ES2218229T3 - ENZYMATIC INHIBITOR OF THE AGRISADO. - Google Patents

Abstract

Use of 20K-cellulase, obtainable from Melanocarpus sp. or from Myriococcum sp. or of the one that presents a homology greater than 80% with it, as an inhibitor of grating in washing agents.

Description

Enzymatic inhibitor of grating.

The invention relates to an enzyme inhibitor. of the gray for use in washing agents containing surfactants as well as washing and / or cleaning agents, which contain the enzymatic inhibitor of the determined grating, in combination with other specially chosen components.

In washing and cleaning agents it is used currently finely divided zeolite, especially zeolite NaA for bonding hardness trainers, first of all calcium and / or magnesium ions, in the waters for washing and in the dirt Of course they are used in considerable quantities, especially in the field of agents for washing textiles, the so-called adjuvants or adjuvant systems, especially to combat unwanted scale.

These inlays are constituted by deposits on the internal walls of the washing machines and, especially on laundry, such as for example soaps calcium or organic waste. Such inlays can influence negatively on touch, on external characteristics, on the smell and on the absorbent capacity of the laundry. The inlays are especially apparent after several washes

Similarly, the gray of the laundry is presents, as a rule, only after frequent washing and, specifically, especially when only the carrying capacity of the dirt in the washing baths, due to a too small dosage of the washing agent and redeposited on the laundry the dirt of the bathroom, which has come off the wash.

To prevent fouling and grinding of the laundry or to keep them in the smallest possible proportion, is the so-called adjuvants are added to the washing agents or adjuvants Concomitant, additional employment of complex formers, to which the salts of the aminocarboxylic acids such as nitrilotriacetic acid and phosphonic acid derivatives. The adjuvant combinations of this type cause the precipitation of calcium salts hardly soluble during the use of the agents washing and cleaning and, thus, oppose the inlays on the textile or on other surfaces, caused by it reason. In addition the washing agents may contain especially also additional agrisado inhibitors, which oppose specifically to the redeposition on the washed textiles of the dirt particles suspended in the bleach of the laundry.

In the published German patent application, no examined DE 33 29 400 is proposed as a protective additive against the grating in laundry agents containing zeolite, use a mixture consisting of methylcellulose, carboxymethyl cellulose and copolymers of (meth) acrylic acid and of maleic acid in mixed proportions of 1: 1.5 to 4: 3 up to 10, the cellulose ether must have certain degrees of substitution.

European patent application EP 054 325 describes the use of ternary mixtures constituted by sodium carboxymethyl cellulose, a linear polycarboxylate and alkylcelluloses with 1 to 3 carbon atoms with degrees of replacement of at least 0.5 and degrees of polymerization of up to 300 in the washing agents to inhibit grating.

In the descriptive reports of the applications German patent documents, not examined DE-A- 43 25 882 and DE-A- 195 20 101 the use of cellulases as inhibitors of grating in washing agents or cleaning.

Even when the measures described in the cited publications present results completely satisfactory in most cases, there is, however, the need to develop graying inhibitor systems more effective.

Surprisingly, it has been found that employment of a very determined cellulase causes a reduction especially good of dirt particle redepositions on laundry washed (redeposition) and gray.

The object of the present invention is the use of 20K-cellulase, obtainable from Melanocarpus sp . or of Myriococcum sp ., as an inhibitor of grating in washing and cleaning agents. Another object of the invention is the corresponding use in washing or cleaning agents, which contain inorganic, water insoluble, finely divided adjuvants, especially zeolite.

Another object of the invention are washing or cleaning agents, containing 20K-cellulase, obtainable from Melanocarpus sp . or Myriococcum , in combination with a protease, if modified by genetic engineering, of Bacillus lentus and / or alkaline percarbonates. When such combinations are used, an even more potent grating inhibitor effect of cellulase to be used according to the invention is achieved.

20K-cellulase, obtainable from Melanocarpus sp . or from Myriococcum sp . It is known by the international patent application WO 97/14804. This has, as described therein, a molecular weight of approximately 20kDa and has at 50 ° C, in the pH range from 4 to 9, at least 80% of its maximum activity, while still maintaining almost 50% of the maximum activity at pH 10. This can be isolated, as described there, from Melanocarpus albomyces and can be produced in Trichoderma reseei transformants, prepared by genetic engineering. Within the meaning of the present invention, cellulases which have a homology greater than 80% with respect to 20K-cellulase are also employable.

As another special advantage of cellulase to be used according to the invention should be considered as presented, with its use a loss even remotely so pronounced of the force of wet tearing of washed textiles as in the case of use of other cellulases, even if you do not detract from your Renewing effect of colors and fabric softener of others cellulases

The 20K-cellulase will preferably be used in amounts such that a finished agent has a cellulolytic activity of 1 NCU / g up to 500 NCU / g (determinable by hydrolysis of carboxymethylcellulose at 1 percent by weight at 50 ° C and neutral pH and determination of the reducing sugars released by dinitrosalicylic acid, as described by MJ Bailey et al . in Enzyme Microb. Technol. 3: 153 (1981); 1 NCU defines the enzymatic amount that generates reducing sugars in such an amount, corresponding to 1 Nmol of glucose per second, especially from 2 NCU / g to 400 NCU / g, especially preferably, from 6 NCU / g to 200 NCU / g In addition, the agent may also contain other cellulases, if appropriate.

An agent according to the invention preferably contains from 0.001 mg to 0.5 mg, especially from 0.02 mg to 0.3 mg of cellulolytic protein per gram of the agent as a whole. The protein concentration can be determined with the aid of known methods, for example according to the bicinconic acid procedure (BCA procedure, Pierce Chemical Co., Rockford, IL) or the biuret procedure (AG Gornall, CC Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).

The protease from Bacillus lentus is stable and active under strongly alkaline conditions; as described in international patent application WO 91/02792 can be produced in Bacillus lentus (DSM 5483). This Bacillus lentus alkaline protease (BLAP) can be obtained by fermentation of Bacillus licheniformis , which is 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 the known BLAP spatial structure (DW Godette et al ., J. Mol. Biol. 228 , 580-595, 1992). This protease is characterized by means of the sequence, described in the cited literature, consisting of 269 amino acids, a numerical molecular weight of 26,823 Daltons and a theoretical isoelectric point of 9.7. Variants of this Bacillus lentus DSM 5483 protease, accessible by mutation, have been described in the specification of US Pat. Among these are protease enzymes that lead especially in the case of repeated treatment of textile laundry, consisting of proteinogenic fibers, for example textile surface structures formed by natural silk or wool, without loss of cleaning power, to deterioration of the substance or destruction of the specially reduced fiber assemblies.

In addition to the naturally occurring proteases of Bacillus lentus , to the employable proteases according to the invention, also genetically modified proteases of the aforementioned BLAP type belong. In which it has been exchanged at position 211 (BLAP numbering), the amino acid leucine (L according to the usual letter code), present in this position in the native type of protease, by asparagineic acid (D) or by acid glutamic (E) (L211D or L211E). These can be prepared as described in international patent application WO 95/23221. Instead or additionally, other modifications may have been made with respect to the original Bacillus lentus protease, such as for example at least one of the exchanges of amino acids S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I. The use of a variant in which at least one of the exchanges of amino acids S3T, V4I, V193M, V199I or L211D has been especially preferred. In the nomenclature of the proteases described above on the exchange of individual amino acids, it should be taken into account that the numbering of amino acid positions in BLAP differs from the numbering frequently found in BPN 'subtilisin. The numbering of positions 1 to 35 is identical in subtilisin BPN 'and BLAP; Due to the absence of the 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' and positions 161 to 269 correspond to positions 167 to 275 in BPN '.

An agent according to the invention preferably has a proteolytic activity in the range from about 100 PE / g to about 10,000 PE / g, especially from 300 PE / g to 8,000 PE / g. Protease activity is determined according to the standardized procedure, described below, as indicated in Tenside 7 (1970). 125: a solution containing 12 g / l of casein and 30 mM of sodium tripolyphosphate in water with a hardness degree of 15 ° dH (containing 0.058% by weight of CaCl 2 2 H) is heated to 70 ° C 2 O, 0.028% by weight MgCl 2 6 H 2 O and 0.042% by weight NaHCO 3), the pH value is adjusted to 8.5, at 50 ° C, by the addition of NaOH 0.1 N. 200 ml of a solution of the agent to be tested is added to 600 ml of the substrate solution for a 2% by weight buffer solution of sodium tripolyphosphate (pH 8.5). The reaction mixture is incubated at 50 ° C for 15 minutes. The reaction is then stopped by the addition of 500 ml of TCA solution (0.44 M trichloroacetic acid and 0.22 M sodium acetate in 3 percent by volume acetic acid) and cooling (ice bath at 0 ° C, 15 minutes). The undissolved TCA protein is separated by centrifugation, 900 ml of the supernatant is diluted with 300 ml of 2N NaOH. The absorption of this solution at 290 nm is determined by means of an absorption spectrometer, the null value of absorption having to be determined by measuring a centrifuged solution, which is prepared by mixing 600 ml of the TCA solution indicated above with 600 ml of the above-mentioned substrate solution and subsequent addition of the enzymatic solution. The proteolytic activity of a solution, which causes, under the conditions indicated above, an absorption of 0.500 OD (optical density units), is defined as 10 PE (protease units) per ml. Preferably, in the agent according to the invention, the ratio between cellulolytic activity, expressed in NCU / g, and proteolytic activity, expressed in PE / g, is between 1: 10,000 to 5: 1, especially 1: 1,600 up to 4: 3.

Enzymes may be absorbed and / or may be embedded in coating substances especially for the use in particle agents, as described, by example, in the specification of European patent EP 0 564 476 or in international patent application WO 94/23005 for other enzymes, for protection against premature inactivation. The combination according to the invention constituted by certain cellulase and, if appropriate, by engineering modified proteases genetics, can be used by incorporating the two separate enzymes or the two made enzymes separately, in a known manner, or by cellulases and proteases made together in a granulate, as it is known, for example, by WO international patent applications 96/00772 or WO 96/00773.

An agent according to the invention contains, preferably, up to 50% by weight, especially from 5% in weight up to 30% by weight of alkaline percarbonates, being Especially preferred is sodium percarbonate. This one can be prepared according to known procedures and, especially, in case desired can be made in granular form or it can be stabilize and / or coat for use in agents in the form of particles, as is known, for example, by requests for International Patent WO 91/15423, WO 92/17400, WO 92/17404, WO 93/04159, WO 93/04982, WO 93/20007, WO 94/03553, WO 94/05594, WO 94/14701, WO 94/14702, WO 94/24044, WO 95/02555, WO 95/02672, WO 95/06615, WO 95/15291 or WO 95/15292 or by patent applications European 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 stability reasons it will be used in form of a granulate, which has been manufactured with the help of sulfates alkaline earth metals, alkali sulfates, alkali silacates, alkaline earth halides, alkali halides, carbonates alkalines, alkali bicarbonates, alkaline phosphates, borates alkaline, alkali perborates, boric acid, aluminosilicates partially hydrated, carboxylic acids, dicarboxylic acids, polymers formed by carboxylic acids and / or dicarboxylic acids unsaturated, or by mixtures thereof, or has been coated. In a preferred embodiment has a morphology index ((MI), as defined in EP 0 451 893, below 0.06.

The proportion between cellulase to be used according to the invention and alkaline percarbonate is in a preferred configuration, in the range from 0.0001 mg to 0.1 mg, especially from 0.001 mg to 0.01 mg of cellulolytic proteins per% by weight of alkali percarbonate in the washing or cleaning agent
za.

Washing or cleaning agents can be, preferably, industrial washing agents or agents for fine wash as well as, if necessary, an agent for rinsing softener that can be used if necessary in a rinsing process afterwards of the laundry. In a preferred embodiment of the present invention, the use of special cellulase refers to the reduction of redeposition in the case of textile laundry with textile laundry agents based on adjuvant components finely divided, inorganic, water insoluble, especially NaA zeolite.

Cellulase, as well as the enzymes used additionally, where appropriate, to which they belong in addition to the cited proteases, especially amylases, lipases, oxidases, peroxidases, cutinases, pululanases, xylanases and / or hemicellulases as well as, where appropriate, other cellulases and / or proteases, and which are present in the agent preferably in amounts from 0.1% in weight up to 2% by weight, can be used in the form of formulations liquids, if necessary with the addition of stabilizers, in agents of washing in the form of particles, however preferably in the form absorbed in support products, embedded in substances of coating or in the form of usual granules with materials inorganic and / or organic support, as described for example in the specification of the German patent DE 16 17 232, in the German patent applications published, not examined DT 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. In this case the enzymes they can be contained in separate particles or they can be used in the form of a poly-enzymatic granulate, such as the one described for example in German patent applications DE 44 22 433 or DE 44 22 609 or in WO international patent applications 90/09440 or WO 90/09428 as well as in the state of the art there aforementioned.

Washing and cleaning agents, according to the invention, which may be presented, especially, in the form of powdery solid products, in the form of compacted particles subsequently, by way of homogeneous solutions or suspensions, they may contain, in addition to the combination used according to the invention, in principle all known and usual components in such agents. The agents according to the invention may contain, especially adjuvant substances, or surfactants with surface activity, bleach activators, solvents water-miscible organic, additional enzymes, agents sequestrants, electrolytes, pH regulators as well as others bleaching agents based on organic peroxo compounds and / or inorganic and other auxiliary products, such as brighteners optics, grating inhibitors, run inhibitors colors, foam regulators, corrosion inhibitors silver as well as dyes and perfumes.

The agents according to the invention may contain a surfactants or various surfactants, coming into consideration, especially anionic surfactants, nonionic surfactants and their mixtures, as well as cationic surfactants, Zwitterionic and amphoteric.

Appropriate anionic surfactants They are especially soaps, and those containing sulfate groups or sulphonate They come into consideration as surfactants of sulfonate type preferably alkyl benzenesulfonate with 9 to 13 carbon atoms, olefin sulfonates, i.e. mixtures constituted by alkenesulfonates and hydroxyalkanesulfonates, as well as disulfonates, as obtained, by way of example, from monoolefins with 12 to 18 carbon atoms with double bond in terminal or internal position, by sulfonation with trioxide gaseous sulfur and its following alkaline or acid hydrolysis of sulfonation products. Sulfonates of alkane, which are obtained from alkanes with 12 to 18 atoms of carbon, by way of example by sulfocloration or sulfooxidation with its next hydrolysis, or neutralized. They are also appropriate acid esters α-sulfograms (ester sulphonates), by example the α-sulphonated methyl esters of hydrogenated coconut fatty acids, palm kernel or tallow, which are obtained by α-sulfonation of the ester of methyl fatty acids of vegetable and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule, and its following neutralized to give water soluble mono-salts. In this case it preferably deals with esters α-sulphonates of hydrogenated fatty acids of coconut, palm, palm seeds or tallow, may be present also sulfonation products of unsaturated fatty acids, to by way of example oleic acid, in small quantities, preferably in amounts not exceeding about 2 Up to 3% by weight. Esters are especially preferred α-sulfograse acid alkyl, which they have an alkyl chain with no more than 4 carbon atoms in the ester group, by way of example methyl ester, ethyl ester, propyl ester and butyl ester. Especially advantageous methyl esters of acids are used α-sulfograms (MES) but also their disals saponified Other suitable anionic surfactants are glyceride esters of sulfated fatty acids, which represent mono-di- and tri-esters, as well as mixtures thereof, as obtained in the obtained by esterification through a monoglycerin with 1 to 3 moles of fatty acid, or in the transesterified triglycerides with 0.3 to 2 moles of glycerin. How alkylsulfates are preferred salts alkaline, and especially sodium, alcohol semisulfate fatty acids with 12 to 18 carbon atoms, by way of example from coconut fatty alcohol, tallow fatty alcohol, lauric alcohol, myristic, cetyl or stearic, or oxoalcohols with 10 to 20 carbon atoms and those semi-esters of secondary alcohols of This chain length. They are also preferred alkylsulfates of said chain length, containing a synthetic straight chain alkyl moiety, obtained on a petrochemical basis, which have a degradation behavior analogous that suitable compounds based on raw materials fat chemicals They are especially preferred for technical interest of washed the alkyl sulfates with 12 to 16 carbon atoms, and the alkyl sulfates with 12 to 15 carbon atoms, as well as alkyl sulfates with 14 to 15 carbon atoms. They are also appropriate anionic surfactants sulfates of 2,3-alkyl, which can be obtained according to US patent applications US 3 234 258 or US 5 075 041, and that can be purchased as commercial products from Shell Oil Company under the name DAN®. Also suitable are the monosulfates of alcohols with 7 to 21 straight chain carbon atoms or branched, ethoxylated with 1 to 6 moles of ethylene oxide, such as alcohols with 9 to 11 carbon atoms, branched with 2-methyl with an average of 3.5 moles of oxide ethylene (EO) or fatty alcohols with 12 to 18 carbon atoms with 1 to 4 EO. They will be used in washing agents, due to their high foam behavior, usually only in quantities relatively small, for example, 1 to 5% by weight. To the Preferred anionic surfactants also belong to salts of alkylsulfosuccinic acid, which are also called sulfosuccinates or esters of sulfosuccinic acid and monoesters and / or diesters of sulfosuccinic acids with alcohols, preferably fatty alcohols, and especially fatty alcohols ethoxylated. Preferred sulfosuccinates contain alcohol residues fatty with 8 to 18 carbon atoms, or mixtures thereof. The Especially preferred sulfosuccinates contain an alcohol moiety fatty, which is derived from ethoxylated fatty alcohols, which represent nonionic surfactants considered by themselves. In this case sulfosuccinates are especially preferred whose traces of fatty alcohol are derived from fatty alcohols ethoxylates with limited homolog distribution. In the same way, it is also possible to use alky (en) ilsuccinic acid preferably with 8 to 18 carbon atoms in the chain of alkyl (en) ilo, or its salts. They come into consideration as additional anionic surfactants acid derivatives amino acid fatty acids, by way of example of N-methyltaurine (taurides) and / or N-methylglycine (sarcosides). In this case they are especially preferred are sarcosides, or sarcosinates, and here especially sarcosinates of higher fatty acids, and in case given mono- or polyunsaturated, such as oleylsarcosinate. Enter in consideration as other anionic surfactants especially soaps Especially suitable are fatty acid soaps saturated, such as salts of lauric acid, myristic acid, acid palmitic acid, stearic acid, hydrogenated erucic acid and acid behenic, as well as, in particular, mixtures of soaps derived from natural fatty acids, for example coconut fatty acids, seeds of palm or tallow. Together with these soaps, or as a substitute for soaps, the known acid salts can also be used alkenyl succinic.

Anionic surfactants, including Soaps can be presented in the form of their sodium salts, from potassium or ammonium, as well as in the form of soluble base salts organic, such as mono-, di- or triethanolamine. Surfactants anionics are preferably presented in the form of their salts of sodium or potassium, especially in the form of sodium salts.

Suitable nonionic surfactants are, especially alkyl glycosides and ethoxylation products and / or propoxylation of alkyl glycosides or linear alcohols or branched, respectively with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10 alkyl ether groups. The corresponding ethoxylation and / or products are also useful N-alkyl amines propoxylation, neighborhood diols, fatty acid esters and acid amides fatty, which correspond to the aforementioned alcohol derivatives of long chain with respect to the alkyl part, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl moiety.

They are preferably used as agents non-ionic alkoxylated alcohols surfactants, advantageously ethoxylates, especially primary, preferably with 8 to 18 atoms of carbon, and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcoholic residue can be linear, or preferably branched with methyl in position 2, or it can contain linear and branched residues with methyl in mixture as well as They usually occur in oxoalcohol residues. However, in Especially preferred are alcoholic ethoxylates with linear residues from alcohols of native origin with 12 to 18 atoms of carbon, for example from coconut alcohol, palm, tallow, or of oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol To the preferred ethoxylated alcohols belong, to by way of example, alcohols with 12 to 14 carbon atoms with 3 EO or 4 EO, alcohols with 9 to 11 carbon atoms with 7 EO, alcohols with 13 to 15 carbon atoms with 3 EO, 5 EO, 7 EO or 8 EO, alcohols with 12 to 18 carbon atoms with 3 EO, 5 EO or 7 EO, and mixtures constituted by them, as mixtures of alcohol with 12 to 14 carbon atoms with 3 EO and alcohol with 12 to 18 carbon atoms with 7 EO. The degrees of ethoxylation indicated represent values statistical means, which can be an integer or fractional number For a special product. Preferred alcohol ethoxylates, have a limited homolog distribution (narrow range ethoxylates, NRE). In addition to these non-surfactants ionic, fatty alcohols with more than 12 can also be used EO Examples of this are fatty alcohols (tallow) with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Especially in agents of cleaning for use in dishwashing procedure a machine, extremely poor compounds are usually used in foam Among these, preferably polyethylene glycol polypropylene glycol ethers of alkyl with 12 to 18 carbon atoms respectively with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But other surfactants can also be used known non-ionic foam poor, such as polyethylene glycol, alkyl polybutylene glycol ether with 12 to 18 carbon atoms, respectively with up to 8 moles of units ethylene oxide and butylene oxide in the molecule, as well as ethers mixed alkylpolyalkylene glycol blocked in their groups terminals Also especially preferred are alcohols. alkoxylates containing hydroxyl groups, as described in the European patent application EP 0 300 305, the so-called ethers mixed hydroxyl. Among the nonionic surfactants they also have alkyl glycosides of the general formula RO (G) x, in which R means an aliphatic moiety linear or branched chain primary with methyl, especially branched with methyl in position 2, with 8 to 22, preferably 12 at 18 carbon atoms, and G represents a glycosal unit with 5 to 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which can also adopt fractional values as magnitude to be determined analytically - between 1 and 10; x is preferably 1.2 to 1.4. Of the same mode polyhydroxy fatty acid amides of the formula are suitable (I), in which R 1 CO represents an aliphatic acyl moiety with 6 to 22 carbon atoms, R2 represents hydrogen, an alkyl moiety or hydroxylalkyl with 1 to 4 carbon atoms, and [Z] represents a linear or branched polyhydroxyalkyl moiety with 3 to 10 atoms of carbon, and 3 to 10 hydroxyl groups:

\uelm{N}{\uelm{\para}{R ^{2} }}

---[Z](I) R1 --- CO ---

 \ uelm {N} {\ uelm {\ para} {R2}} 

--- [Z]

Polyhydroxy fatty acid amides are derived preferably of reducing sugars with 5 or 6 carbon atoms, especially glucose. To the group of polyhydroxy acid amides fatty compounds also belong to the formula (II),

\uelm{N}{\uelm{\para}{R ^{4}  --- O --- R ^{5} }}

--- [Z](II) R3 --- CO ---

 \ uelm {N} {\ uelm {\ para} {R 4} --- O --- R 5}} 

--- [Z]

wherein R 3 represents an alkyl moiety or linear or branched alkenyl with 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkylene moiety, or a arylene radical with 2 to 8 carbon atoms, and R 5 represents a linear, branched or cyclic alkyl moiety, or an aryl moiety or a oxy-alkyl moiety with 1 to 8 carbon atoms, with alkyl radicals having 1 to 4 carbon atoms being preferred or phenyl, and [Z] represents a linear polyhydroxyalkyl moiety, whose alkyl chain is substituted with at least two groups hydroxyl, or alkoxylated derivatives, preferably ethoxylated or propoxylated, of this rest. In this case, [Z] is also obtained preferably by amined by reduction of a sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy compounds N-aryloxy-substituted can be transform then, as an example according to the teaching of International Patent Application WO 95/07331, in the amides of desired polyhydroxy fatty acid by reaction with esters fatty acid methyl in the presence of an alkoxy or as catalyst. Other class of non-ionic surfactants preferably used, which are applied as a surfactant non-ionic isolated or in combination with other surfactants non-ionic, especially together with alkoxylated and / or fatty alcohols alkyl glycosides, are alkyl esters of fatty acids alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated, preferably with 1 to 4 carbon atoms in the alkyl chain, especially methyl ester of fatty acids, as described, by way of example, in the patent application Japanese JP 58/217598, or which are preferably obtained according to procedure described in the international patent application WO 90/13533. Non-surface active agents may also be appropriate. ions of the type of amine oxides, by way of example oxide of N-coco-alkyl-N, N-dimethylamine and oxide of N-tallow-alkyl-N, N-dihydroxyethylamine, and fatty acid alkanolamides. The amount of these agents nonionic surfactants is preferably not greater than that of ethoxylated fatty alcohols, especially does not amount to more than Half of it. They come into consideration as agents additional surfactants called surfactants geminals In general it is understood by these those compounds that They have two hydrophilic groups per molecule. Generally these Groups are separated from each other by a so-called "spacer." As a rule, this spacer is a carbon chain, which must be long enough for hydrophilic groups to have a sufficient distance for them to react independently of each other. Such surfactants are generally distinguished by a critical micellar concentration unusually reduced, and by the ability to greatly reduce The surface tension of the water. In exceptional cases, under the expression geminal surfactants are understood not only such "dimer" surfactants, but also correspondingly "trimer" surfactants. The Suitable Geminal surfactants are, by way of example, sulfated hydroxy mixed ethers according to the patent application German DE 43 21 022, or bis bisulfates of alcohols dimers and tris sulfates of alcohol ether sulfates trimers according to German patent application DE 195 03 061. The mixed dimer and trimer ethers blocked in their terminal groups according to German patent application DE 195 13 391 are distinguished in special for its bi- and multifunctionality. Thus, those cited surfactants blocked in their terminal groups possess good moisturizing properties, and in this case they are poor in foam, so that they are especially suitable for employment in washing or machine cleaning procedures. However, also geminal polyhydroxy fatty acid amides can be used or polyamides of polyhydroxy fatty acid, as described in the international patent applications WO 95/19953, WO 95/19954 and WO 95/19955.

Surfactants are contained in the washing agents according to the invention in quantitative fractions preferably from 5% by weight to 50% by weight, especially from a  8% by weight to 30% by weight, while the agents for hard surface cleaning, especially for cleaning tableware machine, present contents in surfactants more reduced of up to 10% by weight, especially up to 5% in weight, and preferably in the range of 0.5% by weight to 3% weight.

An agent according to the invention contains preferably at least one water soluble and / or insoluble adjuvant in water, organic and / or inorganic. To adjuvant substances Water soluble organic belong polycarboxylic acids, in special citric acid, and saccharic acid, acids aminopolycarboxylic monomers and polymers, especially acid methylglycylacetic acid, nitrilotriacetic acid and acid ethylenediaminetetraacetic acid, as well as polyaspartic acid, acids polyphosphonics, especially aminotris (methylene phosphonic acid), ethylenediamine tetrake (methylene phosphonic acid) and acid 1-hydroxyethane-1,1-diphosphonic, polymeric hydroxy compounds, such as dextrin, as well as acids (poly) carboxylic polymers, especially those polycarboxylates of European patent application EP 0 625 992, or either of the international patent application WO 92/18542 or of the European patent application EP 0 232 202, accessible by oxidation of polysaccharides, or dextrins, acrylic acids polymers, methacrylic acids, maleic acids and mixed polymers a from them, which may also contain fractions reduced polymerizable substances without acid functionality carboxylic incorporated by polymerization. Molecular weight relative of the homopolymers of unsaturated carboxylic acids are it generally places between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, referred respectively free acid. An acid copolymer Acrylic-maleic acid especially preferred has a weight relative molecular from 30,000 to 100,000. Commercial products they are, for example, Sokalan® CP 5, CP 10 and PA 30 of the BASF firm. The Appropriate compounds of this class, although less preferred, are copolymers of acrylic acid or methacrylic acid with ethers vinyl, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid fraction amounts to less than 50% by weight. Terpolymers can also be used as water soluble organic adjuvant substances, containing as monomers two unsaturated acids and / or their salts, as well as, to third monomer mode, vinyl alcohol and / or a vinyl alcohol esterified, or a carbohydrate. The first acid monomer, or well its salt is derived from a carboxylic acid with 3 to 8 atoms of carbon with monoethylenic installation and preferably of an acid monocarboxylic with 3 to 4 carbon atoms, especially acid (meth) acrylic. The second acid monomer, or its salt, it can be a derivative of a dicarboxylic acid with 4 to 8 atoms of carbon, with maleic acid being especially preferred, and / or a derived from an allylsulfonic acid, which is substituted in position 2 with an alkyl or aryl moiety. Such polymers can be obtained, especially according to procedures described in the application German patent DE 42 21 381 and German patent application DE 43 00 772, and generally have a relative molecular weight between 1,000 and 200,000. Other preferred copolymers are those that are described in German patent applications DE 43 03 320 and DE 44 17 734, and which preferably have acrolein monomers and acrylic acid / acrylic acid salts, or vinyl acetate. Organic adjuvants can be used in particular for obtaining liquid agents, in the form of solutions aqueous, preferably in the form of aqueous solutions at 30 Up to 50 percent by weight. All such acids are used generally in the form of its water soluble salts, especially its alkaline salts

Such organic adjuvant substances may be contained, if desired, in amounts up to 40% in weight, especially up to 25% by weight, and preferably 1% by weight to 8% by weight. Amounts are preferably used close to the upper limit mentioned in agents according to the invention pasty or liquid, especially hydrated.

They come into consideration as materials water soluble inorganic adjuvants, especially silicates alkaline, alkali carbonate and alkaline phosphates, which can be present in the form of its alkaline sodium or potassium salts, neutral or acidic. Examples of this are trisodium phosphate, tetrasodium bisphosphate, hydrogen disodium hydrogen, triphosphate pentasodium, the so-called sodium hexametaphosphate, trisodium phosphate oligomer with oligomerized grades 5 to 1,000, especially 5 to 50, as well as the corresponding potassium salts or mixtures constituted by sodium and potassium salts. They are used as water insoluble inorganic adjuvant materials, dispersible in water, especially crystalline alkaline aluminosilicates or amorphous, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents especially 1% in weight at 5% by weight. Among these are preferred crystalline solid aluminosilicates as a washing agent, especially zeolite A, P, and if necessary X, separately or in mixtures, by way of example in the form of a co-crystallized compound for zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta S.p.A), quantities are preferably used close to the upper limit cited in solid agents, in the form of particle. Appropriate aluminosilicates do not present especially particles with a grain size above 30 µm, and are preferably consisting of particles with a size below 10 µm at least 80% by weight. His binding power of calcium, which can be determined based on the data in the application for German patent DE 24 12 837 is generally in the range 100 to 200 mg of CaO per gram.

The substitutes, or partial substitutes suitable for said aluminosilicate are alkali silicates crystals, which can be presented separately or in mixtures with amorphous silicates. Alkali silicates useful as adjuvants in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO2 below from 0.95, especially from 1: 1.1 to 1:12, and can be presented in the form amorphous or crystalline. Preferred alkali silicates are those sodium silicates, especially amorphous sodium silicates, with a molar ratio Na 2 O: SiO 2 from 1: 2 to 1: 2.8. Those with a molar ratio Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can get according to the patent application procedure European EP 0 425 427. Preferably they are used as silicates crystals, which can be presented separately or mixed with amorphous silicates, the crystalline layered silicates of the general formula Na2 Si_ {x} O2x + 1} and H2O, in which x, the so-called module is a number from 1.9 to 22, especially 1.9 to 4, e y is a number from 0 to 33, and the preferred values for x are 2, 3 or 4. The crystalline layered silicates, which correspond to This general formula is described, by way of example, in the European patent application EP 0 164 514. Silicates Preferred crystalline laminates are those in which x in the aforementioned general formula adopts the values 2 or 3. In particular they are Preferred β-disilicates, as well as δ-sodium (Na 2 Si 2 O 5 and H 2 O), being able to obtain β-sodium disilicate, at by way of example, according to the procedure described in the International Patent Application WO 91/08171. Can be obtained δ-sodium silicates with a module between 1.9 and 3.2 according to Japanese patent applications JP 04/238 809 or JP 04/260 610. The agents according to the invention can also be used crystalline alkaline silicates, practically anhydrous, obtained from amorphous alkaline silicates, of the formula general cited above, in which x means a number of 1.9 to 2.1, obtainable as described in patent applications European EP 0 548 599, EP 0 502 325 and EP 0 425 428. In another form of preferred embodiment of agents according to the invention a crystalline stratified sodium silicate with a module of 2 to 3, as can be obtained from sand and soda according to the European patent application procedure EP 0 436 835. In another preferred embodiment of agents according to the invention crystalline sodium silicates with a module in the range from 1.9 to 3.5, as obtainable according to the procedure of European patent applications EP 0 164 552 and / or EP 0 294 753. The crystalline layered silicates of the formula (I) indicated above are distributed by the firm Clariant GmbH under the trade names Na-SKS, for example Na-SKS-1 (Na_2 Si_ {22} O_ {45} xH_ {O}, Kenyaite), Na-SKS-2 (Na_ {Si} {14} O_ {29} xH_ {O}, Magadiita), Na-SKS-3 (Na_2 Si_ {8} O_ {17} xH2 O) or Na-SKS-4 (Na_ {2} Si_ {4} O_ {9} xH_ {2}, Makatita). Of these are appropriate especially Na-SKS-5 (α-Na 2 Si 2 O 5), Na-SKS-7 (β-Na 2 Si 2 O 5, Natrosilite), Na-SKS-9 (NaHSi 2 O 5 .H 2 O), Na-SKS-10 (NaHSi 2 O 5. 3H 2 O, Kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5) and Na-SKS-13 (NaHSi 2 O 5), but especially Na-SKS-6 (δ-Na_ {2} Si_ {2} O_ {5}). One is found compilation on crystalline layered silicates, by example, in the articles published in "Hoechst High Chem Magazine 14/1993 "on pages 33-38, and in "Seifen-Öle-Fette-Wachse, collection 116, No. 20/1990 "on pages 805-808. In a preferred conditioning of agent according to the invention a granulated compound is used constituted with crystalline layered silicate and citrate, by crystalline layered silicate and polycarboxylic acid (co-) polymer cited above, as described, for example, in German patent application DE 198 19 187, or by silicate alkali or alkali carbonate, as described, for example, in the international patent application WO 95/22592, or as is available commercially, by way of example, under the name Nabion® 15.

The adjuvant substances may be contained in the agents according to the invention, where appropriate, in amounts up to 90%. These are preferably contained in amounts up to 75% by weight. Washing agents according to invention present contents in adjuvants especially of 5% in 50% weight by weight. The agents according to the invention for the hard surface cleaning, especially for cleaning tableware machine, the content in adjuvant substances it amounts in particular to 5% by weight up to 88% by weight, not using adjuvant materials preferably in such agents insoluble in water. In a preferred embodiment of Agents according to the invention for cleaning the dishes, in Special machine, is 20% by weight to 40% by weight of water-soluble organic adjuvants, especially citrate alkaline, 5% by weight to 15% by weight alkali carbonate, and a 20% by weight to 40% by weight alkali disilicate.

They come into consideration as compounds of peroxide, suitable for use in agents according to invention, in addition to the alkaline percarbonates, already mentioned, in special, organic peracids, or peracid acid salts organic, such as phthalimidopercapronic acid, perbenzoic acid, or salts of diperdodecanoic acid, hydrogen peroxide, and salts inorganic that emit hydrogen peroxide under the conditions of washing, to which belong perborates, percarbonates, persilicates and / or persulfates, such as carob. While they are due employ solid peroxide compounds, these can be applied in form of powders or granules, which may also be wrapped in way known in principle. If an agent according to the invention contains peroxide compounds, these are present in amounts preferably up to 50% by weight, especially 5% in weight at 30% by weight, and especially preferably 8% by weight to 25% by weight. The addition of reduced amounts of known bleaching agent stabilizers, such as from phosphonates, borates, or metaborates and metasilicates, as well as magnesium salts, such as magnesium sulfate, can be convenient.

Whitening activators can be used compounds that form aliphatic peroxocarboxylic acids under the perhydrolysis conditions with preferably 1 to 10 atoms carbon, especially with 2 to 4 carbon atoms and / or acids if necessary, substituted perbenzoic. Substances are suitable bearing O- and / or N-acyl groups, with the number of cited carbon atoms and / or benzoyl groups if appropriate replaced. Polycylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), acylated derivatives of triazine, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycoluryls, especially tetraacetylglycoluryl (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), phenolsulfonates acylates, especially n-nonanoil- or isononanoylbenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially acid anhydride phthalic, acylated polyvalent alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enolésteres, known by the German requests DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated saccharic derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetylactose as well as acetylated glucamine, if necessary N-alkylated and gluconolactone, and / or lactams N-acylated, for example N-benzoylcaprolactam, which are known by the International patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498. Acylacetals hydrophilic substitutes, known by the patent application German DE 196 16 769 and acillactams, described in the application German patent DE 196 16 770 as well as in the patent application International WO 95/14075, will also be used in a manner preferential. You can also use the combinations of conventional bleach activators, known by the application German patent DE 44 43 177. Such bleaching activators are contained in the usual quantitative range, preferably in amounts from 0.5% by weight to 10% by weight, especially from 1% by weight to 8% by weight, based on agent set.

In addition to bleach activators Conventionals listed above, or instead, may be also the sulfonimines known by the memories Descriptions of European patents EP 0 446 982 and EP 0 453 003 and / or salts of bleaching reinforcing transition metals or transition metal complexes by way of so-called bleaching catalysts.

To the organic solvents that can be used in agents according to the invention, especially when presented in liquid or pasty form, alcohols with 1 to 4 atoms belong carbon, especially methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers that they can be derived from the classes of compounds mentioned. Such water miscible solvents are present in the agents of washing according to the invention, preferably in no larger quantities than 30% by weight, especially from 6% by weight to 20% in weigh.

Additionally, the agents may contain other components, usual in washing and cleaning agents. To these optional components belong, especially stabilizers of enzymes, graying inhibitors, run inhibitors colors, foam inhibitors and optical brighteners as well as dyes and perfumes. To cause protection against corrosion of silver, corrosion inhibitors can be used of silver in dishes cleaning agents, according to the invention. A cleaning agent according to the invention, for hard surfaces, may also contain action components abrasive, especially from the group comprising quartz flour, sawdust, synthetic flour. cretas and microspheres of glass as well as its mixtures. The abrasive products are contained in the cleaning agents according to the invention, preferably, in a proportion not greater than 20% by weight, especially from 5% by weight to 15% by weight.

For setting a desired pH value, which does not It produces itself by mixing the components usual, the agents according to the invention may contain acids compatible with the system and the environment, especially citric acid, acetic acid, tartaric acid, malic acid, acid lactic acid, glycolic acid, succinic acid, glutaric acid and / or acid adipic, as well as mineral acids, especially acid sulfuric acid, or bases, especially ammonium hydroxide or hydroxides alkaline Such pH regulators are contained in the agents. according to the invention preferably in a proportion not greater than the 20% by weight, especially from 1.2% by weight to 17% in weight.

To the inhibitors of the color run that come into consideration for employment in agents according to the invention, especially those for washing textiles, belong especially polyvinylpyrrolidone, polyvinylimidazoles, Polymer N-oxides of poly- (vinylpyridine-N-oxide) and copolymers of vinyl pyrrolidone and vinylimidazole.

In the agents according to the invention may be additional agrisado inhibitors are also present. For it water-soluble colloids are most often of organic nature, for example starches, glues, jellies, salts of ethercarboxylic acids or of ethersulfonic acids of the starches or cellulose or salts of acidic acid esters sulfuric acid from cellulose or starches. Are also suitable for this purpose water soluble polyamides, containing acid groups. In addition, soluble preparations of starch and other starch products other than those above indicated, for example aldehyde starches. However, they will be used, preferably, cellulose ethers such as carboxymethyl cellulose, methyl cellulose (Na salt), methyl cellulose, hydroxyalkylcelluloses and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts from 0.1 to 5% by weight, based on the agent.

Agents for washing textiles, according to the invention may contain, by way of optical brighteners, derivatives of diamino stilbendisufónico acid or its salts with alkali metals. For example, the acid salts 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilben-2,2'-disulfonic acid or similarly constituted compounds that bear, instead of morpholino group, a diethanolamino group, a methylamino group, a aniline group or a 2-methoxyethylamino group. further brighteners of the type of substituted diphenylstyriles, for example the alkaline salts of 4,4'-bis (2-sulfoestyryl) -diphenyl, of the 4,4'-bis (4-chloro-3-sulfoestyryl) -diphenyl, or of 4- (4-Chlorostyryl) -4 '- (2-sulfoestiryl) -diphenyl. Mixtures of the brighteners can also be used previously indicated.

When used in washing procedures mechanical may be convenient to add to the inhibitors of The usual foam. As foam inhibitors are suitable, for for example, soaps of natural or synthetic origin, presenting a high proportion of fatty acids with 18 to 24 atoms of carbon. Suitable non-surfactant foam inhibitors they are, for example, organopolysiloxanes and their mixtures with acid Silicon microfine, if appropriate silanized, as well as with paraffins, waxes, microcrystalline waxes and mixtures with silicic acid silanized or bistenylethylenediamide. Advantageously they will be used also mixtures consisting of various foam inhibitors, for example those constituted by silicones, paraffins or waxes. Preferably foam inhibitors, especially those foam inhibitors containing silicone and / or paraffin, are bonded on a granular, soluble or soluble support substance water dispersible In this case they are especially preferred mixtures consisting of paraffins and bisestearylethylene diamides.

The manufacture of solid agents according to the invention offers no difficulty and can be carried out in known manner, for example by spray drying or by granulation, being added if necessary later, separately enzymes and, eventually, other thermally sensitive components such as for example bleaching agents. For manufacturing of the agents according to the invention with a high bulk weight, especially in the range from 650 g / l to 950 g / l, it is preferably a process presenting an extrusion stage, known for the specification of European patent EP 0 486 592. Other preferred manufacturing with the aid of a process of granulation is described in the patent specification European EP 0 642 576.

For the manufacture of agents according to the invention in the form of tablets, which may be monophasic or polyphasic, of a single color or with several colors and, especially which may consist of one layer or several layers, especially by two layers, it is preferably derived from such so that all the components - if necessary for each layer - are mix together in a mixer and the mixture is pressed by traditional presses for entachating, for example presses eccentric or circular presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN. Especially in the case of multilayer tablets can it is advantageous that the previous pressing is carried out at least one cap. This will preferably be carried out by pressing forces. between 5 and 20 kN, especially 10 to 15 kN. From this way you get, without problems, tablets resistant to breakage and yet soluble quickly enough under the application conditions with breakage resistance and at flexion normally from 100 to 200 N, preferably however above 150 N. Preferably a tablet, manufactured from it. mode, it has a weight from 10 g to 50g, especially from 15 g up to 40 g. The geometric shape of the tablets is arbitrary and it can be round, oval or polygonal, shapes also being possible intermediate. The vertices and edges are advantageously rounded. The round tablets preferably have a diameter from 30 mm to 40 mm. Especially the size of the tablets configured in a polygonal or square way, which introduce, for example, in the machine for dishwashing, predominantly from the dosing device, it is a function of the geometry and volume of this dosing device. From exemplary way the preferred embodiments have a base surface of (20 to 30 mm) x (34 to 40 mm), especially 26x36 mm or 24x38 mm.

Washing or cleaning agents according to the invention, liquid or pasty, in the form of solutions, which they contain the usual solvents, they are manufactured, as a rule, by simple mixing of the components, which can be introduced in an automatic mixer in substance or in the form of dissolution.

Examples Example 1

They were added to a basic washing agent, free of BW1 enzymes, the cellulases indicated in table 1. The cellulases were used, with reference to protein, in a respective amount such that it corresponded to an amount of employment 0.06% by weight of Celluzyme® 0.7T (manufacturer: Novo Nordisk) in the washing agent used in each case. The grating of the tissues - determined by remission after 10 washings-, carrying out the wash tests under the following conditions:

Washing machine: Miele® W918

Temperature: 40ºC

Dosage of washing agent: 76 g

Water hardness: 16ºdH

Load: 2.5 kg of clean laundry (test fabric made of cotton from the Wäschforschungsanstalt Krefeld, cushion covers, terry towels, t-shirts and tea towels)

Dirt: 5 skeins were added to each wash of cotton with normalized dirt of skin dust / grease.

The numerical values of the grating, obtained after washing with the indicated recipes (data as% of remission, average values of all textiles) have been gathered in table 1 following, having also given the initial value of the referral before washing and the value for the base washing agent, exempt of enzymes, for comparative purposes.

TABLE 1

Agent Gray Value initial 87.3 BW1 54.5 BW1 + DAC a) 69.2 BW1 + Carezyme® (manufacturer: Novo Nordisk) 59.5 BW1 + 20K-cellulase 73.0 a) cellulase according to WO 96/34108

It is observed that when cellulase is used, be used according to the invention, a better inhibition is presented than gray when other cellulases are used.

Example 2

Example 1 was repeated, taking place 11 washed unlike the procedure described there and used a base wash agent BW2 containing, unlike BW1, 1.2% by weight of an enzymatic granulate, which contained the protease BLAP with an activity of 200,000 PE / g.

TABLE 2

Agent Gray Value initial 87.0 BW2 54.2 BW2 + DAC a) 73.1 BW2 + 20K-cellulase 75.4 a) cellulase according to WO 96/34108

It is noted that an agent according to the invention it has a grating inhibitory effect better than the agent that contains, instead of the cellulase to be used according to the invention, another cellulase.

Claims (10)

1. Use of 20K-cellulase, obtainable from Melanocarpus sp . or from Myriococcum sp . or of the one that presents a homology greater than 80% with it, as an inhibitor of grating in washing agents. 2. Use of 20K-cellulase, obtainable from Melanocarpus sp . or from Myriococcum sp . or of that which has a homology greater than 80% with respect to it, as an inhibitor of grating in washing agents, containing inorganic, water insoluble, finely divided adjuvants, especially zeolite. 3. Use of 20K-cellulase, obtainable from Melanocarpus sp . or from Myriococcum sp . or of the one that has a homology greater than 80% with it, to reduce the redeposition during the laundry of textiles with washing agents for textiles based on inorganic, water insoluble, finely divided adjuvant components. 4. Use according to one of claims 1 to 3, characterized in that the washing agent contains, as an adjuvant, from 10% by weight to 50% by weight, especially from 10% by weight to 40% by weight. weight of inorganic adjuvant material, water dispersible, insoluble in water, as a washing agent, especially crystalline alkali silicates, crystalline alkaline aluminosilicates and / or amorphous, especially zeolite A, zeolite P and / or zeolite X. 5. Washing or cleaning agent, containing 20K-cellulase obtainable from Melanocarpus sp . or from Myriococcum sp . or a cellulase that has a homology greater than 80% with it, in combination with a protease, if modified by genetic engineering, from Bacillus lentus and / or alkaline percarbonates. 6. Agent according to claim 5, characterized in that it has a cellulolytic activity, due to 20K-cellulase, obtainable from Melanocarpus sp . or from Myriococcum sp . or to a cellulase, which has a homology greater than 80% with it, from 1 NCU / g to 500 NCU / g, especially from 5 NCU / g to 400 NCU / g. 7. Agent according to claims 5 or 6, characterized in that at least one of the exchanges of amino acids S3T, V4I, V193M, V199I or L211D has been carried out in the protease, modified by genetic engineering, from Bacillus lentus . 8. Agent according to one of claims 5 to 7, characterized in that the ratio between cellulolytic activity, expressed in NCU / g, and proteolytic activity, expressed in PE / g, is in the range from 1: 10,000 to 5: 1, especially from 1: 600 to 4: 3. 9. Agent according to one of claims 5 to 8, characterized in that it contains 50% by weight, especially from 5% by weight to 30% by weight of alkali percarbonates, especially sodium percarbonate. 10. Agent according to one of claims 5 to 9, characterized in that it contains from 0.0001 mg to 0.1 mg, especially from 0.001 mg to 0.01 mg of cellulolytic protein for each% by weight of alkali percarbonate.