at least one layer, preferably 5 to 20 kN, more preferably 1
It is advantageous to pre-compress at a pressure of 0 to 15 kN. By doing so, it is possible to easily produce a crush-resistant tablet that dissolves sufficiently quickly under the conditions of use. Such tablets usually have a crushing and bending strength of 100-200N, preferably about 150N. The tablets thus produced are preferably 10-50
It is preferred to have a mass of g, more preferably 15-40 g. Tablets may be of any shape, including round, oval or prismatic and variations thereof. The corners or edges are advantageously rounded. Round tablets are preferably 30 mm-40
It has a diameter of mm. The size of a rectangular or square tablet, which is mainly introduced from the dispensing component of a dishwasher, for example, depends on the shape and dimensions of the dispensing component. For example, in a preferred embodiment, the bottom surface is (20 to 30 mm) x (34 to 4).
0 mm), especially 26 × 36 mm, or 24 × 38 mm.

The liquid or pasty detergents of the invention in solution with typical solvents can usually be prepared simply by mixing the ingredients, which can be introduced into the automatic mixer as such or as a solution.

[0062]

【Example】

Example 1 Cellulases shown in Table 1 were added to the enzyme-free basic detergent BW1. Cellulase is based on protein at 0.6% by weight of Celluzyme (in the particular detergent used).
It was used in an amount equivalent to registered trademark) 0.7T (manufactured by Novo Nordisk). The discoloration of the cloth is
After washing 10 times, the reflectance was measured and determined. The washing test was carried out under the following conditions: Washing machine: Miele (registered trademark) W918 Temperature: 40 ° C Detergent usage: 76 g Water hardness: 16 ° dH Washing: 2.5 kg of clean washing (Waescheforschungsanstalt Krefeld) Cotton test cloth, pillowcase, pile hand towel, vest and kitchen towel) Stain: 5 skeins of cotton cloth with standard dust / sebum stain were added at each wash.

The discoloration values (% reflectance averaged over all fabric products) obtained after laundering with the indicated formulation are shown in Table 1 below. The initial reflectance before washing and the reflectance for the enzyme-free base detergent are also shown for comparison.

[0064]

[Table 1]

It can be seen that the cellulases used according to the invention give better results in inhibiting redeposition than other cellulases.

Example 2 except that the washing was performed 11 times and the basic detergent BW2 containing 1.2% by weight of enzyme granules containing the protease BLAP having an activity of 200,000 PU / g (as opposed to BW1) was used. The procedure described in Example 1 was repeated.

[0067]

[Table 2]

It can be seen that the detergents of the invention have a better redeposition prevention effect than detergents containing cellulases other than the cellulases used according to the invention.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), AU, BR, C N, CZ, DZ, HU, ID, IL, IN, JP, KR , MX, PL, RO, RU, SG, SI, SK, TR, UA, US, ZA (72) Inventor Karl-Heinz Maurer             Federal Republic of Germany Day 40699 Erkhler             No. 5, Dechenstraße F-term (reference) 4H003 DA01 EA16 EA28 EC02 EC03                       EE05 FA06

Claims (10)

[Claims] 1. A method obtained from Melanocarpus sp. Or Myriococcum sp.
Use of 0K-cellulase or a cellulase having a homology of more than 80% thereto as a redeposition inhibitor in detergents. 2. Obtained from Melanocarps sp. Or Millionococcum sp.
Use of 0K-cellulase or a cellulase having a homology of more than 80% thereto as a redeposition inhibitor in a detergent containing a particulate water-insoluble inorganic builder, especially zeolite. 3. 2 obtained from Melanocarps sp. Or Millionococcum sp.
Use of 0K-cellulase or cellulase having a homology of more than 80% thereto for reducing redeposition in washing of laundry with a laundry detergent comprising a particulate water-insoluble inorganic builder component. 4. The detergent as a builder is a water-insoluble, water-dispersible, detergent-quality inorganic builder material, in particular crystalline alkali metal silicates, crystalline and / or amorphous alkali metal alumosilicates, in particular zeolite A, zeolites. 10 to 50% by weight, in particular 10 to 40% by weight, of P and / or zeolite X.
Use according to any one of. 5. Obtained from Melanocarps sp. Or Millionococcum sp.
A detergent containing 0K-cellulase or a cellulase having a homology of more than 80% thereto together with an optionally genetically modified protease and / or an alkali metal percarbonate from Bacillus lentus. 6. 2 obtained from Melanocarps sp. Or Millionococcum sp.
The detergent according to claim 5, wherein the cellulolytic activity derived from 0K-cellulase or a cellulase having a homology of more than 80% thereto is 1 to 500 NCU / g, particularly 5 to 400 NCU / g. 7. The detergent according to claim 5 or 6, wherein at least one of the amino acid exchanges S3T, V4I, V193M, V199I or L211D has been carried out in a genetically engineered protease from Bacillus lentus. 8. The ratio of cellulolytic activity expressed in NCU / g to proteolytic activity expressed in PU / g is preferably 1: 10,000 to 5: 1, in particular 1.
: 1600 to 4: 3, The detergent according to any one of claims 5 to 7. 9. Detergent according to claim 5, which contains up to 50% by weight, in particular 5 to 30% by weight, of alkali metal percarbonates, in particular sodium percarbonate. 10. The amount of 0.0001 to 0. 0 per 1% by mass of alkali metal percarbonate.
10. Detergent according to any of claims 5 to 9, comprising 1 mg, especially 0.001 to 0.01 mg of cellulolytic protein.