DE4224947A1 - Particulate washing compsn. contg. synthetic anionic sulphate or sulphonate tenside - nonionic tenside, water soluble organic builder, water insol. inorganic builder, protease and cellulase - Google Patents

Abstract

Compsn. contains (a) 12-25 wt.% of synthetic sulphate and/or sulphonate anionic surfactant, (b) nonionic surfactant in ratio of (a) to (b) of 1.5-6:1, (c) a water-soluble organic builder, (d) a water-insol. inorganic builder, (e) protease to give proteolytic activity of 500-2000 PF/g, and (f) cellulase to give cellulolytic activity of 1-14 CEVU/g. Pref., (a) the component is above 15 (16-22) wt.% of alkylbenzene sulphonate with linear 9-15C alkyl gps., alpha-sulpho esters from 8-22C (12-18C) fatty acids and 1-6C (1-4C) linear alcohols, or sulpho-fatty acid di-salts from these, ether sulphates and/or 10-20C (12-18C) prim. alkyl sulphates, esp. 12-19% of alkylbenzene sulphonate and 1-5% of alkyl sulphate, or up to 25% (10-25%) of anionic tenside comprising solely alkyl sulphate, or contg. a small amt., pref. not above 30%, w.r.t. the alkyl sulphate, of ether sulphate and/or alkylbenzene sulphonate. (b) The component is 2-15% of an alkylglycoside and/or alkoxylate, esp. an ethoxylate and/or propoxylate of a 10-22C (12-18C) alcohol, with degree of alkoxylation of 1-20 (3-10). Part, esp. below 50% (10-35%), is an alkoxylate of an unsatd. fatty alcohol. The component may be a mixt. of more than 50% (60-90%) of an alkoxylate of a fatty alcohol with degree of alkoxylation below 7 (4-6), and an alkoxylate of a fatty alcohol with degree of alkoxylation above 7 (9-12). The ratio of (a) or (b) is 3-6:1 (4-5:1). ADVANTAGE - The compsn. does not affect fabrics or colours, has high cleaning power, gives a softer wash, and can be stored for several months without change in properties.

Description

The invention relates to particulate detergents, the anionic surfactant Sulfate and / or sulfonate type, nonionic surfactant, water soluble or ganic builder, water-insoluble inorganic builder, proteolytic enzyme and cellulolytic enzyme included.

Detergents and washing aids that contain enzymes have been around since known for a long time. In particular, proteolytic enzymes have been used for over Used in textile detergents for 60 years and have proven to be very clean Proven cleaning ingredient against protein soiling. The the beneficial effect of cellulolytic enzymes is opposite not primarily in the field of removing textile stains, son Rather, it relies on the fabric softening, color refreshing and tex Properties of this enzyme which improve the surface image. Cellulase detergents containing are, for example, from the European patent applications EP 120 528, relating to a fabric softening detergent, wel ches 2 to 50 wt .-% anionic surfactant and / or nonionic surfactant, 0.5 to Contains 15% by weight of a tertiary amine and a cellulase, EP 177 165, regarding a fabric softening detergent containing a clay mineral and contains cellulase, EP 173 398, relating to a detergent, the Cellu lase and a mono- or di-long chain, primary or secondary amine contains, EP 173 397, relating to an alkaline detergent containing 2 to 50% by weight anionic surfactant and / or nonionic surfactant, 0.5 to 15% by weight cationic fabric softener, up to 80% by weight builder and a cellula contains mushrooms, and EP 269 169, relating to a detergent which Cellulase and a diamine or polyamine with tertiary nitrogen or one contains corresponding ammonium compound, known. These well-known means have a cleaning performance that is not always satisfactory the disadvantage that in addition to the fabric softening cellulase  fabric softening substances must be used. There is also at simultaneous presence of cellulase and because of its good cleaning performance preferred anionic surfactants of the sulfate or sulfonate type in Detergent increases the risk of enzyme deactivation and thus loss Softening performance, which in the presence of proteoly tical enzyme is enhanced.

It was therefore the task of a highly cleaning-efficient builder, Detergent containing anionic surfactant and nonionic surfactant wrap, which is soft to avoid the disadvantages mentioned contains cellulase and protein-removing protease.

This task was accomplished by optimizing the surfactant system certain mixture of synthetic anionic surfactant from sulfate and / or Dissolved sulfonate type and nonionic surfactant.

The invention therefore relates to a particulate enzyme-containing enzyme Detergent containing synthetic anionic surfactant from sulfate and / or Sulfonate type, non-ionic surfactant, water-soluble organic builders substance, water-insoluble inorganic builder substance, proteolytic Enzyme and cellulolytic enzyme, which is characterized in that it 12% to 25% by weight anionic surfactant and so much nonionic surfactant contains the weight ratio of anionic surfactant to nonionic Surfactant is 1.5: 1 to 6: 1, and protease in such an amount considers that it has a proteolytic activity of 500 PE / g to 2000 PE / g and Contains cellulase in such an amount that it is a cellulolytic Activity from 1 CEVU / g to 14 CEVU / g, preferably 1 CEVU / g to 8 CEVU / g having.

The particulate detergents according to the invention contain synthetic anionic surfactants of the sulfate or sulfonate type in amounts of from 12% by weight to 25% by weight, preferably above 15% by weight and in particular from 16% by weight to 22% by weight. %. Suitable sulfonate surfactants are, in particular, alkylbenzene sulfonates with linear C ₉ to C ₁₅ alkyl groups on the benzene nucleus, which are present as alkali metal or ammonium salts. Suitable anionic surfactants of the sulfonate type also include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, and the sulfofatty acid disalts derivable from these.

Useful sulfate-type surfactants include, in particular, primary ones Alkyl sulfates with preferably linear alkyl radicals with 10 to 20 carbon atoms, which is an alkali, ammonium or alkyl or hydroxyalkyl sub have substituted ammonium ion as a counter cation. Are particularly suitable the derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. Useful Accordingly, the sulfation products of primary fatty alcohols in particular with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and their mixtures. Particularly preferred alkyl sulfates contain tallow alkyl radical, that is mixtures with essentially hexadecyl and octa decyl residues. The alkyl sulfates can in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, especially sulfur trioxide or chlorosulfonic acid, and subsequent new tralization with alkali, ammonium or alkyl or hydroxy alkyl-substituted ammonium bases can be produced.

In addition, the sulfated alkoxylation products of the Al alcohols, so-called ether sulfates, can be contained in the agents. Preferential such ether sulfates contain 2 to 30, in particular 4 to 10, Ethylene glycol groups per molecule.

The agents according to the invention preferably contain 12% by weight to 19% by weight alkyl benzene sulfonate and 1% by weight to 5% by weight alkyl sulfate.

In a further preferred embodiment contains a fiction moderate average up to 25% by weight, in particular 10% by weight to 25% by weight, Anionic surfactant, which preferably consists entirely of alkyl sulfate, however small proportions, especially not more than 30 wt .-%, based on the Alkyl sulfate component, other anionic surfactant, especially ether sulfate and / or alkylbenzenesulfonate.  

To the nonionic surfactants in question, which in the Invention contemporary agents preferably in amounts of 2 wt .-% to 15 wt .-% and ins Particular from 3% to 8% by weight are included include alkyl glycosides and the alkoxylates, especially the ethoxylates and / or propoxylates of linear or branched chain alcohols with 10 to 22 carbon atoms, preferred have 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols lies here between 1 and 20, preferably between 3 and 10. You can in known Way by reacting the corresponding saturated or unsaturated Alcohols are prepared with the corresponding alkylene oxides, where the alkoxy used in connection with the present invention Degree of lation corresponds to the molar ratio of alcohol to alkylene oxide. Derivatives of fatty alcohols are particularly suitable, although also their branched chain isomers for the preparation of alkoxylates which can be used can be used. Accordingly, ethoxy in particular can be used late primary alcohols with linear dodecyl, tetradecyl, or hexadecyl Octadecyl residues and their mixtures. It is advantageous if a Part, preferably below 50 wt .-% and in particular 10 wt .-% to 35 wt .-% of the nonionic surfactants used an alkoxylation pro product, especially an ethoxylation product, one or more un saturated fatty alcohol, such as oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and Eruca include alcohol is. In addition, corresponding ethoxylation and / or Propoxylation products of alkylamines, vicinal diols and carboxylic acid amides which correspond to the alcohols mentioned with regard to the alkyl part usable. The erfin have particularly good cleaning properties Agents according to the invention if the nonionic surfactant component from a Ge mixed low alkoxylated fatty alcohols (degree of alkoxylation below 7, before preferably 4 to 6) with higher alkoxylated fatty alcohols (alkoxylation degree above 7, preferably 9 to 12), in which more than 50% by weight, in particular 60% by weight to 90% by weight of the low alkoxylated fraction is included.

With the anionic surfactants and nonionic surfactants mentioned it is important that they are in the inventive compositions in weight ratios of Anionic surfactant to nonionic surfactant from 1.5: 1 to 6: 1, preferably 3: 1 to 6: 1 and in particular 4: 1 to 5: 1 are included.  

In addition to the surfactants mentioned, the agents according to the invention preferably contain up to 6% by weight of soap, that is to say an alkali metal or ammonium salt of a C ₈ -C ₂₂ -carboxylic acid. A particularly good washing-in behavior of the agents is observed with soap contents of at least 2% by weight. Such soap contents are therefore particularly preferred and also because of the foam-regulating effect.

The cellulase which can be used according to the invention can be one of bacteria or Pil zen recoverable enzyme, which is a pH optimum preferably in the fast has neutral to weakly alkaline range from 6 to 9.5. Derarti ge cellulases are, for example, from the German published documents DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or the European Patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 known. They are in the agent according to the invention in sol Chen amounts used that the finished agent a cellulolytic Akti Quantity from 1 CEVU / g to 14 CEVU / g ("Cellulose Viscosity Units" per gram, based on the enzymatic hydrolysis of carboxymethyl cellulose pH 9.0 and 40 ° C, as described in Novo Nordisk publication AF 253), preferably 1.1 CEVU / g to 4.5 CEVU / g and in particular 1.5 CEVU / g to 4 CEVU / g.

The protease which can be used according to the invention is also a microorganism Men, especially bacteria or fungi, recoverable enzyme with a pH optimum in the alkaline range. Suitable proteases are, for example from international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 are known. Protease is invented agents used in such amounts that the finished agent 500 PE / g to 2000 PE / g (protease units per gram, determined according to the in Tenside 7, 125 (1970) described method), preferably 600 PE / g bis 1800 PE / g and in particular 750 PE / g to 1250 PE / g.

The enzymes mentioned are particulate in the invention Detergents in the form adsorbed on carrier substances, in coating substances bedded or in the form of conventional granules with inorganic and / or orga African carrier materials, such as in the German patent  document DE 16 17 232, the German patent application DT 20 32 766 or DE 40 41 752 or the European patent applications EP 168 526, EP 170 360, EP 270 608 or EP 304 331 described used. Here Cellulase and protease can be contained in two separate particles or in the form of a multi-enzyme granulate, such as in the inter national patent applications WO 90/09440 or WO 90/09428 as well as there described cited prior art, are used.

The agents according to the invention contain as water-insoluble, water dis pergeable inorganic builder material crystalline or amorphous Al Potassium aluminosilicate in amounts of preferably 10 to 65% by weight, in particular 12 to 60% by weight and particularly preferably from 45 to 55% by weight. Among the are the crystalline aluminosilicates, in particular zeolite NaA and NaX, prefers. Suitable aluminosilicates in particular have no particles a grain size over 30 microns and preferably exist at least 80 wt .-% of particles with a size below 10 microns. Your calcium binder like that be according to the details of German Patent DE 24 12 837 can be agreed, is in the range of 100 to 200 mg CaO per gram.

In addition to the inorganic builder mentioned, other water soluble Liche or water-insoluble inorganic substances in the Invention appropriate means are used. In this context, the Alkali silicates, alkali carbonates, alkali hydrogen carbonates and alkali sulfates as well as their mixtures. Such additional inorganic material can in amounts up to 60% by weight, preferably up to 30% by weight and in particular from 1% to 15% by weight.

Suitable water-soluble organic builder substances are in particular those from the class of polycarboxylic acids, especially citric acid as well as polymeric acrylic acids, methacrylic acids, maleic acids and mixed poly mere from these, which also contain small proportions of polymerizable substances may contain copolymerized without carboxylic acid functionality. The Acids mentioned are usually in the form of their alkali salts, esp special their sodium or potassium salts used. Such organic Builder substances are preferably in amounts of 1% by weight to 10% by weight,  in particular from 2% by weight to 8% by weight and particularly preferably from Contain 2.5 wt .-% to 5.5 wt .-%.

The agents according to the invention normally have a pH (1-ge weight percent solution in distilled water) from 8.5 to 11. For Adjustment of a weakly alkaline pH, if desired, from in particular especially about 8.0 to 9.5 in 1 weight percent aqueous solution the agents according to the invention solid inorganic and / or organic acids or acidic salts, for example alkali hydrogen sulfates, succinic acid, Adipic acid or glutaric acid. Such acidic substances are in the agents according to the invention preferably not in amounts 6 wt .-%, in particular from 1 wt .-% to 5 wt .-%, contain.

In addition, the agents according to the invention can be used in detergents contain customary ingredients, in particular other surfactants, preferably amphoteric surfactants, complexing agents for heavy metals, for example se aminopolycarboxylic acids and / or polyphosphonic acids or their salts, Graying inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinylpyrrolidone, and foam inhibitors, for example organopolysiloxanes or paraffins. Such In In the agents according to the invention, substances can be present in amounts of up to 5 wt .-%, in particular from 0.1 wt .-% to 4 wt .-% may be included. The incorporation of further enzymes, including lipase in particular computing is possible.

The preparation of the agents according to the invention can be known in principle Way made by spray drying aqueous slurries those that contain the thermally resilient ingredients, and on final mixing of the base powder obtained with the thermal sensitive components, primarily the enzymatic ones Ingredients, but also colors and fragrances belong in a usual Mixer, in particular a drum, roller, belt or free-fall mixer, with liquid or liquefied constituents added by spraying can be mixed. Spray drying for surfactant and builder maintenance Aqueous slurry carrying basic powder is usually carried out systems intended for this purpose, so-called spray towers, in their upper part  the slurry is sprayed into fine droplets by pressure nozzles, the under the influence of gravity in the lower part of the spray tower move and come into contact with hot drying gases, which in the Co-current or preferably counter-current to the parts to be dried be led out.

The particulate detergents according to the invention thus produced have preferably bulk weights of 300 g / l to 600 g / l. They are color and gentle to the application, excellent cleaning performance results in significantly softer laundry than correspondingly built, cellulase-free or a non-inventive surfactant system containing detergents and also lose their positive properties after storage for several months.  

Examples

example 1

Table 1

Composition of funds [% by weight]

Means M1 characterized in Table 1 by their composition to M3 with the properties given in Table 2 were by Ver Mix a spray-dried base powder, which contains the components 1) to 15) and was subsequently sprayed onto component 16) was produced with components 17) to 18). The specified quantities Shares relate to finished funds.

Table 2

properties

Claims (13)

1. Particulate enzyme-containing detergent containing synthetic anionic surfactant of the sulfate and / or sulfonate type, nonionic surfactant, water-soluble organic builder substance, water-insoluble inorganic builder substance, characterized in that it contains 12% by weight to 25% by weight anionic surfactant and so on much nonionic surfactant that the weight ratio of anionic surfactant to nonionic surfactant is 1.5: 1 to 6: 1, and protease in such an amount that it has a proteolytic activity of 500 PE / g to 2000 PE / g and cellulase in contains such an amount that it has a cellulolytic activity of 1 CEVU / g to 14 CEVU / g. 2. Composition according to claim 1, characterized in that it contains over 15% by weight, in particular from 16% by weight to 22% by weight, of anionic surfactant in the form of alkylbenzenesulfonate with linear C ₉ -C ₁₅ -alkyl groups are derived from fatty acids with 8 to 22 carbon atoms, in particular 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, α-sulfoesters, the sulfo fatty acid derivatives which can be derived from these , Ether sulfate and / or primary alkyl sulfate containing 10 to 20 carbon atoms, in particular 12 to 18 carbon atoms. 3. Means according to claim 1 or 2, characterized in that it 12% by weight to 19% by weight of alkylbenzenesulfonate and 1% by weight to 5% by weight Contains alkyl sulfate or up to 25 wt .-%, in particular 10 wt .-% to 25 wt .-%, contains anionic surfactant, either completely from alkyl sul fat exists or small proportions, in particular not more than 30% by weight, based on the alkyl sulfate component, ether sulfate and / or alkyl benzenesulfonate. 4. Agent according to one of claims 1 to 3, characterized in that it 2% by weight to 15% by weight of nonionic surfactant in the form of alkylgly cosides and / or alkoxylates, in particular ethoxylates and / or Propoxylates of linear or branched chain alcohols with 10 to 22 carbon atoms, in particular 12 to 18 carbon atoms, in which the alkoxylie  degree of alcohol between 1 and 20, in particular between 3 and 10 is included. 5. Agent according to one of claims 1 to 4, characterized in that a part, especially below 50 wt .-% and preferably 10 wt .-% to 35% by weight of the nonionic surfactant is an alkoxylation product mono- or polyunsaturated fatty alcohol. 6. Agent according to one of claims 1 to 5, characterized in that the nonionic surfactant component from a mixture of low alkoxy gated fatty alcohol with a degree of alkoxylation below 7, in particular 4 to 6, with a higher alkoxylated fatty alcohol with a Degree of alkoxylation above 7, in particular 9 to 12, in which more than 50 wt .-%, in particular 60 wt .-% to 90 wt .-% of the lower alk oxylated portion is included. 7. Composition according to one of claims 1 to 6, characterized in that the weight ratio of anionic surfactant to nonionic surfactant 3: 1 to 6: 1 and in particular 4: 1 to 5: 1. 8. Agent according to one of claims 1 to 7, characterized in that it has a proteolytic activity of 600 PE / g to 1800 PE / g, in particular which has from 750 PE / g to 1250 PE / g. 9. Agent according to one of claims 1 to 8, characterized in that it prefers a cellulolytic activity of 1 CEVU / g to 8 CEVU / g 1.1 CEVU / g to 4.5 CEVU / g and in particular from 1.5 CEVU / g to 4 CEVU / g having. 10. Composition according to one of claims 1 to 9, characterized in that it contains 2 wt .-% to 6 wt .-% of an alkali or ammonium salt of a C ₈ - to C ₂₂ carboxylic acid. 11. Agent according to one of claims 1 to 10, characterized in that it 10 to 65 wt .-% crystalline or amorphous alkali alumosilicate, until 60% by weight of further water-soluble or water-insoluble inorganic  Substances, 1 wt .-% to 10 wt .-% polycarboxylic acid salts as water-soluble organic builders and not more than 6% by weight solid anor contains ganic and / or organic acids or acidic salts. 12. Composition according to claim 11, characterized in that it is 12 wt .-% to 60% by weight, in particular 45% by weight to 55% by weight, of alkali alumosilicate, up to 30% by weight, in particular 1% by weight to 15% by weight, of further water soluble or water-insoluble inorganic substances, and 2% by weight up to 8% by weight, in particular 2.5% by weight to 5.5% by weight, of polycarboxylic acid contains salts. 13. Composition according to one of claims 1 to 12, characterized in that it 1 wt .-% to 5 wt .-% solid inorganic and / or organic acids or contains acidic salts.