EP0822973B1 - Cellulase-containing washing agents - Google Patents

Abstract

PCT No. PCT/EP96/01616 Sec. 371 Date Nov. 21, 1997 Sec. 102(e) Date Nov. 21, 1997 PCT Filed Apr. 18, 1996 PCT Pub. No. WO96/34080 PCT Pub. Date Oct. 31, 1996In washing agents containing tensides and cellulase, the properties of the cellulase which are relevant to the application were to be improved. This was essentially achieved in that use was made of a cellulase mixture in which the first component, with a CMCase activity of 1 U per liter and a protein concentration of a most 3 mg per liter, gives an increase in remission of at least 5 units in the secondary washing test and the second component, with a CMCase activity of 20 U per liter gives an increase in absorption in the cellulose decomposition test of at least 0.075.

Description

The invention relates to a detergent which is a combination of at least two cellulases contains, a washing process using the cellulase combination and the use the cellulase combination for the production of detergents.

Enzymes, especially proteases, lipases and cellulases, are used extensively in detergents, washing aids and cleaning agents. During proteases and lipases primarily for Removal of protein or fat stains is used To see the task of cellulases in the washing process more differentiated.

Because of their ability to break down cellulose, cellulases have long been considered Aviva active ingredients for cotton fabrics, for example from the German patent DE 21 48 278 or the German patent application DE 31 17 250, known. For the relevant mechanism of action, it is assumed that laundry softening Cellulases prefer to attack microfibrous cellulose, so-called fibrils, hydrolytically and remove that protrude from the surface of the cotton fiber and free sliding hinder the cotton fibers on top of each other. A side effect of this fibril breakdown is the deepening of the optical color impression, for example in the European patent specification So-called color refreshment described in EP 220 016, which occurs during the treatment dyed cotton textiles with cellulases then results from fiber damage originating, undyed fibrils originating from the inside of the fibers are removed.

On the other hand, cellulases are also known which are notable for the fact that, as for example in German published patent application DE3207828 describes a cleaning effect to the extent that they are able to remove inorganic solid dirt to remove cleaning textile.

In order to achieve both of the cellulase effects which are desirable in the washing process, is have already been proposed several times to use mixtures of cellulases. An example in this context is the international patent application WO 95/02675 referenced. This document deals with detergents with two cellulase components, wherein the first cellulase component has the ability to remove has particulate dirt and the second cellulase component color refreshing properties owns. However, the selection of cellulases based on these criteria leaves important ones Unanswered questions about washing practice.

To the problematic stains that are only insufficiently removed with conventional detergents soiling of cellulose and paper must be expected. These arise usually only during the washing process, when papers such as Banknotes or cellulose handkerchiefs randomly, for example in pockets, in the to cleaning items of laundry remain and can be washed. The problems are based on the formation of large, optically recognizable flakes that stick to the laundry and not be rinsed out.

The property of removing dirt from the textile to be cleaned is usually called Primary washing ability called. In addition to ingredients with this for the washing process As a rule, indispensable properties are also of central importance in detergents Contain active ingredients that contribute to the secondary washing ability. That means the Property, dirt detached from the textile thus dissolved or suspended in the wash liquor to be able to keep that it does not affect the cleaned textile. This effect will also known as anti-redeposition. With detergents, it is desirable if as many of their ingredients as possible, including the cellulase used, due to their anti-redeposition effect contribute an amount to the detergent's secondary washing ability.

The present invention seeks to remedy this by using cellulase mixtures, the first component having a pronounced secondary washing ability has and the second component is capable of hydrolysis of pulp.

It is irrelevant whether the components mentioned are pure substances in the sense of chemical individual substances, that is to say in the present case in particular when used genetic engineering processes from a single gene cellulases, or around enzyme mixtures acts as they are in the majority of commercially available cellulases.

In its first aspect, the invention relates to detergents, the surfactant and a cellulase mixture included, the first component at a CMCase activity of 1 U per liter and a protein concentration of at most 3 mg per liter, preferably 0.0001 mg per Liters to 0.6 mg per liter, in the secondary wash test a remission increase of at least 5 units, in particular from 5.0 to 10.0 units, and their second component with a CMCase activity of 20 U per liter, preferably at a protein concentration of at most 20 mg per liter, an increase in absorption in the pulp degradation test of at least 0.075 results.

A second object of the invention is a washing process, which thereby is characterized in that in an aqueous, preferably surfactant-containing solution, a cellulase mixture, their first component with a CMCase activity of 1 U per liter and one Protein concentration of at most 3 mg per liter, preferably 0.0001 mg per liter to 0.6 mg per liter, in the secondary wash test a remission increase of at least 5 units, in particular from 5.0 to 10.0 units, and their second component a CMCase activity of 20 U per liter, preferably at a protein concentration of at most 20 mg per liter an increase in absorption in the cellulose degradation test of results in at least 0.075, has an effect on textiles. It is possible to use the invention Means in such a procedure.

Another object of the invention is a test method for finding for the Use in cellulase mixtures suitable for detergents, one being used to determine the first component performs the secondary wash test and selects a cellulase that a CMCase activity of 1 U per liter and a protein concentration of at most 3 mg per liter, preferably 0.0001 mg per liter to 0.6 mg per liter, one in the secondary wash test Reflectance increase of at least 5 units, in particular from 5.0 to 10.0 units, results, and to determine the second component performs the cellulose degradation test and one Selects cellulase with a CMCase activity of 20 U per liter, preferably at one Protein concentration of at most 20 mg per liter increases the absorption in the cellulose degradation test of at least 0.075. The cellulase mixtures mentioned are preferably used for the production of detergents.

The protein content of the cellulase components can be determined using the determination method of Pierce, published by RE Brown et al. in anal. Biochem. 180: 136-139 (1989).

The activity determination of the cellulase components (CMCase activity) is based on modifications by M.Lever in Anal. Biochem. 47 (1972), 273-279 and Anal. Biochem. 81 (1977), 21-27. A 2.5% by weight solution of carboxymethyl cellulose (obtained from Sigma, C-5678) in 50 mM glycine buffer (pH 9.0) is used for this. 250 ml of this solution are incubated for 30 minutes at 40 ° C. with 250 ml of a solution containing the enzyme to be tested. Then 1.5 ml of a 1 percent by weight solution of p-hydroxybenzoic acid hydrazide (PAHBAH) in 0.5 M NaOH, which contains 1 mM bismuth nitrate and 1 mM potassium sodium tartrate, are added and the solution is heated to 70 ° C. for 10 minutes. After cooling (2 minutes at 0 ° C), the absorption at 410 nm (for example using a Uvikon® 930 photometer) is determined against a blank value at room temperature. A solution is used as the blank value, which was prepared like the measurement solution, with the difference that both the PAHBAH solution and the CMC solution are added in this order only after the incubation of the enzyme and heated to 70.degree. In this way, possible activities of the cellulase with media components are also recorded in the blank value and deducted from the total activity of the sample, so that in fact only the activity against CMC is determined. 1 U corresponds to the amount of enzyme that produces 1 mmol glucose per minute under these conditions.

The secondary wash test is performed using standardized pigment soils (containing 86% kaolin, 8% flame black 101 from Degussa, 4% iron oxide black and 2% iron oxide yellow, manufacturer Henkel Genthin GmbH) and white cotton fabric (Manufacturer Windelbleiche, Krefeld). Containing 19 ml of a dirty liquor 0.5% by weight of the pigment soiled and 5 g / l of a bleach and enzyme-free Detergent powder, for example consisting of 12 wt .-% alkylbenzenesulfonate, 9 wt .-% 3-bis 5-fold ethoxylated fatty alcohol, 2% by weight soap, 32% by weight zeolite Na-A, 10% by weight Trisodium citrate, 12% by weight sodium carbonate, 8% by weight sodium sulfate, 4% by weight Dicarboxylic acid mixture Sokalan® DCS and 11% by weight water, together with 1 round (diameter 5 cm) punched out piece of the named cotton fabric, the 1 time with the detergent powder mentioned at 40 ° C and a concentration of 5 g / l has been prewashed at pH 8.5 and 40 ° C after adding 1 ml of a solution Contains 20 U / liter of cellulase in crystallizing dishes (diameter 6 cm) for 30 minutes incubated with shaking (90 rpm). Then the piece of cotton is flowing Rinsed out water and ironed. With the help of a color measuring device (Micro color, manufacturer Dr. Long) the remission (expressed in% REM) is determined and by subtracting the Remission value of a piece of cotton treated accordingly without the addition of enzyme Remission difference determined. 4 measuring points are taken per piece of cotton Increasing the significance of the values for the remission difference can lead to duplicate determinations be performed. The composition of the detergent used is not particularly critical, since this essentially determines the absolute position of the reflectance values influenced and it does not depend on the absolute remission for the described secondary washing test, but also on the remission differences between the use of enzyme-free Detergent and cellulase-containing detergent arrives.

The cellulose breakdown test is carried out using cellulose handkerchiefs (brand Tempo®, Manufacturer and sales VP Schickedanz AG, Nümberg), from which pieces (1-ply) with Diameter 5 mm were punched out. 1 such round piece of cellulose is used with 0.9 ml of a wash liquor, the 5.56 g / l of the secondary wash test Detergent contains, at pH 8.5 and 30 ° C after adding 0.1 ml of a solution that Contains 200 U / liter of cellulase, incubated for 4 hours and then centrifuged (3 minutes, 14000 rpm). In the supernatant, as described when determining the CMCase activity, the reducing sugar is determined with PAHBAH, whereby the value of a Serves solution that has been treated accordingly without the addition of cellulase. The absorption difference is a measure of the breakdown of the pulp.

The secondary detergent and pulp degradation test procedures described above have compared to known tests, for example the one in the European one Patent EP 350 098 described evaluation method, which is based essentially on measurement of the cellulolytic degradation of the non-natural substrate carboxymethyl cellulose limit the great advantage that they are the performance evaluation of cellulases on the basis of parameters relevant to practice, that is, by the end user of the cellulase-containing Allow detergents to be experienced directly. Because of this, they are Results of the test procedures presented here directly with practical results at Household laundry or commercial laundry correlated. Another subject of The invention is therefore a test method for selecting suitable ones for use in detergents Cellulase mixtures, which is characterized in that a first Component selects that they with a CMCase activity of 1 U per liter and preferably at a protein concentration of at most 0.6 mg per liter in Secondary wash test results in an increase in remission of at least 5 units, and one selects the second component so that it with a CMCase activity of 20 U per Liter, preferably at a protein concentration of 20 mg per liter, an increase in absorption results in a pulp degradation test of at least 0.075.

The proportions in which the according to this inventive method selected cellulases are essentially dependent on which of the with the individual tests proven achievements one in the detergent respectively Wants to put washing processes in the foreground. It is preferred if the weight ratio said first component to said second component, each based on Protein, 1: 100 to 1:10, in particular 1:60 to 1:20.

Detergents which contain the cellulase mixture mentioned can be all conventional contain other ingredients of such agents that are not undesirable with the Cellulases interact. Surprisingly, it was found that such cellulase mixtures the effect of certain other washing and cleaning agent ingredients synergistically influence and that conversely the effect of the cellulase mixture through certain other detergent ingredients are synergistically enhanced. These effects occur in particular in the case of nonionic surfactants, in the case of additional enzymatic active ingredients, in particular Proteases and lipases, in water-insoluble inorganic builders, in water-soluble ones inorganic and organic builders, especially those based on oxidized Carbohydrates, for bleaching agents based on peroxygen, in particular for alkali percarbonate, and in the case of synthetic anionic surfactants of the sulfate and sulfonate type, but not or only little pronounced in alkylbenzenesulfonates, which is why the use of the aforementioned Ingredients together with the cellulase mixtures is preferred.

In a preferred embodiment, an agent according to the invention contains nonionic Surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, especially in an amount in the range from 2% by weight to 25% by weight.

Another embodiment of such agents involves the presence of synthetic Anionic surfactant of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, Fatty alkyl ether sulfate, sulfofatty acid esters and / or sulfofatty acid disalts, especially in one Amount in the range of 2 wt% to 25 wt%. The anionic surfactant is preferred from the Alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates selected, in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.

The nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes of US Pat. No. 1,985,424. US 2 016 962 and US 2 703 798 and the international patent application WO 92/06984 can be considered. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) _n -OR ¹ , in which R ^{1 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828. The glycoside component (G) _n is an oligomer or polymer from a naturally occurring aldose or ketose monomer, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Xylose and Lyxose belong to. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization n generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl part R ^{1 of} the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R ¹ = dodecyl and R ¹ = tetradecyl.

Nonionic surfactant is preferably in agents containing the cellulase mixture in Contain amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 wt .-%.

Instead or in addition, such agents can include further surfactants, preferably synthetic ones Anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight, in each case based on the total Means included. As synthetic, particularly suitable for use in such agents Anionic surfactants are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which are an alkali, Ammonium or alkyl or hydroxyalkyl substituted ammonium ion as Wear counter cation, to name. The derivatives of fatty alcohols are particularly preferred 12 to 18 carbon atoms and their branched chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can in a known manner by reaction of the corresponding Alcohol component with a conventional sulfating reagent, especially sulfur trioxide or chlorosulfonic acid, followed by neutralization with alkali, ammonium or alkyl or Hydroxyalkyl-substituted ammonium bases can be produced. Such Alkyl and / or alkenyl sulfates are preferably in amounts according to the invention Contain 0.1 wt .-% to 20 wt .-%, in particular from 0.5 wt .-% to 18 wt .-%.

The sulfated alkoxylation products also belong to the usable surfactants of the sulfate type of the alcohols mentioned, so-called ether sulfates. Preferably contain such Ether sulfates 2 to 30, in particular 4 to 10 ethylene glycol groups per molecule. To the Suitable anionic surfactants of the sulfonate type include those by reacting fatty acid esters α-sulfoesters obtainable with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, deriving sulfonation products, as well as by formal saponification from them emerging sulfo fatty acids.

Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. Soap mixtures are particularly preferred which are composed of 50% by weight to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid agents according to the invention, higher amounts of soap of generally up to 20% by weight can also be present.

In a further embodiment, an agent according to the invention contains water-soluble and / or water-insoluble builders, especially selected from alkali alumosilicate, crystalline Alkaline silicate with module over 1, monomeric polycarboxylate, polymeric polycarboxylate and their mixtures, in particular in amounts in the range from 2.5% by weight to 60% by weight.

An agent according to the invention preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances in copolymerized form without carboxylic acid functionality. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, preferably a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred. 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight, of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular mass between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They can be used, in particular for the preparation of liquid compositions, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances are preferably in amounts of up to 40% by weight, in particular Contain up to 25 wt .-% and particularly preferably from 1 wt .-% to 5 wt .-%. Amounts close to the above upper limit are preferably in paste or liquid, in particular water-containing agents used in which the cellulase mixture is included.

In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular from 1% by weight to 5% by weight used. Among these, the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the above upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the compositions preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. They are preferably added as a solid and not in the form of a solution during production. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _{2x + 1} yH ₂ O are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates, in which x, the so-called module, is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 described. can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or European patent application EP0294753, are used in a further preferred embodiment of agents according to the invention. Their alkali silicate content is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali alumosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

In addition to the inorganic builder mentioned, other water-soluble or water-insoluble ones inorganic substances are used in agents according to the invention. Suitable in this context are the alkali carbonates, alkali hydrogen carbonates and alkali sulfates as well as their mixtures. Such additional inorganic material can in Amounts of up to 70% by weight are present, but are preferably missing entirely.

In addition, the detergents can contain other constituents customary in detergents and cleaning agents contain. These optional components include, in particular, further enzymes, Enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example Aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, Color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyridine-N-oxide, Foam inhibitors, for example organopolysiloxanes or paraffins, so-called soil release active ingredients, for example polymers based on terephthalic acid, polyglycols and Glycols, solvents, fabric softening auxiliaries, for example from the class the quaternary ammonium compounds or clays, and optical brighteners, for example Stilbene disulfonic acid derivatives. Preferably up to 1% by weight are in agents according to the invention, in particular 0.01% by weight to 0.5% by weight of optical brighteners, in particular compounds from the class of the substituted 4,4'-bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 15 wt .-%, in particular 0.5 wt .-% to 10 wt .-% fabric softening Excipients, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for Heavy metals, especially aminoalkylenephosphonic acids and their salts, up to 3% by weight, in particular 0.5% by weight to 2% by weight of graying inhibitors, up to 3% by weight, in particular 0.5% by weight to 2% by weight of soil release active ingredients and up to 2% by weight, in particular Contain 0.1 to 1% by weight of foam inhibitors, the weight percentages mentioned refer to the entire average.

Solvents which are used in particular in the case of liquid agents according to the invention, in addition to water are preferably those which are water-miscible. These include lower alcohols, for example ethanol, propanol, isopropanol, and the isomers Butanols, glycerin, lower glycols, for example ethylene and propylene glycol, and those from the aforementioned classes of derivable ether.

Any enzymes additionally present are preferably included in the group Protease, amylase, lipase, hemicellulase, oxidase, peroxidase or mixtures of selected this. Primarily comes from microorganisms, such as bacteria or fungi, protease obtained in question. You can in a known manner by fermentation processes can be obtained from suitable microorganisms, for example in the German DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, the U.S. patents US 3,632,957 and US 4,264,738, European Patent application EP 006 638 and the international patent application WO 91/02792 are. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem® available. The lipase that can be used can be from Humicola lanuginosa, such as in European Patent applications EP 258 068, EP 305 216 and EP 341 947 Bacillus species, such as in international patent application WO 91/16422 or European patent application EP 384 717, from Pseudomonas species, such as for example in European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international patent application WO 90/10695 Fusarium species, such as, for example, in European patent application EP 130 064 described from Rhizopus species, such as in the European patent application EP 117 553 described, or from Aspergillus species, such as in the European Patent application EP 167 309 described can be obtained. Suitable lipases are, for example under the names Lipolase®, Lipozym®, Lipomax, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito® lipase and Diosynth® lipase commercially available. The applicable amylase can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Suitable Amylases are commercially available, for example, under the names Maxamyl® and Termamyl®.

Regarding the usual ones, especially those present in liquid funds Enzyme stabilizers include amino alcohols, e.g. mono-, di-, triethanol- and - propanolamine and mixtures thereof, lower carboxylic acids, such as from the European patent applications EP 376 705 and EP 378 261 known boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from the European patent application EP 451 921 known boric acid esters, such as from the international patent application WO 93/11215 or the European patent application EP 511 456 known, boronic acid derivatives, such as from the European Patent application EP 583 536 known calcium salts, for example those from the European patent EP 28 865 known Ca-formic acid combination, Magnesium salts, as known, for example, from European patent application EP 378 262, and / or sulfur-containing reducing agents, such as from the European Patent applications EP 080 748 or EP 080 223 are known.

Suitable foam inhibitors include long-chain soaps, especially behave soap, Fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and their Mixtures that are also microfine, optionally silanized or otherwise May contain hydrophobized silica. For use in particulate agents such foam inhibitors preferably on granular, water-soluble carrier substances bound, such as in German Offenlegungsschrift DE 34 36 194, the European patent applications EP 262 588, EP 301 414, EP 309 931 or the European patent EP 150 386 described.

An agent according to the invention can also contain additional graying inhibitors. For this are water-soluble colloids mostly organic in nature, for example the water-soluble Salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose. Soluble starch preparations and others can also be used use the above-mentioned starch products, for example partially hydrolyzed starch. Na carboxymethyl cellulose, Methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferred.

Another embodiment of an agent according to the invention contains bleaching agents based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight. These bleaches in question are usually those in detergents used per compounds such as hydrogen peroxide, perborate, which as a tetra or monohydrate Percarbonate, perpyrophosphate and persilicate, which are usually available as Alkali salts, especially as sodium salts, are present. Such bleaching agents are in the invention Detergents preferably in amounts up to 25 wt .-%, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight, in each case based on the total Medium, available. The optional component of the bleach activators includes the commonly used N- or O-acyl compounds, for example multiple acylated Alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, Sulfurylamides and cyanurates, also carboxylic anhydrides, in particular Phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, especially pentaacetyl glucose. The bleach activators can to avoid the interaction with the per-compounds during storage in known Were coated or granulated with coating substances, with the help Medium grain size tetraacetylethylenediamine granulated from carboxymethyl cellulose from 0.01 mm to 0.8 mm, as is the case, for example, in the European patent specification EP 37 026 described method can be prepared, and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as it is according to the DD 255 884 described method can be produced, is particularly preferred. In Such bleach activators are preferably in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total average.

In a preferred embodiment, an agent according to the invention is particulate and contains 20% by weight to 55% by weight of inorganic builder, up to 15% by weight, in particular 2% by weight to 12% by weight of water-soluble organic builder, 2.5% by weight to 20% by weight synthetic anionic surfactant, 1% by weight to 20% by weight nonionic surfactant, up to 25% by weight, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight up to 6% by weight bleach activator and up to 20% by weight, in particular 0.1% by weight to 15% by weight inorganic salts, especially alkali carbonate and / or sulfate.

In a further preferred embodiment, such a powdery agent contains especially for use as a mild detergent, 20 wt .-% to 55 wt .-% inorganic Builder, up to 15 wt .-%, in particular 2 wt .-% to 12 wt .-% water-soluble organic builder, 4 wt% to 24 wt% nonionic surfactant, up to 15 wt%, in particular 1% to 10% synthetic anionic surfactant, up to 65% by weight, in particular 1% by weight to 30% by weight of inorganic salts, in particular alkali carbonate and / or sulfate, and neither bleach nor bleach activator.

Another preferred embodiment comprises a liquid agent containing 5% by weight to 35% by weight of water-soluble organic builder, up to 15% by weight, in particular 0.1% by weight up to 5% by weight of water-insoluble inorganic builders, up to 15% by weight, in particular 0.5 wt% to 10 wt% synthetic anionic surfactant, 1 wt% to 25 wt% nonionic Surfactant, up to 15% by weight, in particular 4% by weight to 12% by weight of soap and up to 30% by weight, in particular 1% by weight to 25% by weight of water and / or water-miscible Solvent.

Examples Example 1: Results of the secondary washing test

The secondary washing test described above was carried out using a detergent consisting of 12% by weight alkylbenzenesulfonate, 9% by weight 3 to 5-fold ethoxylated fatty alcohol, 2% by weight soap, 32% by weight zeolite Na-A, 10% by weight of trisodium citrate, 12% by weight of sodium carbonate, 8% by weight of sodium sulfate, 4% by weight of dicarboxylic acid mixture Sokalan® DCS and 11% by weight of water. The values listed in Table 1 (mean value from 2 determinations) of the reflectance difference (Delta REM) for various cellulases were obtained. It is clear from the protein concentrations (in mg / l) also given in Table 1 that Celluzyme® by far does not meet the conditions for the first component of the cellulase mixture. Remission difference in the secondary wash test Cellulase Delta REM Protein concentration Celluzyme® 0.7T 5.0 4.5 N1 cellulase 6.2 <0.5 N4 cellulase 5.0 <0.5

Example 2: Results of the pulp degradation test

The pulp degradation test described above was carried out using various cellulases. The values given in Table 2 (mean values from 2 determinations in each case) resulted from the absorption difference (Delta A). It can be seen that both cellulases meet the criteria for a second cellulase component according to the invention. Absorption difference in the pulp degradation test Cellulase Delta A Celluzyme ^(R) 0.7T 0.236 Denimax ^(R) ultra 0.084

Claims (10)

1. Detergents containing surfactant and a cellulase mixture, characterized in that the first component of the cellulase mixture produces an increase in reflectance in the multiple cycle washing test of at least 5 units for a CMCase activity of 1 U liter and a protein concentration of at most 3 mg per liter and the second component of the cellulase mixture produces an increase in absorption in the cellulase degradation test of at least 0.075 for a CMCase activity of 20 U per liter.
2. Detergents as claimed in claim 1, characterized in that the first component of the cellulase mixture produces an increase in reflectance in the multiple cycle washing test of at least 5 units for a protein concentration of 0.0001 mg per liter to 0.6 mg per liter.
3. Detergents as claimed in claim 1 or 2, characterized in that the first component of the cellulase mixture produces an increase in reflectance in the multiple cycle washing test of 5.0 to 10.0 units.
4. Detergents as claimed in any of claims 1 to 3, characterized in that the second component of the cellulase mixture produces an increase in absorption in the cellulose degradation test of at least 0.075 at a protein concentration of at most 20 mg per liter.
5. Detergents as claimed in any of claims 1 to 4, characterized in that the ratio by weight of the first component to the second component, based on protein, is from 1:100 to 1:10 and, more particularly, from 1:60 to 1:20.
6. A washing process, characterized in that a cellulase mixture of which the first component produces an increase in reflectance in the multiple cycle washing test of at least 5 units for a CMCase activity of 1 U per liter and a protein concentration of at most 3 mg per liter and of which the second component produces an increase in absorption in the cellulose degradation test of at least 0.075 for a CMCase activity of 20 U per liter is allowed to act on fabrics in aqueous, more particularly surfactant-containing solution.
7. A process as claimed in claim 6, characterized in that the ratio by weight of the first component mentioned to the second component mentioned in the aqueous solution, based on protein, is from 1:100 to 1:10 and, more particularly, from 1:60 to 1:20.
8. The use of the detergent claimed in any of claims 1 to 6 in the process claimed in claim 6 or 7.
9. A test for finding cellulase mixtures suitable for use in detergents, the first component being determined by carrying out a multiple cycle washing test and selecting a cellulase which produces an increase in reflectance in the multiple cycle washing test of at least 5 units and, more particularly, between 5.0 to 10.0 units for a CMCase activity of 1 U per liter and at a protein concentration of at most 3 mg per liter and the second component being determined by carrying out the cellulose degradation test and selecting a cellulase which produces an increase in absorption in the cellulose degradation test of at least 0.075 for a CMCase activity of 20 U per liter.
10. The use of cellulase mixtures of which the first component produces an increase in reflectance in the multiple cycle washing test of at least 5 units for a CMCase activity of 1 U per liter and at a protein concentration of at most 3 mg per liter while the second component produces an increase in absorption in the cellulose degradation test of at least 0.075 for a CMCase activity of 20 U per liter for the production of detergents.