CA2324767A1 - Enzymatic redeposition inhibitor - Google Patents

Abstract

The invention relates to use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto as a redeposition inhibitor in detergents. In combination with optionally genetically modified protease and/or alkali metal percarbonate, this cellulase reduces the redeposition of soil particles onto washed laundry.

Description

ENZYMATIC REDEPOSITION INHIBITOR
Field of the Invention This invention relates to a certain enzymatic redeposition inhibitor for use in surfactant-containing laundry detergents and to detergents containing the certain enzymatic redeposition inhibitor in combination with other specially selected ingredients.
Background of the Invention At the present time, one-particle zeolite, more particularly zeolite NaA, is used in detergents to bind hardness sources, above all calcium andlor magnesium ions, in the washing water and soil. However, so-called co-builders or co-builder systems are used to a considerable extent, especially in laundry detergents, above all to counteract unwanted incrustations.
These incrustations are deposits on inner walls of washing machines and especially on the laundry, such as for example lime soap or organic residues.
Such incrustations can have an adverse effect on the feel, appearance, smell and absorption capacity of the laundry and are particularly noticeable after repeated washing.
In general, the discoloration of laundry also occurs after frequent washing, particularly when the soil suspending capacity of the wash liquor is inadequate as a result of detergent deficiency and the soil detached from the laundry is redeposited thereon from the liquor.
In order to avoid or minimize incrustations and discoloration, the above-mentioned builders or co-builders are added to the detergents. The additional use of complexing agents, including salts of aminocarboxylic acids, such as nitrilotriacetic acid and phosphonic acid derivatives, is known. In the practical application of detergents, co-builder combinations of this type counteract the precipitation of poorly soluble calcium salts and the resulting incrustations on fabrics or other surfaces. In addition, laundry detergents in particular may contain additional redeposition inhibitors which are specifically intended to counteract the redeposition of soil particles suspended in the wash liquor on the washed textiles.

It is proposed in DE-A 33 29 400 to use a mixture of methyl cellulose, carboxymethyl cellulose and copolymers of (meth)acrylic acid and malefic acid in a ratio of 1:1.5-4:3-10 as a redeposition-inhibiting additive in zeolite-containing detergents, the cellulose ethers having to have certain degrees of substitution.
European patent application EP 054 325 describes the use of ternary mixtures of sodium carboxymethyl cellulose, a linear polycarboxylate and C~_3 alkyl cellulose with degrees of substitution of at least 0.5 and degrees of polymerization of up to 300 in detergents for preventing redeposition.
DE-A-43 25 882 proposes the use of cellulase as a redeposition inhibitor in detergents.
Although the measures described in the documents cited above produce entirely satisfactory results in most cases, there is still a need to develop more effective redeposition inhibitor systems.
Summary of the Invention It has now surprisingly been found that the use of a certain cellulase leads to a particularly effective reduction in the redeposition of soil particles on washed laundry and in discoloration.
The present invention relates to the use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. as a redeposition inhibitor in detergents.
The present invention also relates to the corresponding use in detergents containing fine-particle water-insoluble inorganic builders, particularly zeolite.
The present invention also relates to detergents containing the 20K
cellulase obtainable from Melanocarpus sp. or Myriococcum sp. in combination with an optionally genetically modified protase from Bacillus lentus andlor alkali metal percarbonate. The use of such combinations leads to a further enhanced redeposition-inhibiting effect of the cellulase to be used in accordance with the invention.
The 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp.
is known from International patent application WO 97114804. As described therein, it has a molecular weight of about 20 kDa and develops about 80% of its maximal activity at 50°C/pH 4-9, almost 50% of the maximal activity remaining in tact at pH 10. It can be isolated from Melanocarpus albomyces and produced in genetically made Trichoderma reseei-transformants, again as described in WO
97114804. Cellulases with a homology to the 20K cellulase of more than 80%
may also be used for the purposes of the invention.
Another particular advantage of the cellulase to be used in accordance with the invention is that, where it is used, the loss of wet tear strength of washed textiles is nowhere near as great as it is where other cellulases are used although the cellulase to be used in accordance with the invention is in no way inferior to other cellulases in its color-freshening and fabric-softening effect.
20K cellulase is preferably used in such quantities that the final detergent has a cellulolytic activity of 1 NCUIg to 500 NCUIg (measurable by the hydrolysis of 1 % by weight carboxymethyl cellulose at 50°C and at a neutral pH
and determination of the reducing sugars released using dinitrosalicylic acid, as described by M.J. Bailey et al. in Enzyme Microb. Technol. 3: 153 (1981); 1 NCU defines the quantity of enzyme which produces reducing sugars in a quantity corresponding to 1 nmole of glucose per second), preferably 2 NCUIg to 400 NCUIg and more preferably 6 NCUIg to 200 NCUIg. The detergent may additionally contain other cellulases.
A detergent according to the invention preferably contains 0.001 mg to 0.5 mg and, more particularly, 0.02 mg to 0.3 mg of cellulolytic protein per gram of the detergent as a whole. The protein concentration may be determined by known methods, for example by the bicinchonic acid process (BCA process, Pierce Chemical Co., Rockford, IL.) or by the biuret process (A.G. Gornall, C.S.
Bardawill and M.M. David, J. Biol. Chem. 177, 751-766, 1948).
The protease from Bacillus lentus is stable and active under strongly alkaline conditions; it can be produced in Bacillus lentus (DSM 5483) as described in International Patent Application WO 91!02792. This Bacillus lentus alkaline protease (BLAP) can be produced by fermentation of Bacillus licheniformis transformed with an expression plasmid which carries the gene for BLAP under the control of the promoter from Bacillus licheniformis ATCC 53926.
The composition and three-dimensional structure of BLAP are known (D.W.
Godette et al., J. Mol. Biol. 228, 580-595, 1992). This protease is characterized by the sequence of 269 amino acids described in the literature, a calculated molecular weight of 26,823 dalton and a theoretical isoelectric point of 9.7.

Variants of this Bacillus lentus DSM 5483 protease obtainable by mutation are described in US 5,340,735. Included among these are protease enzymes which, in the washing - particularly repeated washing - of textiles of proteinogenic fibers, for example fabrics of silk or wool, cause minimal substance damage and destruction of the fiber structure without any loss of cleaning performance.
Besides the naturally occurring protease from Bacillus lentus, proteases suitable for use in accordance with the invention include genetically modified proteases of the above-mentioned BLAP type in which - in position 211 (BLAP
counting) - the amino acid leucine (L in the standard one-letter code) present in that position in the wild-type protease is replaced by aspartic acid (D) or glutamic acid (E) (L211 D or L211 E). These proteases may be produced as described in International Patent Application WO 95123221. In addition, further modifications may have been made in relation to the original Bacillus lentus protease, such as for example at least one of the amino acid exchanges S3T, V41, R99G, R99A, R99S, A188P, V193M and/or V1991. The variant in which at least one of the amino acid exchanges S3T + V41 + A188P + V193M + V1991 + L211 D was made is particularly preferred. Regarding the above-described protease nomenclature on the exchange of individual amino acids, it is important to bear in mind that the numbering of the amino acid positions in BLAP differs from that of the frequently encountered subtilisin BPN'. The numbering of positions 1 to 35 is identical in subtilisin BPN' and SLAP; through the absence of corresponding amino acids, positions 36 to 54 in BLAP correspond to positions 37 to 55 in BPN'.
Similarly, positions 55 to 160 in BLAP correspond to positions 57 to 162 in BPN' while positions 161 to 269 correspond to positions 167 to 275 in BPN'.
A detergent according to the invention preferably has a proteolytic activity of about 100 PUIg to about 10,000 PU/g and, more particularly, 300 PUIg to 8,000 PUIg. The protease activity is measured by the following standardized method described in Tenside 7 (1970), 125: a solution containing 12 g/l casein and 30 mM sodium tripolyphosphate in water with a hardness of 15°dH
(containing 0.058% by weight CaCl2 ~ 2 H20, 0.028% by weight MgCl2 ~ 6H20 and 0.042% by weight NaHC03) is heated to 70°C and the pH value is adjusted to 8.5 by addition of 0.1 N NaOH at 50°C. 200 ml of a solution of the enzyme to be tested in 2% by weight sodium tripolyphosphate buffer solution (pH 8.5) are added to 600 ml of the substrate solution. The reaction mixture is incubated for minutes at 50°C. The reaction is then terminated by addition of 500 ml TCA
solution (0.44 M trichloroacetic acid and 0.22 M sodium acetate in 3% by volume acetic acid) and cooling (ice bath at 0°C, 15 minutes). The TCA-insoluble protein 5 is removed by centrifugation. 900 ml of the supernatant phase are diluted with 300 ml of 2 N NaOH. The absorption of this solution at 290 nm is determined with an absorption spectrometer, the zero absorption value being determined by measuring the centrifuged solution which is prepared by mixing 600 ml of the above-mentioned TCA solution with 600 ml of the above-mentioned substrate 10 solution and subsequently adding the enzyme solution. The proteolytic activity of a protease solution which produces an absorption of 0.500 OD under the described measuring conditions is defined as 10 PU (protease units) per ml.
The ratio of cellulolytic activity expressed in NCOIg to proteolytic activity expressed in PU/g in the detergent according to the invention is preferably 1:10,000 to 5:1 and 15 more particularly 1:1,600 to 4:3.
The enzymes may be adsorbed onto supports andlor encapsulated in membrane materials to protect them against premature inactivation, particularly where they are to be used in particulate detergents, as described, for example, in European patent EP 0 564 476 or in International patent application WO
94!23005 for other enzymes. The combination according to the invention of a particular cellulase and optionally genetically modified protease may be used in detergents according to the invention through incorporation of the two separate enzymes or the two enzymes separately made up in known manner or through cellulase and protease made up together in the same granules, as known for example from International patent applications WO 96100772 or WO 96100773.
A detergent according to the invention preferably contains up to 50% by weight and more particularly 5% by weight to 30% by weight of alkali metal percarbonate, sodium percarbonate being particularly preferred. It may be produced in known manner and, above all for use in particulate detergents, may optionally be made up in granular form or stabilized andlor coated, as known for example from International patent applications WO 91115423, WO 92117400, WO
92117404, WO 93104159, WO 93!04982, W093120007, WO 94!03553, WO
94105594, WO 94114701, WO 94114702, WO 94124044, WO 95102555, WO

95102672, WO 95106615, WO 95115291 or WO 95115292 or European patent applications EP 0 459 625, EP 0 487 256, EP 0 567 140, EP 0 623 553, EP 0 592 969 or EP 0 748 764. For reasons of stability, it is preferably used in the form of granules produced or coated using alkaline earth metal sulfate, alkali metal sulfate, alkali metal silicate, alkaline earth metal halide, alkali metal halide, alkali metal carbonate, alkali metal hydrogen carbonate, alkali metal phosphate, alkali metal borate, alkali metal perborate, boric acid, partly hydrated alumosilicate, carboxylic acids, dicarboxylic acids, polymers of unsaturated carboxylic and/or dicarboxylic acids or mixtures thereof. In one preferred embodiment, it has a morphology index (MI) as defined in EP 0 451 893 of 0.06.
In one preferred embodiment, the ratio of cellulase to be used in accordance with the invention to alkali metal percarbonate is in the range from 0.0001 mg to 0.1 mg and more particularly in the range from 0.001 mg to 0.01 mg of cellulolytic protein per % by weight of alkali metal percarbonate in the detergent.
The detergents may advantageously be perborate-containing or light-duty laundry detergents and optionally fabric softeners used in a post-wash rinse cycle. In one preferred embodiment of the present invention, the use of the special cellulase is aimed at reducing redeposition in the washing of laundry with laundry detergents based on fine-particle water-insoluble inorganic builder components, more particularly zeolite NaA.
The cellulase and the other enzymes optionally used, which besides the protease mentioned include in particular amylase, lipase, oxidase, peroxidase, cutinase, pullulanase, xylanase andlor hemicellulase and optionally other cellulases andlor proteases and which are preferably present in the detergent in quantities of 0.1 % by weight to 2% by weight, may be used in the form of optionally stabilizer liquid formulations in particulate detergents, but are preferably adsorbed onto supports, encapsulated in membrane materials or used as typical granules with inorganic andlor organic carrier materials as described, for example, in German patent DE 16 17 232, DE-A 20 32 766 or DE 40 41 752 or in European patent applications EP 168 526, EP 170 360, EP 270 608 or EP
304 331. The enzymes may be contained in separate particles or may be used in the form of multienzyme granules as described, for example, in German patent applications DE 44 22 433 or DE 44 22 609 or in International patent applications WO 90109440 or WO 90109428 and the literature cited therein.
Besides the combination used in accordance with the invention, the detergents according to the invention - which may be present as, in particular, powder-form solids, as post-compacted particles or as homogeneous solutions or suspensions - may in principle contain any known ingredients typically encountered in detergents. More particularly, the detergents according to the invention may contain builders, surfactants, bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH
adjusters and other bleaching agents based on organic and/or inorganic peroxygen compounds and other auxiliaries, such as optical brighteners, redeposition inhibitors, dye transfer inhibitors, foam regulators, silver corrosion inhibitors and dyes and perfumes.
The detergents according to the invention may contain one or more surfactants, more particularly anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
Detailed Description of the Invention Suitable anionic surfactants are in particular soaps and those containing sulfate or sulfonate groups. Suitable surfactants of the sulfonate type are preferably C9_~3 alkyl benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C~2_~8 monoolefins with an internal or terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Other suitable surfactants of the sulfonate type are the alkane sulfonates obtained from C~2_~s alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of a-sulfofatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow acids, which are obtained by a-sulfonation of the methyl esters of fatty acids of vegetable andlor animal origin containing 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble monosalts are also suitable. The esters in question are preferably the a-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow acid, although sulfonation products of unsaturated fatty acids, for example oleic acid, may also be present in small quantities, preferably in quantities of not more than about 2 to 3% by weight. a-Sulfofatty acid alkyl esters with an alkyl chain of not more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters, are particularly preferred. The methyl esters of a-sulfofatty acids (MES) and saponified disalts thereof are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, i.e. the monoesters, diesters and triesters and mixtures thereof which are obtained where production is carried out by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C~2_~8 fatty alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or Coo-2o oxoalcohols and the corresponding semiesters of secondary alcohols with the same chain length. Other preferred alk(en)yl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical and which are similar in their degradation behavior to the corresponding compounds based on oleochemical raw materials. C~2_~s alkyl sulfates and C~2_~5 alkyl sulfates and also C~4_~5 alkyl sulfates are particularly preferred from the washing performance point of view. Other suitable anionic surfactants are 2,3-alkyl sulfates which may be produced, for example, in accordance with US
3,234,258 or US 5,075,041 and which are commercially obtainable as products of the Shell Oil Company under the name of DAN~. The sulphuric acid monoesters of linear or branched C~_2~ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9_~~ alcohols containing on average 3.5 moles of ethylene oxide (EO) or C~2_~g fatty alcohols containing 1 to 4 EO, are also suitable. In view of their high foaming power, they are normally used in laundry detergents in only relatively small quantities, for example in quantities of 1 to 5% by weight. Other preferred anionic surfactants are the salts of alkyl sulfosuccinic acid which are also known as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters andlor diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates contain C$_~8 fatty alcohol molecules or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol molecule derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants. Of these sulfosuccinates, those of which the fatty alcohol molecules are derived from narrow-range ethoxylated fatty alcohols are particularly preferred. Alk(en)yl succinic acid preferably containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may also be used. Other suitable anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) andlor of N-methyl glycine (sarcosides). The sarcosides or rather sarcosinates, above all sarcosinates of higher and optionally mono-or poly-unsaturated fatty acids, such as oleyl sarcosinate, are particularly preferred.
Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are, in particular, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and soap mixtures derived in particular from natural fatty acids, for example coconut, palm kernel or tallow acids. The known alkenyl succinic acid salts may be used together with or as a substitute for soaps.
The anionic surfactants, including the soaps, may 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 surfactants are preferably present in the form of their sodium or potassium salts and, more preferably, in the form of their sodium salts.
Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation andlor propoxylation products of alkyl glycosides or linear or branched alcohols containing 12 to 18 carbon atoms in the alkyl moiety and 3 to 20 and preferably 4 to 10 alkyl ether groups. Corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned in regard to the alkyl moiety, and of alkyl phenols containing 5 to 12 carbon atoms in the alkyl group are also suitable.
Preferred nonionic surfactants are alkoxylated, advantageously ethoxy-lated, more particularly primary alcohols preferably containing 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol group may be linear or, preferably, 2-methyl-branched or may contain linear and methyl-branched groups in the form of the 5 mixtures typically present in oxoalcohol groups. However, alcohol ethoxylates containing linear groups of alcohols of native origin with 12 to 18 carbon atoms, for example coconut alcohol, palm alcohol, tallow alcohol or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C~Z_~4 alcohols containing 3 EO or 10 EO, C9_» alcohols containing 7 EO, 03_15 alcohols containing 3 EO, 5 EO, 7 EO
or 8 EO, C~2_~8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C~2_~4 alcohol containing 3 EO and C~2_~8 alcohol containing 7 EO. The degrees of ethoxylation mentioned are statistical mean values which, for a special product, may be either a whole number or a broken number.
Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used. Examples of such fatty alcohols are (tallow) fatty alcohols containing 14 EO, 16E0, 20E0, 25 EO, 30 EO or 40 EO. In dishwasher detergents in particular, extremely low-foaming surfactants are normally used. These preferably include C~2_~8 alkyl polyethylene glycol polypropylene glycol ethers containing up to 8 moles ethylene oxide and up to moles propylene oxide units in the molecule. However, other known low-foaming nonionic surfactants, for example C~2_~g alkyl polyethylene glycol polybutylene glycol ethers containing up to 8 moles ethylene oxide and up to 8 moles butylene oxide units in the molecule and end-capped alkyl polyalkylene glycol mixed ethers, may also be used. The hydroxyfunctional alkoxylated alcohols described in European patent application EP 0 300 305, so-called hydroxy mixed ethers, are also particularly preferred. The nonionic surfactants also include alkyl glycosides with the general formula RO(G)x where R is a primary, linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G is a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of mono- and oligoglycosides, is a number (which, as an analytically determined quantity, may also be a broken number) of 1 to 10; preferably x = 1.2 to 1.4. Other suitable nonionic surfactants are polyhydroxyfatty acid amides corresponding to formula (I):

R~-CO-N-[Z] (I) in which R'CO is an aliphatic acyl group containing 6 to 22 carbon atoms, RZ
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. The polyhydroxyfatty acid amides are preferably derived from reducing sugars containing 5 or 6 carbon atoms, more particularly from glucose. The group of polyhydroxy-fatty acid amides also includes compounds corresponding to formula (II):
R4-O-Rs (II) R3-CO-N-[Z]
in which R3 is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R4 is a linear, branched or cyclic alkylene group or an arylene group containing 2 to 8 carbon atoms and R5 is a linear, branched or cyclic alkyl group or an aryl group or a hydroxyalkyl group containing 1 to 8 carbon atoms, C» alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl group, of which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of such a group.
Again, [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst, for example in accordance with the teaching of International patent application WO-A-95107331. Another class of preferred nonionic surfactants which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, particularly together with alkoxylated fatty alcohols andlor alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more particularly the fatty acid methyl esters which are described, for example, in Japanese patent application JP 581217598 or which are preferably produced by the process described in International patent application WO 90113533. Nonionic surfactants of the amine oxide type, for example N-coconutalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl amine oxide, and the fatty acid alkanolamide type are also suitable. The quantity in which these nonionic surfactants are used is preferably no more, in particular no more than half, the quantity of ethoxylated fatty alcohols used. Other suitable surfactants are so-called gemini surfactants. Gemini surfactants are generally understood to be compounds which contain two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called "spacer". The spacer is generally a carbon chain which should be long enough for the hydrophilic groups to have a sufficient spacing to be able to act independently of one another.
Gemini surfactants are generally distinguished by an unusually low critical micelle concentration and by an ability to reduce the surface tension of water to a considerable extent. In exceptional cases, however, gemini surfactants are not only understood to be "dimeric" surfactants, but also "trimeric" surfactants.
Suitable gemini surfactants are, for example, the sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 and the dimer alcohol bis-and trimer alcohol tris-sulfates and -ether sulfates according to earlier German patent application DE 195 03 061. The end-capped dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are distinguished in particular by their bifunctionality and multifunctionality. Thus, the end-capped surfactants mentioned exhibit good wetting properties and are low-foaming so that they are particularly suitable for use in machine washing or cleaning processes. However, the gemini polyhydroxyfatty amides or poly-polyhydroxyfatty acid amides described in International patent applications WO
95119953, WO 95119954 and WO 95119955 may also be used.
Surfactants are present in the laundry detergents according to the invention in quantities of preferably 5% by weight to 50% by weight and more preferably in quantities of 8% by weight to 30% by weight whereas detergents for cleaning hard surfaces, particularly dishwasher detergents, have lower surfactant contents of up to 10% by weight, preferably up to 5% by weight and more preferably in the range from 0.5% by weight to 3% by weight.
A detergent according to the invention preferably contains at least one water-soluble andlor water-insoluble, organic andlor inorganic builder.
Suitable water-soluble organic builders include polycarboxylic acids, more particularly citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, more particularly methyl glycine diacetic acid, nitrilotriacetic acid and ethylenediamine tetraacetic acid and polyaspartic acid, polyphosphonic acids, more especially aminotris(methylene phosphonic acid), ethylenediamine tetrakis(methylene phosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds, such as dextrin, and polymeric (poly)carboxylic acids, more particularly the polycarboxylates obtainable by oxidation of polysaccharides or dextrins according to European patent 0 625 992 or International patent application WO 92118542 or European patent EP 0 232 202, polymeric acrylic acids, methacrylic acids, malefic acids and copolymers thereof which may also contain small amounts of polymerizable substances with no carboxylic acid functionality in copolymerized form. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000 while the relative molecular weight of the copolymers is between 2,000 and 200,000 and preferably between 30,000 and 120,000, based on free acid. A particularly preferred acrylic acidlmaleic acid copolymer has a relative molecular weight of 30,000 to 100,000. Commercial products are, for example, Sokalan~ CP 5, CP 10 and PA 30 of BASF. Suitable, but less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight. Other suitable water-soluble organic builders are terpolymers which contain two unsaturated acids and/or salts thereof as monomers and vinyl alcohol andlor an esterified vinyl alcohol or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3_$ carboxylic acid and preferably from a C3~ monocarboxylic acid, more especially (meth)acrylic acid. The second acidic monomer or its salt may be a derivative of a C4_$
dicarboxylic acid, malefic acid being particularly preferred, andlor a derivative of an allylsulfonic acid substituted in the 2-position by an alkyl or aryl group.
Polymers such as these can be produced in particular by the processes described in German patents DE 42 21 381 and German patent application DE
43 00 772 and generally have a relative molecular weight of 1,000 to 200,000.
Other preferred copolymers are the copolymers which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acidlacrylic acid salts or vinyl acetate as monomers. The organic builders may advantageously be used in the form of aqueous solution, preferably in the form of 30 to 50% by weight aqueous solutions, particularly for the production of liquid detergents. All the acids mentioned are generally used in the form of their water-soluble salts, more especially their alkali metal salts.
If desired, organic builders of the type in question may be present in quantities of up to 40% by weight, preferably in quantities of up to 25% by weight and more preferably in quantities of 1 % by weight to 8% by weight. Quantities near the upper limit are preferably used in paste-form or liquid, more particularly water-containing detergents according to the invention.
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 their alkaline, neutral or acidic sodium or potassium salts.
Examples of such builders are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1,000 and more particularly 5 to 50 and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal alumosilicates in quantities of up to 50% by weight and preferably not more than 40% by weight and, in liquid detergents in particular, in quantities of 1 to 5% by weight are used as water-insoluble, water-dispersible inorganic builder materials. Of these inorganic builders, crystalline sodium alumosilicates in detergent quality, more particularly zeolite A, P and optionally X, individually or in the form of mixtures, for example in the form of a co-crystallizate of the zeolites A and X (Vegobond~ AX, a product of Condea Augusta S.P.A.), are preferred. Quantities near the upper limit mentioned are preferably used in solid particulate detergents. Suitable alumosilicates contain no particles larger than 30 Nm in size, at least 80% by weight preferably consisting of particles smaller than 10 Nm in size. Their calcium binding capacity, which may be 5 determined in accordance with German patent DE 24 12 837, is generally in the range from 100 to 200 mg Ca0 per gram.
Suitable substitutes or partial substitutes for the alumosilicate mentioned are crystalline alkali metal silicates which may be present either on their own or in the form of a mixture with amorphous silicates. The alkali metal silicates suitable 10 as builders in the detergents according to the invention preferably have a molar ratio of alkali metal oxide to Si02 of less than 0.95:1 and, more particularly, in the range from 1:1.1 to 1:12 and may be amorphous or crystalline. Preferred alkali metal silicates are sodium silicates, more especially amorphous sodium silicates, with a molar Na20 : Si02 ratio of 1:2 to 1:2.8. Those with a molar NaZO : Si02 15 ratio of 1:1.9 to 1:2.8 can be produced by the method according to European patent application EP 0 425 427. Crystalline layered silicates with the general formula Na2Six02X..~~ y H20, in which x - the so-called modulus - is a number of 1.9 to 22 and more particularly 1.9 to 4 and y is a number of 0 to 33, preferred values for x being 2, 3 or 4, are preferably used as crystalline silicates which may be present either on their own or in admixture with amorphous silicates.
Crystalline layered silicates which correspond to this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x in the general formula shown above assumes a value of 2 or 3. Both ~- and *-sodium disilicates (Na2Si205 yH20) are particularly preferred, ~-sodium disilicate being obtainable for example by the process described in International patent application WO 91108171.
*-Sodium silicates with a modulus of 1.9 to 3.2 may be produced in accordance with Japanese patent applications JP 04!238 809 or JP 04!260 610.
Substantially water-free crystalline alkali metal silicates corresponding to the above general formula, in which x is a number of 1.9 to 2.1, obtainable from amorphous alkali metal silicates as described in European patent applications EP
0 548 599, EP 0 502 325 and EP 0 425 428 may also be used in detergents according to the invention. Another preferred embodiment of the detergents according to the invention is characterized by the use of a crystalline sodium layered silicate with a modulus of 2 to 3 which may be produced from sand and soda by the process according to European patent application EP 0 436 835.
The crystalline sodium silicates with a modulus of 1.9 to 3.5 which may be obtained by the processes according to European patents EP 0 164 552 andlor EP 0 294 753 are used in a another preferred embodiment of the detergents according to the invention. Crystalline layer silicates corresponding to formula (I) are marketed, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, including for example Na-SKS-1 (Na2S122O45'xH2O, kenyaite) Na-SKS-2 (Na2Si~4029.xH20, magadiite), Na-SKS-3 (Na2Si80»~xH20), Na-SKS-4 (Na2Si409~xH20, makatite). Of these, Na-SKS-5 ('d-Na2Si205), Na-SKS-7 (~-Na2Si205 natrosilite), Na-SKS-9 (NaHSi205 ~ H20), Na-SKS-10 (NaHSi205 3H20, kanemite), Na-SKS-11 (~-Na2Si205) and Na-SKS-13 (NaHSi205), but especially Na-SKS-6 (*-Na2Si205), are particularly suitable. An overview of crystalline layer silicates can be found, for example, in the articles published in "Hoechst High Chem Magazin 1411993", pages 33-38 and in "Seifen-Ole-Fette-Wachse", Vol. 116, No. 2011990", pages 805-808. Another preferred embodiment of the detergents according to the invention is characterized by the use of the granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the above-mentioned (co)polymeric polycarboxylic acid, as described for example in German patent application DE 198 19 187, or of alkali metal silicate and alkali metal carbonate, as described, for example, in International patent application WO 95122592 or as commercially obtainable, for example, under the name of Nabion~ 15.
Builders may optionally be present in the detergents according to the invention in quantities of up to 90% by weight and are preferably present in quantities of up to 75% by weight. Laundry detergents according to the invention have builder contents of, in particular, 5% by weight to 50% by weight. In hard-surface cleaning compositions, more particularly dishwasher detergents, according to the invention, the builder content is in particular between 5% by weight and 88% by weight, such compositions preferably being free from water-insoluble builders. Another preferred embodiment of the dishwasher detergents according to the invention contains 20% by weight to 40% by weight of a water-soluble organic builder, more particularly alkali metal citrate, 5% by weight to 15% by weight of alkali metal carbonate and 20% by weight to 40% by weight of alkali metal disilicate.
Besides the alkali metal percarbonate already mentioned, peroxygen compounds suitable for use in detergents according to the invention include, in particular, organic per acids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under washing conditions, including perborates, percarbonates, persilicates andlor persulfates, such as caroate. If solid peroxygen compounds are to be used, they may be used in the form of powders or granules which may also be coated in known manner. If a detergent according to the invention contains peroxygen compounds, they are present in quantities of preferably up to 50% by weight and more preferably from 5% by weight to 30% by weight. The addition of small quantities of known bleach stabilizers, for example phosphonates, borates or metaborates and metasilicates, and magnesium salts, such as magnesium sulfate, can be useful.
Compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 4 carbon atoms andlor optionally substituted perbenzoic acid under perhydrolysis conditions may be used as bleach activators. Substances bearing O- andlor N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol-urils, more particularly tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, more particularly 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 the mixtures thereof (SORMAN) described in European patent application EP 0 525 239, acylated sugar derivatives, more particularly pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, andlor N-acylated lactams, for example N-benzoyl caprolactam, which are known from International patent applications WO 94127970, WO 94128102, WO 94128103, WO 95100626, WO 95114759 and WO 95117498. The substituted hydrophilic acyl acetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and in International patent application WO 95114075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 may also be used. Bleach activators such as these are present in the usual quantities, preferably in quantities of 0.5% by weight to 10%
by weight and more preferably in quantities of 1% by weight to 8% by weight, based on the detergent as a whole.
In addition to or instead of the conventional bleach activators mentioned above, the sulfonimines known from European patents EP 0 446 982 and EP 0 453 003 andlor bleach-boosting transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.
The organic solvents suitable for use besides water in the detergents according to the invention, particularly where they are present in liquid or paste-like form, include C~_4 alcohols, more especially methanol, ethanol, isopropanol and tert. butanol, C2~ diols, more especially ethylene glycol and propylene glycol, and mixtures thereof and ethers derived from the classes of compound mentioned. Water-miscible solvents such as these are present in the detergents according to the invention in quantities of preferably not more than 30% by weight and, more preferably, between 6% by weight and 20% by weight.
The detergents may additionally contain other typical detergent ingredients. These optional constituents include, in particular, enzyme stabilizers, redeposition inhibitors, dye transfer inhibitors, foam inhibitors and optical brighteners and also dyes and perfumes. To protect silverware against corrosion, dishwasher detergents according to the invention may contain silver corrosion inhibitors. In addition, a hard-surface detergent according to the invention may contain abrasive ingredients, more especially from the group consisting of silica flours, wood flours, polymer powders, chalks and glass microbeads and mixtures thereof. Abrasives are present in the dishwasher detergents according to the invention in quantities of preferably not more than 20% by weight and, more particularly, in quantities of 5% by weight to 15% by weight.
To establish a desired pH value which is not spontaneously adjusted by the mixture of the other components, the detergents according to the invention may contain system-compatible and environmentally compatible acids, more particularly citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid andlor adipic acid and also mineral acids, more especially sulfuric acid, or bases, more especially ammonium or alkali metal hydroxides. pH regulators such as these are present in the detergents according to the invention in quantities of preferably not more than 20% by weight and, more preferably, between 1.2% by weight and 17% by weight.
Dye transfer inhibitors suitable for use in laundry detergents according to the invention include, in particular, polyvinyl pyrrolidones, polyvinyl imidazoles, polymeric N-oxides, such as poly-(vinylpyridine-N-oxide), and copolymers of vinyl pyrrolidone with vinyl imidazole.
Additional redeposition inhibitors may be present in the detergents according to the invention. Suitable additional redeposition inhibitors are water-soluble, generally organic colloids, for example starch, glue, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Other starch derivatives than those mentioned above, for example aldehyde starches, may also be used. Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, are also preferably used, for example in quantities of 0.1 to 5% by weight, based on the detergent.
Laundry detergents according to the invention may contain derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof as optical brighteners.
Suitable optical brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar structure which contain a diethanolamino group, a methylamino group and 5 anilino group or a 2- methoxyethylamino group instead of the morpholino group.
Brighteners of the substituted diphenyl styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)-diphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl, may also be present. Mixtures of the brighteners mentioned may also be used.
10 Particularly where the detergents are used in washing machines, it can be of advantage to add typical foam inhibitors to them. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high percentage content of C~8_24 fatty acids. Suitable non-surface-active foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally 15 silanized, silica and also paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bisfatty acid alkylenediamides. Mixtures of different foam inhibitors, for example mixtures of silicones, paraffins and waxes, may also be used with advantage. The foam inhibitors, more particularly silicone-and/or paraffin-containing foam inhibitors, are preferably fixed to a granular 20 water-soluble or water-dispersible support. Mixtures of paraffins and bis-stearyl ethylenediamide are particularly preferred.
The production of solid detergents according to the invention does not involve any difficulties and may be carried out in known manner, for example by spray drying or granulation, the enzymes and any other heat-sensitive ingredients, for example bleaching agents, optionally being separately added at a later stage. Detergents according to the invention having a high bulk density, more particularly in the range from 650 to 950 gll, are preferably produced by the process comprising an extrusion step which is known from European patent EP 0 486 592. Another preferred production process is the granulation process according to European patent EP 0 642 576.
To produce detergents according to the invention in the form of tablets which comprise one or more phases and are colored in one or more colors and, in particular, may consist of one layer or several layers, more particularly two layers, all the ingredients - optionally for each layer - may tablet presses, for example eccentric presses or rotary presses, be mixed together in a mixer and the resulting mixture tabletted in conventional under pressures of about 50 to kN and preferably under pressures of 60 to70 kN. In the case of multilayer tablets in particular, it can be of advantage if at least one layer is compressed in advance, preferably under pressures of 5 to 20 kN and more particularly 10 to kN. Fracture-resistant tablets which still dissolve sufficiently quickly under in-use conditions are readily obtained in this way; they have fracture and flexural strengths of normally 100 to 200 N and preferably above 150 N. A tablet produced in this way preferably has a weight of 10 g to 50 g and, more particularly, 15 g to 40 g. The tablets may be of any shape, including round, oval or angular and variations thereof. Corners and edges are advantageously rounded off. Round tablets preferably have a diameter of 30 mm to 40 mm. The size of rectangular or square tablets in particular, which are mainly introduced from dispensing compartments, for example of dishwashers, is dependent on the geometry and the size of the dispensing compartment. For example, preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm) and, more particularly, 26 x 36 mm or 24 x 38 mm.
Liquid or paste-form detergents according to the invention in the form of solutions containing typical solvents are generally prepared simply by mixing the ingredients which may be introduced into an automatic mixer either as such or in the form of a solution.
Examples Example 1 The cellulases specified in Table 1 were added to an enzyme-free basic detergent BW1. The cellulases were used in a quantity - based on protein -which corresponded to 0.6% by weight of Celluzyme~ 0,7T (manufacturer: Novo Nordisk) in the particular detergent used. Fabric discoloration was determined by measuring reflectance after 10 washes, washing tests being carried out under the following conditions:
washing machine: Miele~ W918 temperature: 40°C

detergent dose: 76 g water hardness: 16°dH
load: 2.5 kg clean laundry (cotton test fabric of Wascheforschungsanstalt Krefeld, pillow slips, terry hand towels, vests and kitchen towels) soil: 5 skeins of cotton with standardized dustlsebum soil were added to each wash.
The discoloration figures (% reflectance averaged over all the textiles) obtained after washing with the formulations shown are set out in Table 1 below, the initial reflectance value before washing and the value for the enzyme-free basic detergent also being shown for comparison.
Table 1 Detergent Discoloration Initial value 87.3 BW1 54.5 BW1 + DACa~ 69.2 BW1 + Carezyme~ (Novo Nordisk)59.5 BW1 + 20K celulase 73.0 a~ cellulase according to WO 96134108 It can be seen that the cellulase to be used in accordance with the invention leads to better inhibition of redeposition than other cellulases.
Example 2 The procedure was as described in Example 1 except that 11 washes were carried out and a basic detergent BW2 containing - in contrast to BW1 -1.2% by weight of enzyme granules containing the protease BLAP with an activity of 200,000 PUIg was used.

Table 2 Detergent Discoloration Initial value 87.0 BW2 54.2 BW2 + DACa~ 73.1 BW2 + 20 K cellulase 75.4 a~ cellulase according to WO 96134108 It can be seen that a detergent according to the invention has a better redeposition-inhibiting effect than a detergent containing a cellulase other than the cellulase to be used in accordance with the invention.

Claims (18)

1. The use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto as a redeposition inhibitor in detergents.

2. The use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto as a redeposition inhibitor in detergents containing fine-particle water-insoluble inorganic builders, particularly zeolite.

3. The use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto for reducing redeposition in the washing of laundry with laundry detergents based on fine-particle water-insoluble inorganic builder components.

4. The use as claimed in any of claims 1 to 3, wherein the detergent comprises as builder 10% by weight to 50% by weight of water-insoluble, water-dispersible detergent-quality inorganic builder material.

5. The use as claimed in claim 4, wherein the builder comprises 10 to 40%
by weight of water-insoluble, water-dispersible detergent-quality inorganic builder material.

6. The use as claimed in any of claims 1 to 5, wherein the inorganic builder material is selected from crystalline alkali metal silicate, crystalline and/or amorphous alkali metal alumosilicate.

7. The use as claimed in claim 6, wherein the builder material is zeolite A, zeolite P and/or zeolite X.

8. A detergent composition comprising 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto in combination with an optionally genetically modified protease from Bacillus lentus and/or alkali metal percarbonate.

9. A detergent composition as claimed in claim 8, wherein a cellulolytic activity attributable to the 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or to a cellulase more than 80% homologous thereto of 1 NCU/g to 500 NCU/g is present.

10. A detergent composition as claimed in claim 8, wherein the cellulase more than 80% homologous thereto is 5 NCU/g to 400 NCU/g.

11. A detergent composition as claimed in any of claims 8 to 10, wherein at least one of the amino acid exchanges S3T, V41, V193M, V1991 or L211D has been made in the genetically modified protease from Bacillus lentus.

12. A detergent composition as claimed in any of claims 8 to 11, wherein the ratio of cellulolytic activity expressed in NCO/g to proteolytic activity expressed in PU/g is 1:10,000 to 5:1.

13. A detergent composition as claimed in claim 12, wherein the proteolytic activity expressed in PU/g is 1:1,600 to 4:3.

14. A detergent composition as claimed in any of claims 8 to 13, wherein 50%
by weight of alkali metal percarbonate is present.

15. A detergent composition as claimed in claim 14, wherein 5 to 30% by weight of alkali metal percarbonate is present.

16. A detergent composition as claimed in claim 14 or 15, wherein sodium percarbonate is present.

17. A detergent composition as claimed in any of claims 8 to 16, wherein there is present 0.0001 mg to 0.1 mg of cellulolytic protein per % by weight of alkali metal percarbonate.

18. A detergent composition as claimed in claim 17, wherein 0.001 mg to 0.01 mg is present.