EP0694060B1 - Enzymatic washing agent - Google Patents

Enzymatic washing agent Download PDF

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Publication number
EP0694060B1
EP0694060B1 EP94913117A EP94913117A EP0694060B1 EP 0694060 B1 EP0694060 B1 EP 0694060B1 EP 94913117 A EP94913117 A EP 94913117A EP 94913117 A EP94913117 A EP 94913117A EP 0694060 B1 EP0694060 B1 EP 0694060B1
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EP
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Prior art keywords
weight
detergent
activity
washing
surfactant
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EP94913117A
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German (de)
French (fr)
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EP0694060A1 (en
Inventor
Heidi Andexer
Horst Upadek
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the invention relates to an enzyme-based detergent which contains protease, lipase, amylase and cellulase and optionally surfactant and / or builder.
  • Detergents and washing aids that contain enzymes have been known for a long time.
  • proteolytic enzymes have been used in textile detergents for over 60 years and have proven to be a very effective cleaning component against protein soiling.
  • Detergents which, in addition to protease, additionally contain amylase as an active ingredient for removing starch-based soiling are known, for example, from German Offenlegungsschrift DE 27 27 463.
  • EP 478 050 relating to a preferably liquid detergent with lipase and a stabilizer, which reversibly complexes with the catalytically active site of the enzyme
  • EP 468 102 relating to detergents with anionic and / or nonionic surfactant and lipase from Pseudomonas plantarii and optionally Builder
  • EP 381 431 relating to aqueous liquid detergents with certain lipase, 0.1-10% polyalkylene glycol ester and 5-35% surfactant and optionally protease
  • EP 376 705 relating to liquid detergents with 10-90% surfactant, which consists of at least 50% non-ionic surfactant, 1-10% C 1-4 alcohol, 0.1-5% C 1-3 carboxylic acid, lipase and protease
  • EP 373 850 Detergent which contains 1-60% by weight of surfactants
  • Cellulase-containing detergents are known, for example, from European patent applications EP 120 528, relating to a textile-softening detergent which contains 2 to 50% by weight of anionic surfactant and / or nonionic surfactant, 0.5 to 15% by weight of a tertiary amine and a cellulase 177 165, relating to a fabric softening detergent which contains a clay mineral and cellulase, EP 173 398, relating to a detergent containing cellulase and a mono- or di-long-chain, primary or secondary amine, EP 173 397, relating to an alkaline detergent which Contains 2 to 50% by weight of anionic surfactant and / or nonionic surfactant, 0.5 to 15% by weight of cationic fabric soften
  • Detergents which contain a combination of enzymes are also known, for example the combination of 0.1 to 2% by weight of protease, 0.2 to 1% by weight of cellulase and up to 2% by weight of amylase European patent application EP 365 103 and the combination of protease, amylase and lipase or cellulase from European patent application EP 425 214, which also discloses agents with the combination of all four of the enzymes mentioned.
  • the US Pat. No. 4,566,985 relates to liquid agents which contain protease, amylase, lipase and cellulase.
  • Japanese patent application JP-A-62/269 684 discloses a process for the preparation of enzyme granules which may contain protease, amylase, lipase or cellulase.
  • Japanese patent application JP-A-05 025 776 relates to textiles which clean themselves largely without washing, which is to be achieved by applying protease, lipase, amylase and cellulase to the textile. The latter can be done by bringing an aqueous solution of the four enzymes mentioned into contact with the textile.
  • International patent application WO 92/18597 discloses polyvinylpyrrolidone-containing detergents with a high bulk density, which may contain protease, lipase, amylase and cellulase.
  • the invention accordingly relates to an enzyme-containing detergent, containing protease, lipase, amylase and cellulase, which is in particle form and does not contain more than 5% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and / or not more than 20% by weight.
  • -% Builder contains, where the enzymes are used in granular form, adsorbed on carrier materials.
  • Another object of the invention is the use of an enzymatic washing aid which contains not more than 5% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and / or not more than 20% by weight of builder and which has a proteolytic activity of in particular 10,000 PE / g to 75,000 PE / g, a lipolytic activity of in particular 10,000 LU / g to 90,000 LU / g, an amylolytic activity of in particular 1 KNU / g to 20 KNU / g and a cellulolytic activity of in particular 5 IU / g to 150 IU / g, as a cleaning-enhancing additive to detergents or bleaches or aqueous liquors which contain detergents or bleaches.
  • an enzymatic washing aid which contains not more than 5% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and / or not more than 20% by weight of builder and which has a
  • the protease which can be used according to the invention is an enzyme which can be obtained from microorganisms, in particular bacteria or fungi, with an optimum pH in the alkaline range. Suitable proteases are known, for example, from international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or European patent applications EP 471 265, EP 416 967 or EP 394 352.
  • Protease is preferably used in the agent according to the invention in amounts such that the finished agent 10,000 PE / g to 75,000 PE / g (protease units per gram, determined according to the method described in Tenside 7, 125 (1970)), in particular 12 500 PE / g to 65,000 PE / g and particularly preferably 15,000 PE / g to 45,000 PE / g.
  • Usable proteases are commercially available, for example under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase® or Alcalase®.
  • the lipase contained in the agent according to the invention is also an enzyme that can be obtained from microorganisms, in particular bacteria or fungi. Such are known, for example, from European patent applications EP 204 208, EP 214 761, EP 258 068, EP 407 225 or international patent application WO 87/859.
  • Useful lipases commercially available include Lipolase® and Lipozym®.
  • Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10,000 LU / g to 90,000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 after the method mentioned in EP 258 068), in particular 15,000 LU / g to 80,000 LU / g and particularly preferably 20,000 LU / g to 55,000 LU / g.
  • the amylase which can be used according to the invention is an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the alkaline range up to about pH 10.
  • Useful commercial products include Termamyl® and Maxamyl®.
  • Amylase is preferably used in the agent according to the invention in amounts such that the finished agent 1 KNU / g to 20 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme, degrades the 5.26 g starch at pH 5.6 and 37 ° C, based on the method described by P.
  • the cellulase which can be used according to the invention is an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the almost neutral to weakly alkaline pH range from 6 to 9.5.
  • Such cellulases are known, for example, from German published applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 known.
  • the agent according to the invention are preferably used in the agent according to the invention in amounts such that the finished agent has a cellulolytic activity of 5 IU / g to 150 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na carboxymethyl cellulose at pH 9.0 and 40 ° C as described in Agric. Biol. Chem. 53 , 1275 (1989) by S. Ito et al. ), in particular 7.5 IU / g to 140 IU / g and particularly preferably 12 IU / g to 130 IU / g.
  • Suitable commercial products include Celluzyme® from Novo Industri or KAC® from Kao.
  • the presence of conventional enzyme stabilizers such as, for example, boron compounds, for example organoboronic acids or boric acid or alkali borates, alkali metal carboxylates, for example sodium formate, glycols, for example glycerol, ethylene glycol or propylene glycol, amino alcohols, for example mono-, di- or triethanol or propanolamine , or alkaline earth metal ions, for example calcium ions, may be desirable.
  • boron compounds for example organoboronic acids or boric acid or alkali borates
  • alkali metal carboxylates for example sodium formate
  • glycols for example glycerol
  • amino alcohols for example mono-, di- or triethanol or propanolamine
  • alkaline earth metal ions for example calcium ions
  • the detergents according to the invention are in particle form.
  • the enzymes mentioned are embedded in a form adsorbed on carrier substances, in coating substances or in the form of customary granules with inorganic and / or organic carrier materials, such as, for example, in German patent specification DE 16 17 232, German patent application DT20 32 766 or DE 40 41 752 or the European patent applications EP 168 526, EP170 360, EP 270 608 or EP 304 331 are used.
  • the enzymes can be contained separately in up to four separate particles or in the form of multi-enzyme granules, as described, for example, in international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein.
  • the detergents according to the invention can contain all known ingredients that are usually present in detergents.
  • only surfactant and / or builder is preferably present, these also being able to be used in significantly smaller amounts than is customary in conventional detergents.
  • the detergents according to the invention contain no more than 10% by weight, in particular from 0.5% by weight to 5% by weight, based on the total agent, of surfactant.
  • builders and surfactants are preferably entirely absent.
  • the surfactant optionally contained in the agents according to the invention is anionic, nonionic, cationic or amphoteric surfactant or mixtures thereof, preferably nonionic surfactant of the alkyl polyalkoxylate type, optionally in a mixture with synthetic anionic surfactant of sulfate or sulfonate. Type is used.
  • the nonionic surfactants in question include alkyl glycosides and the alkoxylates, in particular the ethoxylates and / or propoxylates of 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 between 1 and 20, preferably between 3 and 10.
  • fatty alcohols can be prepared in a known manner by reacting the corresponding saturated or unsaturated alcohols with the corresponding alkylene oxides.
  • Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers can also be used to prepare usable alkoxylates. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • the alkoxylation products in particular the ethoxylation products, of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and eruca alcohol, can be used.
  • ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used.
  • the ethoxylation and / or propoxylation products of fatty acid C 1 to C 4 alkyl esters such as can be prepared by the process described in international patent application WO 90/13533, and / or fatty acid polyhydroxyamides, as are used in the international patent application WO 92/6984 can be used.
  • the agents according to the invention have particularly good cleaning properties if the nonionic surfactant component is an alkoxylated, in particular ethoxylated, fatty alcohol with an average degree of alkoxylation of 5 to 10, preferably 6 to 8.
  • Suitable sulfonate surfactants are, in particular, alkylbenzenesulfonates 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 the ⁇ -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 having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, and the sulfofatty acid disalts derivable from these.
  • the useful surfactants of the sulfate type include, in particular, primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation.
  • the derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octadecyl radicals.
  • the alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • ether sulfates can be present in the compositions.
  • Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • the agents according to the invention can contain up to 40% by weight, preferably not more than 20% by weight and in particular 1% by weight to 5% by weight, of builder.
  • Suitable water-soluble organic builder substances are, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the acids mentioned are usually in the form of their alkali metal salts, in particular their sodium or potassium salts used.
  • Such organic builder substances are preferably present in amounts of up to 30% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight.
  • crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of not more than 40% by weight, preferably not more than 20% by weight and in particular from 1% by weight to 5% by weight.
  • the crystalline aluminosilicates in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, granular detergents.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • alkali silicates alkali carbonates, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable.
  • additional inorganic material can be present in amounts up to 10% by weight, but is preferably absent entirely.
  • the agents according to the invention can be used to set a weakly alkaline pH, if desired, in particular from about 8.0 to 9.5 in 1% by weight aqueous solution, solid inorganic and / or organic acids or acidic salts, for example alkali metal bisulfates, succinic acid, adipic acid or glutaric acid and the like Mixtures included.
  • Such Acidic substances are contained in the agents according to the invention preferably in amounts not exceeding 5% by weight, in particular from 0.1% by weight to 3% by weight.
  • the detergents according to the invention can contain further constituents customary in detergents, in particular complexing agents for heavy metals, for example aminopolycarboxylic acids and / or polyphosphonic acids or salts thereof, graying inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinylpyrrolidone, foam inhibitors, for example organopolysiloxanes or paraffins, and further ene , in particular oxidase, peroxidase and / or collagenase, belong.
  • Such ingredients can be present in the agents according to the invention in amounts of up to 5% by weight, in particular from 0.1% to 4% by weight.
  • the agents according to the invention can be produced in the simplest manner by mixing the enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery components and, if desired, also liquid or liquefied components, in particular nonionic surfactants , but also colors and fragrances belong, can be mixed by spraying.
  • the detergent according to the invention is to contain further components in addition to the enzymatic active ingredients, it is preferred to convert these components, insofar as they are thermally resilient, into a powder product in a known manner by spray drying an aqueous slurry and to mix this with the enzymatic active ingredients and optionally further ones to mix thermally sensitive components, which include bleaching agents, for example alkali perborates or alkali percarbonate.
  • thermally sensitive components which include bleaching agents, for example alkali perborates or alkali percarbonate.
  • the incorporation of the other ingredients by admixing a granulate or extrudate containing them with the enzymatic ingredients is also possible and is particularly preferred for the production of detergents according to the invention with a relatively high bulk density of preferably 650 g / l to 900 g / l.
  • the detergents according to the invention are gentle on the color and fabric, have excellent cleaning performance, possess, probably particularly due to their lipase content, graying-inhibiting action and, probably particularly due to their cellulase content, give soft laundry. It is noteworthy that these positive effects already occur at doses that are significantly below the dosage of about 6 g / l to 8 g / l wash liquor customary for typical European household universal detergents.
  • compositions M1 to M4 characterized in Table 1 below by their composition were prepared by simply mixing the enzyme granules in the stated proportions.
  • Table 1 Composition of funds [% by weight] M1 M2 M3 M4 Protease a) 25th 30th 30th - Protease b) - - - 25th Lipase c) 25th 54 50 25th Amylase d) 25th 10th 12th 25th Cellulase e) 25th 6 8th - Cellulase f) - - - 25th a) BLAP (R) granules (manufacturer Biozym), activity 147,000 PE / g b) BLAP (R) granules (manufacturer Biozym), activity 170,000 PE / g c) Lipolase (R) granules (manufacturer Novo), activity 100,000 LU / g d) Termamyl (R) granules (manu
  • Cotton textile pieces provided with standardized soiling were washed in a launderometer using the washing liquors listed in Table 2 ( W1 : 0.32 g / l sodium lauryl sulfate, 0.16 g / l 7-fold ethoxylated C 12-18 alcohol, 1.2 g / l zeolite Na-A; W2 : W1 and 1.6 g / l enzyme mixture M1 ; W3 : 0.64 g / l sodium lauryl sulfate, 0.32 g / l 7-fold ethoxylated C 12-18 alcohol, 1.2 g / l zeolite Na-A; W4 : W3 and 1.6 g / l enzyme mixture M1 ) washed (test conditions: 2 g soiled fabric and 6 g non-soiled filler fabric, 100 ml washing liquor, water hardness 16 ° d, temperature 40 ° C, Washing time heating time 30 minutes; Evaluation by remission measurement at
  • a liquid detergent containing 25% by weight of 7-fold ethoxylated C 12-18 fatty alcohol, 2% by weight of C 12/14 alkyl glucoside, 5% by weight was used .-% Na-C12 / 14-alkyl sulfate, 16 wt .-% soap, 5 wt .-% glycerol, 7 wt .-% ethanol, balance to 100 wt .-% water, perfume and salts.
  • Example 1 In a commercial household washing machine (Miele W701), the artificial soiling specified in the table below, fixed on barley grain towels, was washed together with 3.5 kg of clean household laundry at 40 ° C (colored washing program normal, water volume 20 l, Düsseldorf city water). The evaluation of the primary washing result was carried out as indicated in Example 1 via the remission (average of 3 determinations). The dosage was 1.5 g / l of the liquid detergent and 1.6 g / l of the agent M4 from Example 1.
  • the washing performance using the washing aid according to the invention was significantly better in all cases than that of the liquid detergent alone, even if 0.1% by weight of amylase (Termamyl (R) LDX 300) and 2% by weight were reduced in it. Protease (Alkalase (R) 2.5 LDX) and incorporated the resulting enzymatic liquid detergent in a significantly higher dosage (4.6 g / l).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

The aim of the invention is to provide a washing agent which is based on enzymes alone and avoids, as far as possible, other usual washing-agent components, and which has a washing power at least equal to that of ordinary washing agents with an optimized composition. The enzymatic washing agent according to the invention contains protease, lipase, amylase and cellulase plus, optionally, small quantities of surfactants and/or builders. Washing agents with this kind of composition can be used as stand-alone washing agents or as washing auxiliaries in addition to ordinary washing agents.

Description

Die Erfindung betrifft ein Waschmittel auf Enzymbasis, welches Protease, Lipase, Amylase und Cellulase sowie gegebenenfalls Tensid und/oder Builder enthält.The invention relates to an enzyme-based detergent which contains protease, lipase, amylase and cellulase and optionally surfactant and / or builder.

Waschmittel und Waschhilfsmittel, welche Enzyme enthalten, sind seit langer Zeit bekannt. Insbesondere proteolytische Enzyme werden seit über 60 Jahren in Textilwaschmitteln eingesetzt und haben sich als sehr reinigungswirksamer Bestandteil gegenüber Eiweißanschmutzungen bewährt. Lediglich beispielhaft sei in diesem Zusammenhang auf die deutsche Offenlegungsschrift DT 16 17 189, aus der Protease- und Bleichmittel-haltige Waschmittel bekannt sind, verwiesen. Waschmittel, die neben Protease zusätzlich Amylase als Wirkstoff zur Entfernung von Anschmutzungen auf Stärkebasis enthalten, sind beispielsweise aus der deutschen Offenlegungsschrift DE 27 27 463 bekannt. Im Zusammenhang mit Waschmitteln, welche Lipase als fettentfernenden Wirkstoff enthalten, sei beispielsweise auf die europäischen Patentanmeldungen EP 478 050, betreffend ein vorzugsweise flüssiges Waschmittel mit Lipase und einem Stabilisator, der mit der katalytisch aktiven Stelle des Enzyms reversibel komplexiert, EP 468 102, betreffend Waschmittel mit anionischem und/oder nichtionischem Tensid und Lipase aus Pseudomonas plantarii sowie gegebenenfalls Builder, EP 381 431, betreffend wäßrige Flüssigwaschmittel mit bestimmter Lipase, 0,1-10 % Polyalkylenglykolester und 5-35 % Tensid sowie gegebenenfalls Protease, EP 376 705, betreffend Flüssigwaschmittel mit 10-90 % Tensid, welches zu mindestens 50 % aus Niotensid besteht, 1-10 % C1-4-Alkohol, 0,1-5 % C1-3-Carbonsäure, Lipase und Protease, EP 373 850, betreffend ein Waschmittel, das neben üblichen Bestandteilen 1-60 Gew.-% Tenside, welche ein primäres Alkylsulfat enthalten, und eine Lipase in bestimmten Mengen enthält, EP 368 589, betreffend granulare Waschmittel mit Lipase, 6-35 Gew.-% seifenfreiem anionischen und/oder nichtionischem Tensid und mindestens 45 Gew.-% Builder, der zu mindestens 28 Gew.-% aus Na-Zeolith, Zitrat, Carbonat und/oder Schichtsilikat besteht, verwiesen.Detergents and washing aids that contain enzymes have been known for a long time. In particular, proteolytic enzymes have been used in textile detergents for over 60 years and have proven to be a very effective cleaning component against protein soiling. In this context, reference is made, by way of example only, to German Offenlegungsschrift DT 16 17 189, from which detergents containing protease and bleaching agents are known. Detergents which, in addition to protease, additionally contain amylase as an active ingredient for removing starch-based soiling are known, for example, from German Offenlegungsschrift DE 27 27 463. In connection with detergents which contain lipase as a fat-removing active ingredient, reference is made, for example, to European patent applications EP 478 050, relating to a preferably liquid detergent with lipase and a stabilizer, which reversibly complexes with the catalytically active site of the enzyme, EP 468 102, relating to detergents with anionic and / or nonionic surfactant and lipase from Pseudomonas plantarii and optionally Builder, EP 381 431, relating to aqueous liquid detergents with certain lipase, 0.1-10% polyalkylene glycol ester and 5-35% surfactant and optionally protease, EP 376 705, relating to liquid detergents with 10-90% surfactant, which consists of at least 50% non-ionic surfactant, 1-10% C 1-4 alcohol, 0.1-5% C 1-3 carboxylic acid, lipase and protease, EP 373 850 Detergent which contains 1-60% by weight of surfactants, which contain a primary alkyl sulfate and a lipase in certain amounts, in addition to the usual ingredients, E P 368 589, relating to granular detergents with lipase, 6-35% by weight of soap-free anionic and / or nonionic surfactant and at least 45% by weight of builder, which consists of at least 28% by weight of Na zeolite, citrate, carbonate and / or layered silicate.

Demgegenüber liegt die vorteilhafte Wirkung von cellulolytischen Enzymen nicht primär auf dem Gebiet der Entfernung von Textilanschmutzungen, sondern beruht eher auf den textilweichmachenden, farbauffrischenden und textiloberflächenbildverbesssernden Eigenschaften dieses Enzyms. Cellulasehaltige Waschmittel sind beispielsweise aus den europäischen Patentanmeldungen EP 120 528, betreffend ein textilweichmachendes Waschmittel, welches 2 bis 50 Gew.-% Aniontensid und/oder nichtionisches Tensid, 0,5 bis 15 Gew.-% eines tertiären Amins und eine Cellulase enthält, EP 177 165, betreffend ein textilweichmachendes Waschmittel, welches ein Tonmineral und Cellulase enthält, EP 173 398, betreffend ein Waschmittel, das Cellulase und ein mono- oder di-langkettiges, primäres oder sekundäres Amin enthält, EP 173 397, betreffend ein alkalisches Waschmittel, das 2 bis 50 Gew.-% Aniontensid und/oder nichtionisches Tensid, 0,5 bis 15 Gew.-% kationischen Gewebeweichmacher, bis zu 80 Gew.-% Builder und eine Cellulase aus Pilzen enthält, und EP 269 169, betreffend ein Waschmittel, das Cellulase und ein Di- oder Polyamin mit tertiärem Stickstoff bzw. eine entsprechende Ammoniumverbindung enthält, bekannt. Auch Waschmittel, welche eine Kombination von Enzymen enthalten, sind bekannt, so zum Beispiel die Kombination aus 0,1 bis 2 Gew.-% Protease, 0,2 bis 1 Gew.-% Cellulase und bis zu 2 Gew.-% Amylase aus der europäischen Patentanmeldung EP 365 103 sowie die Kombination aus Protease, Amylase und Lipase oder Cellulase aus der europäischen Patentanmeldung EP 425 214, welche auch Mittel mit der Kombination aller vier genannten Enzyme offenbart. Die US-amerikanische Patentschrift US 4 566 985 betrifft flüssige Mittel, die Protease, Amylase, Lipase und Cellulase enthalten. Aus der japanischen Patentanmeldung JP-A-62/269 684 ist ein Verfahren zur Herstellung von Enzymgranulaten bekannt, die Protease, Amylase, Lipase oder Cellulase enthalten können. Die japanische Patentanmeldung JP-A-05 025 776 betrifft Textilen, die sich unter weitgehendem Verzicht auf das Waschen selbst reinigen, was durch Aufbringen von Protease, Lipase, Amylase und Cellulase auf das Textil erreicht werden soll. Letzteres kann dadurch geschehen, daß man eine wäßrige Lösung der vier genannten Enzyme mit dem Textil in Kontakt bringt. Aus der internationalen Patentanmeldung WO 92/18597 sind polyvinylpyrrolidonhaltige Waschmittel mit hoher Schüttdichte bekannt, die Protease, Lipase, Amylase und Cellulase enthalten können.In contrast, the advantageous effect of cellulolytic enzymes is not primarily in the field of removing textile stains, but rather is due to the textile softening, color-refreshing and textile surface image-improving properties of this enzyme. Cellulase-containing detergents are known, for example, from European patent applications EP 120 528, relating to a textile-softening detergent which contains 2 to 50% by weight of anionic surfactant and / or nonionic surfactant, 0.5 to 15% by weight of a tertiary amine and a cellulase 177 165, relating to a fabric softening detergent which contains a clay mineral and cellulase, EP 173 398, relating to a detergent containing cellulase and a mono- or di-long-chain, primary or secondary amine, EP 173 397, relating to an alkaline detergent which Contains 2 to 50% by weight of anionic surfactant and / or nonionic surfactant, 0.5 to 15% by weight of cationic fabric softener, up to 80% by weight of builder and a cellulase from fungi, and EP 269 169 relating to a detergent, which contains cellulase and a diamine or polyamine with tertiary nitrogen or a corresponding ammonium compound. Detergents which contain a combination of enzymes are also known, for example the combination of 0.1 to 2% by weight of protease, 0.2 to 1% by weight of cellulase and up to 2% by weight of amylase European patent application EP 365 103 and the combination of protease, amylase and lipase or cellulase from European patent application EP 425 214, which also discloses agents with the combination of all four of the enzymes mentioned. The US Pat. No. 4,566,985 relates to liquid agents which contain protease, amylase, lipase and cellulase. Japanese patent application JP-A-62/269 684 discloses a process for the preparation of enzyme granules which may contain protease, amylase, lipase or cellulase. Japanese patent application JP-A-05 025 776 relates to textiles which clean themselves largely without washing, which is to be achieved by applying protease, lipase, amylase and cellulase to the textile. The latter can be done by bringing an aqueous solution of the four enzymes mentioned into contact with the textile. International patent application WO 92/18597 discloses polyvinylpyrrolidone-containing detergents with a high bulk density, which may contain protease, lipase, amylase and cellulase.

Alle diese bekannten Mittel weisen den Nachteil auf, daß sie außer den Enzymkomponenten eine Vielzahl weiterer Inhaltsstoffe aufweisen, die in ihren Mengen und ihrer Zusammensetzung einer sorgfältigen Optimierung bedürfen, um das gewünschte Reinigungsergebnis zu erhalten. Die Anmelderin hatte sich zum Ziel gesetzt, ein Waschmittel zu entwickeln, welches möglichst allein auf Enzymbasis, unter möglichst weitgehendem Verzicht auf sonstige übliche Waschmittelbestandteile, eine Waschleistung aufweist, welche diejenige von üblichen, in ihrer Zusammensetzung hochoptimierten Waschmitteln zumindest erreicht. Diese Aufgabe wurde durch die Bereitstellung eines Waschmittels mit einer Kombination aus mindestens vier verschiedenartigen Enzymen gelöst.All of these known agents have the disadvantage that they have, in addition to the enzyme components, a large number of other ingredients which, in terms of their amounts and their composition, require careful optimization in order to obtain the desired cleaning result. The applicant had set itself the goal of developing a detergent which, as far as possible on an enzyme basis alone, with the greatest possible avoidance of other conventional detergent components, has a washing performance which at least achieves that of conventional detergents which are highly optimized in their composition. This object was achieved by providing a detergent with a combination of at least four different types of enzyme.

Gegenstand der Erfindung ist demgemäß ein enzymhaltiges Waschmittel, enthaltend Protease, Lipase, Amylase und Cellulase, welches in Partikelform vorliegt und nicht mehr als 5 Gew.-% anionisches, nichtionisches, kationisches und/oder amphoteres Tensid und/oder nicht mehr als 20 Gew.-% Builder enthält, wobei die Enzyme in granularer, an Trägermaterialien adsorbierter Form eingesetzt werden.The invention accordingly relates to an enzyme-containing detergent, containing protease, lipase, amylase and cellulase, which is in particle form and does not contain more than 5% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and / or not more than 20% by weight. -% Builder contains, where the enzymes are used in granular form, adsorbed on carrier materials.

Ein weiterer Gegenstand der Erfindung ist die Verwendung eines enzymatischen Waschhilfsmittels, das nicht mehr als 5 Gew.-% anionisches, nichtionisches, kationisches und/oder amphoteres Tensid und/oder nicht mehr als 20 Gew.-% Builder enthält und das eine proteolytische Aktivität von insbesondere 10 000 PE/g bis 75 000 PE/g, eine lipolytische Aktivität von insbesondere 10 000 LU/g bis 90 000 LU/g, eine amylolytische Aktivität von insbesondere 1 KNU/g bis 20 KNU/g und eine cellulolytische Aktivität von insbesondere 5 IU/g bis 150 IU/g aufweist, als reinigungsverstärkender Zusatz zu Wasch- oder Bleichmitteln beziehungsweise wäßrigen Flotten, die Wasch- oder Bleichmittel enthalten.Another object of the invention is the use of an enzymatic washing aid which contains not more than 5% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and / or not more than 20% by weight of builder and which has a proteolytic activity of in particular 10,000 PE / g to 75,000 PE / g, a lipolytic activity of in particular 10,000 LU / g to 90,000 LU / g, an amylolytic activity of in particular 1 KNU / g to 20 KNU / g and a cellulolytic activity of in particular 5 IU / g to 150 IU / g, as a cleaning-enhancing additive to detergents or bleaches or aqueous liquors which contain detergents or bleaches.

Die erfindungsgemäß brauchbare Protease ist ein aus Mikroorganismen, insbesondere Bakterien oder Pilzen, gewinnbares Enzym mit einem pH-Optimum im alkalischen Bereich. Geeignete Proteasen sind beispielsweise aus den internationalen Patentanmeldungen WO 92/07067, WO 91/02792, WO 88/03947 oder WO 88/03946 oder den europäischen Patentanmeldungen EP 471 265, EP 416 967 oder EP 394 352 bekannt. Protease wird im erfindungsgemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das fertige Mittel 10 000 PE/g bis 75 000 PE/g (Protease-Einheiten pro Gramm, bestimmt nach der in Tenside 7, 125 (1970) beschriebenen Methode), insbesondere 12 500 PE/g bis 65 000 PE/g und besonders bevorzugt 15 000 PE/g bis 45 000 PE/g aufweist. Brauchbare Proteasen sind im Handel erhältlich, beispielsweise unter den Namen BLAP®, Savinase®, Esperase®, Maxatase®, Optimase® oder Alcalase®.The protease which can be used according to the invention is an enzyme which can be obtained from microorganisms, in particular bacteria or fungi, with an optimum pH in the alkaline range. Suitable proteases are known, for example, from international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or European patent applications EP 471 265, EP 416 967 or EP 394 352. Protease is preferably used in the agent according to the invention in amounts such that the finished agent 10,000 PE / g to 75,000 PE / g (protease units per gram, determined according to the method described in Tenside 7, 125 (1970)), in particular 12 500 PE / g to 65,000 PE / g and particularly preferably 15,000 PE / g to 45,000 PE / g. Usable proteases are commercially available, for example under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase® or Alcalase®.

Auch bei der im erfindungsgemäßen Mittel enthaltenen Lipase handelt es sich um aus Mikroorganismen, insbesondere Bakterien oder Pilzen, gewinnbare Enzyme. Solche sind beispielsweise aus den europäischen Patentanmeldungen EP 204 208, EP 214 761, EP 258 068. EP 407 225 oder der internationalen Patentanmeldung WO 87/859 bekannt. Brauchbare im Handel erhältliche Lipasen sind zum Beispiel Lipolase® und Lipozym®. Lipase wird im erfindungsgemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das fertige Mittel 10000 LU/g bis 90 000LU/g ("Lipase-activity Units" pro Gramm, bestimmt über die enzymatische Hydrolyse von Tributyrin bei 30 °C und pH 7 nach der in EP 258 068 genannten Methode), insbesondere 15 000 LU/g bis 80 000 LU/g und besonders bevorzugt 20 000 LU/g bis 55 000 LU/g aufweist.The lipase contained in the agent according to the invention is also an enzyme that can be obtained from microorganisms, in particular bacteria or fungi. Such are known, for example, from European patent applications EP 204 208, EP 214 761, EP 258 068, EP 407 225 or international patent application WO 87/859. Useful lipases commercially available include Lipolase® and Lipozym®. Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10,000 LU / g to 90,000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 after the method mentioned in EP 258 068), in particular 15,000 LU / g to 80,000 LU / g and particularly preferably 20,000 LU / g to 55,000 LU / g.

Die erfindungsgemäß brauchbare Amylase ist ein aus Bakterien oder Pilzen gewinnbares Enzym, welches ein pH-Optimum vorzugsweise im alkalischen Bereich bis etwa pH 10 aufweist. Brauchbare Handelsprodukte sind beispielsweise Termamyl® und Maxamyl®. Amylase wird im erfindungsgemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das fertige Mittel 1 KNU/g bis 20 KNU/g ("Kilo-Novo-Units" pro Gramm gemäß der Standard-Methode der Firma Novo, wobei 1 KNU die Enzymmenge ist, die 5,26 g Stärke bei pH 5,6 und 37 °C abbaut, basierend auf der von P. Bernfeld in S.P. Colowick und N.D. Kaplan, Methods in Enzymology, Band 1, 1955, Seite 149 beschriebenen Methode), insbesondere 1,5 KNU/g bis 18 KNU/g und besonders bevorzugt 3 KNU/g bis 16 KNU/g aufweist.The amylase which can be used according to the invention is an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the alkaline range up to about pH 10. Useful commercial products include Termamyl® and Maxamyl®. Amylase is preferably used in the agent according to the invention in amounts such that the finished agent 1 KNU / g to 20 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme, degrades the 5.26 g starch at pH 5.6 and 37 ° C, based on the method described by P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, page 149), in particular 1.5 KNU / g to 18 KNU / g and particularly preferably 3 KNU / g to 16 KNU / g.

Ebenso ist die erfindungsgemäß brauchbare Cellulase ein aus Bakterien oder Pilzen gewinnbares Enzym, welches ein pH-Optimum vorzugsweise im fast neutralen bis schwach alkalischen pH-Bereich von 6 bis 9,5 aufweist. Derartige Cellulasen sind beispielsweise aus den deutschen Offenlegungsschriften DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 oder den europäischen Patentanmeldungen EP 265 832, EP 269 977, EP 270 974, EP 273 125 sowie EP 339 550 bekannt. Sie werden im erfindungsgemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das fertige Mittel eine cellulolytische Aktivität von 5 IU/g bis 150 IU/g ("International Units" pro Gramm, basierend auf der enzymatischen Hydrolyse von Na-Carboxymethylcellulose bei pH 9,0 und 40 °C, wie in Agric. Biol. Chem. 53, 1275 (1989) von S. Ito et al. beschrieben), insbesondere 7,5 IU/g bis 140 IU/g und besonders bevorzugt 12 IU/g bis 130 IU/g aufweist. Geeignete Handelsprodukte sind beispielsweise Celluzyme® der Novo Industri oder KAC® von Kao.Likewise, the cellulase which can be used according to the invention is an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the almost neutral to weakly alkaline pH range from 6 to 9.5. Such cellulases are known, for example, from German published applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 known. They are preferably used in the agent according to the invention in amounts such that the finished agent has a cellulolytic activity of 5 IU / g to 150 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na carboxymethyl cellulose at pH 9.0 and 40 ° C as described in Agric. Biol. Chem. 53 , 1275 (1989) by S. Ito et al. ), in particular 7.5 IU / g to 140 IU / g and particularly preferably 12 IU / g to 130 IU / g. Suitable commercial products include Celluzyme® from Novo Industri or KAC® from Kao.

In erfindungsgemäßen Mitteln kann die Anwesenheit üblicher Enzymstabilisatoren, wie beispielsweise Borverbindungen, zum Beispiel Organoboronsäuren oder Borsäure beziehungsweise Alkaliborate, Alkalicarboxylate, zum Beispiel Natriumformiat, Glykole, zum Beispiel Glycerin, Ethylenglykol oder Propylenglykol, Aminoalkohole, zum Beispiel Mono-, Di- oder Triethanolbeziehungsweise -propanolamin, oder Erdalkaliionen, zum Beispiel Calciumionen, wünschenswert sein.In the agents according to the invention, the presence of conventional enzyme stabilizers, such as, for example, boron compounds, for example organoboronic acids or boric acid or alkali borates, alkali metal carboxylates, for example sodium formate, glycols, for example glycerol, ethylene glycol or propylene glycol, amino alcohols, for example mono-, di- or triethanol or propanolamine , or alkaline earth metal ions, for example calcium ions, may be desirable.

Die erfindungsgemäßen Waschmittel liegen in Partikelform vor. In derartigen Waschmitteln werden die genannten Enzyme in an Trägerstoffe adsorbierter Form, in Hüllsubstanzen eingebettet oder in Form üblicher Granulate mit anorganischen und/oder organischen Trägermaterialien, wie beispielsweise in der deutschen Patentschrift DE 16 17 232, den deutschen Offenlegungsschriften DT20 32 766 oder DE 40 41 752 oder den europäischen Patentanmeldungen EP 168 526, EP170 360, EP 270 608 oder EP 304 331 beschrieben, eingesetzt. Dabei können die Enzyme separat in bis zu vier getrennten Partikeln enthalten sein oder in Form von Mehrenzym-Granulaten, wie beispielsweise in den internationalen Patentanmeldungen WO 90/09440 oder WO 90/09428 sowie dem dort zitierten Stand der Technik beschrieben, eingesetzt werden.The detergents according to the invention are in particle form. In detergents of this type, the enzymes mentioned are embedded in a form adsorbed on carrier substances, in coating substances or in the form of customary granules with inorganic and / or organic carrier materials, such as, for example, in German patent specification DE 16 17 232, German patent application DT20 32 766 or DE 40 41 752 or the European patent applications EP 168 526, EP170 360, EP 270 608 or EP 304 331 are used. The enzymes can be contained separately in up to four separate particles or in the form of multi-enzyme granules, as described, for example, in international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein.

Die erfindungsgemäßen Waschmittel können zusätzlich zu den enzymatischen Wirkstoffen alle bekannten und üblicherweise in Waschmitteln vorhandenen Inhaltsstoffe enthalten. Vorzugsweise ist jedoch außer den gegebenenfalls stabilisierten Enzymen lediglich Tensid und/oder Builder enthalten, wobei auch diese in deutlich geringeren Mengen als in herkömmlichen Waschmitteln üblich eingesetzt werden können. In der Regel reicht die Anwesenheit sehr geringer Tensidmengen völlig aus, um Waschleistungen zu erzielen, die denen bekannter Universalwaschmittel mit deutlich höheren Tensidgehalten nicht nachstehen. Daher ist in den erfindungsgemäßen Waschmitteln nicht mehr als 10 Gew.-%, insbesondere von 0,5 Gew.-% bis 5 Gew.-%, bezogen auf gesamtes Mittel, Tensid enthalten. In den erfindungsgemäßen Waschhilfsmitteln fehlen Builder und Tensid vorzugsweise ganz. Die nachfolgend genannten Eventualbestandteile und ihre Mengen sind ausschließlich der gegebenenfalls in den Enzympartikeln enthaltenen Mengen derartiger Inhaltsstoffe zu verstehen.In addition to the enzymatic active ingredients, the detergents according to the invention can contain all known ingredients that are usually present in detergents. In addition to the optionally stabilized enzymes, however, only surfactant and / or builder is preferably present, these also being able to be used in significantly smaller amounts than is customary in conventional detergents. As a rule, the presence of very small amounts of surfactant is sufficient to achieve washing performance that is not inferior to that of known universal detergents with significantly higher surfactant contents. Therefore, the detergents according to the invention contain no more than 10% by weight, in particular from 0.5% by weight to 5% by weight, based on the total agent, of surfactant. In the washing aids according to the invention, builders and surfactants are preferably entirely absent. The contingent components mentioned below and their amounts are to be understood exclusively as the amounts of such ingredients that may be contained in the enzyme particles.

Bei dem in den erfindungsgemäßen Mitteln fakultativ enthaltenem Tensid handelt es sich um anionisches, nichtionisches, kationisches oder amphoteres Tensid oder um deren Mischungen, wobei vorzugsweise nichtionisches Tensid vom Alkyl-polyalkoxylat-Typ, gegebenenfalls in Mischung mit synthetischem anionischem Tensid des Sulfat- oder Sulfonat-Typs, eingesetzt wird. Zu den in Frage kommenden nichtionischen Tensiden gehören Alkylglykoside und die Alkoxylate, insbesondere die Ethoxylate und/oder Propoxylate von linearen oder verzweigtkettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Der Alkoxylierungsgrad der Alkohole liegt dabei zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Sie können in bekannter Weise durch Umsetzung der entsprechenden gesättigten oder ungesättigten Alkohole mit den entsprechenden Alkylenoxiden hergestellt werden. Geeignet sind insbesondere die Derivate der Fettalkohole, obwohl auch deren verzweigtkettige Isomere zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß insbesondere die Ethoxylate primärer Alkohole mit linearen Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Auch die Alkoxylierungsprodukte, insbesondere die Ethoxylierungsprodukte, von ein- oder mehrfach ungesättigten Fettalkoholen, zu denen beispielsweise Oleylalkohol, Elaidylalkohol, Linoleylalkohol, Linolenylalkohol, Gadoleylalkohol und Erucaalkohol gehören, sind einsetzbar. Außerdem sind entsprechende Ethoxylierungs- und/ oder Propoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbonsäureamiden, die hinsichtlich des Alkylteils den genannten Alkoholen entsprechen, verwendbar. Auch die Ethoxylierungs- und/oder Propoxylierungsprodukte von Fettsäure-C1-bis-C4-alkylestern, wie sie nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden können, und/oder Fettsäurepolyhydroxyamide, wie sie gemäß der internationalen Patentanmeldung WO 92/6984 hergestellt werden können, sind einsetzbar. Besonders gute Reinigungseigenschaften besitzen die erfindungsgemäßen Mittel, wenn die nichtionische Tensidkomponerte ein alkoxylierter, insbesondere ethoxylierter, Fettalkohol mit einem mittleren Alkoxylierungsgrad von 5 bis 10, vorzugsweise 6 bis 8, ist.The surfactant optionally contained in the agents according to the invention is anionic, nonionic, cationic or amphoteric surfactant or mixtures thereof, preferably nonionic surfactant of the alkyl polyalkoxylate type, optionally in a mixture with synthetic anionic surfactant of sulfate or sulfonate. Type is used. The nonionic surfactants in question include alkyl glycosides and the alkoxylates, in particular the ethoxylates and / or propoxylates of 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 between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding saturated or unsaturated alcohols with the corresponding alkylene oxides. Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers can also be used to prepare usable alkoxylates. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. The alkoxylation products, in particular the ethoxylation products, of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and eruca alcohol, can be used. Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. The ethoxylation and / or propoxylation products of fatty acid C 1 to C 4 alkyl esters, such as can be prepared by the process described in international patent application WO 90/13533, and / or fatty acid polyhydroxyamides, as are used in the international patent application WO 92/6984 can be used. The agents according to the invention have particularly good cleaning properties if the nonionic surfactant component is an alkoxylated, in particular ethoxylated, fatty alcohol with an average degree of alkoxylation of 5 to 10, preferably 6 to 8.

Geeignete Sulfonat-Tenside sind insbesondere Alkylbenzolsulfonate mit linearen C9- bis C15-Alkylgruppen am Benzolkern, die als Alkali- oder Ammoniumsalze vorliegen. Zu den geeigneten Aniontensiden des Sulfonat-Typs gehören weiterhin die durch Umsetzung von Fettsäureestern mit Schwefeltrioxid und anschließender Neutralisation erhältlichen α-Sulfoester, insbesondere die sich von Fettsäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, und linearen Alkoholen mit 1 bis 6 C-Atomen, vorzugsweise 1 bis 4 C-Atomen, ableitenden Sulfonierungsprodukte, sowie die von diesen ableitbaren Sulfofettsäuredisalze.Suitable sulfonate surfactants are, in particular, alkylbenzenesulfonates 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 the α-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 having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, and the sulfofatty acid disalts derivable from these.

Zu den brauchbaren Tensiden vom Sulfat-Typ gehören insbesondere primäre Alkylsulfate mit vorzugsweise linearen Alkylresten mit 10 bis 20 C-Atomen, die ein Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion als Gegenkation besitzen. Besonders geeignet sind die Derivate der linearen Alkohole mit insbesondere 12 bis 18 C-Atomen und deren verzweigtkettiger Analoga, der sogenannten Oxoalkohole. Brauchbar sind demgemäß insbesondere die Sulfatierungsprodukte primärer Fettalkohole mit linearen Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Besonders bevorzugte Alkylsulfate enthalten einen Talgalkylrest, das heißt Mischungen mit im wesentlichen Hexadecyl- und Octadecylresten. Die Alkylsulfate können in bekannter Weise durch Reaktion der entsprechenden Alkoholkomponente mit einem üblichen Sulfatierungsreagenz, insbesondere Schwefeltrioxid oder Chlorsulfonsäure, und anschließende Neutralisation mit Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituierten Ammoniumbasen hergestellt werden.The useful surfactants of the sulfate type include, in particular, primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation. The derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octadecyl radicals. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.

Außerdem können die sulfatierten Alkoxylierungsprodukte der genannten Alkohole, sogenannte Ethersulfate, in den Mitteln enthalten sein. Vorzugsweise enthalten derartige Ethersulfate 2 bis 30, insbesondere 4 bis 10, Ethylenglykol-Gruppen pro Molekül.In addition, the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates, can be present in the compositions. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.

Die erfindungsgemäßen Mittel können bis zu 40 Gew.-%, vorzugsweise nicht über 20 Gew.-% und insbesondere 1 Gew.-% bis 5 Gew.-% Builder enthalten. Geeignete wasserlösliche organische Buildersubstanzen sind insbesondere solche aus der Klasse der Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren sowie polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die genannten Säuren werden üblicherweise in Form ihrer Alkalisalze, insbesondere ihrer Natrium- oder Kaliumsalze eingesetzt. Derartige organische Buildersubstanzen sind vorzugsweise in Mengen bis zu 30 Gew.-%, insbesondere bis zu 25 Gew.-% und besonders bevorzugt von 1 Gew.-% bis 5 Gew.-% enthalten.The agents according to the invention can contain up to 40% by weight, preferably not more than 20% by weight and in particular 1% by weight to 5% by weight, of builder. Suitable water-soluble organic builder substances are, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The acids mentioned are usually in the form of their alkali metal salts, in particular their sodium or potassium salts used. Such organic builder substances are preferably present in amounts of up to 30% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight.

Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von nicht über 40 Gew.-%, vorzugsweise nicht über 20 Gew.-% und insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Alumosilikate, insbesondere Zeolith NaA und gegebenenfalls NaX, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, granularen Waschmitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 µm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 µm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden kann, liegt im Bereich von 100 bis 200 mg CaO pro Gramm. Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline, schichtförmige Alkalisilikate, wie sie beispielsweise in der europäischen Patentanmeldung EP 164 514 beschrieben werden und gemäß dem Verfahren der internationalen Patentanmeldung WO 91/8171 erhalten werden können.In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of not more than 40% by weight, preferably not more than 20% by weight and in particular from 1% by weight to 5% by weight. Among these, the crystalline aluminosilicates, in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, granular detergents. 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 alumosilicate mentioned are crystalline, layered alkali silicates, as are described, for example, in European patent application EP 164 514 and can be obtained by the process of international patent application WO 91/8171.

Zusätzlich zum genannten anorganischen Builder können weitere wasserlösliche oder wasserunlösliche anorganische Substanzen in den erfindungsgemäßen Mitteln eingesetzt werden. Geeignet sind in diesem Zusammenhang die Alkalisilikate, Alkalicarbonate, Alkalihydrogencarbonate und Alkalisulfate sowie deren Gemische. Derartiges zusätzliches anorganisches Material kann in Mengen bis zu 10 Gew.-% vorhanden sein, fehlt jedoch vorzugsweise ganz.In addition to the inorganic builder mentioned, other water-soluble or water-insoluble inorganic substances can be used in the agents according to the invention. In this context, the alkali silicates, alkali carbonates, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable. Such additional inorganic material can be present in amounts up to 10% by weight, but is preferably absent entirely.

Die erfindungsgemäßen Mittel können zur Einstellung eines gewünschtenfalls schwach alkalischen pH-Werts von insbesondere etwa 8,0 bis 9,5 in 1-gewichtsprozentiger wäßriger Lösung feste anorganische und/oder organische Säuren beziehungsweise saure Salze, beispielsweise Alkalihydrogensulfate, Bernsteinsäure, Adipinsäure oder Glutarsäure sowie deren Gemische, enthalten. Derartige saure Substanzen sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen nicht über 5 Gew.-%, insbesondere von 0,1 Gew.-% bis 3 Gew.-%, enthalten.The agents according to the invention can be used to set a weakly alkaline pH, if desired, in particular from about 8.0 to 9.5 in 1% by weight aqueous solution, solid inorganic and / or organic acids or acidic salts, for example alkali metal bisulfates, succinic acid, adipic acid or glutaric acid and the like Mixtures included. Such Acidic substances are contained in the agents according to the invention preferably in amounts not exceeding 5% by weight, in particular from 0.1% by weight to 3% by weight.

Zusätzlich können die erfindungsgemäßen Mittel weitere in Waschmitteln übliche Bestandteile enthalten, zu denen insbesondere Komplexbildner für Schwermetalle, beispielsweise Aminopolycarbonsäuren und/oder Polyphosphonsäuren bzw. deren Salze, Vergrauungsinhibitoren, beispielsweise Celluloseether, Farbübertragungsinhibitoren, beispielsweise Polyvinylpyrrolidon, Schauminhibitoren, beispielsweise Organopolysiloxane oder Paraffine, und weiteres Enzym, insbesondere Oxidase, Peroxidase und/oder Kollagenase, gehören. Derartige Inhaltsstoffe können in den erfindungsgemäßen Mitteln in Mengen von jeweils bis zu 5 Gew.-%, insbesondere von 0,1 Gew.-% bis 4 Gew.-% enthalten sein.In addition, the detergents according to the invention can contain further constituents customary in detergents, in particular complexing agents for heavy metals, for example aminopolycarboxylic acids and / or polyphosphonic acids or salts thereof, graying inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinylpyrrolidone, foam inhibitors, for example organopolysiloxanes or paraffins, and further ene , in particular oxidase, peroxidase and / or collagenase, belong. Such ingredients can be present in the agents according to the invention in amounts of up to 5% by weight, in particular from 0.1% to 4% by weight.

Die Herstellung der erfindungsgemäßen Mittel kann in einfachster Weise durch Vermischen der Enzympartikel in einem üblichen Mischer, insbesondere einem Trommel-, Rollen-, Band- oder Freifallmischer erfolgen, wobei fakultative sonstige pulverförmige Bestandteile und gewünschtenfalls auch flüssige beziehungsweise verflüssigte Bestandteile, zu denen insbesondere nichtionische Tenside, aber auch Farb- und Duftstoffe gehören, durch Aufsprühen zugemischt werden können. Falls das erfindungsgemäße Waschmittel außer den enzymatischen Wirkstoffen weitere Komponenten enthalten soll, ist es bevorzugt, diese Komponenten, soweit sie thermisch belastbar sind, in im Prinzip bekannter Weise durch Sprühtrocknung einer wäßrigen Aufschlämmung in ein Pulverprodukt zu überführen und dieses mit den enzymatischen Wirkstoffen und gegebenenfalls weiteren thermisch empfindlichen Bestandteilen, zu denen insbesondere Bleichmittel, beispielsweise Alkaliperborate oder Alkalipercarbonat, zu rechnen sind, zu vermischen. Auch die Einarbeitung der sonstigen Bestandteile durch Zumischen eines diese enthaltenden Granulats beziehungsweise Extrudats zu den enzymatischen Bestandteilen ist möglich und insbesondere zur Herstellung von erfindungsgemäßen Waschmitteln mit relativ hohem Schüttgewicht von vorzugsweise 650 g/l bis 900 g/l bevorzugt.The agents according to the invention can be produced in the simplest manner by mixing the enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery components and, if desired, also liquid or liquefied components, in particular nonionic surfactants , but also colors and fragrances belong, can be mixed by spraying. If the detergent according to the invention is to contain further components in addition to the enzymatic active ingredients, it is preferred to convert these components, insofar as they are thermally resilient, into a powder product in a known manner by spray drying an aqueous slurry and to mix this with the enzymatic active ingredients and optionally further ones to mix thermally sensitive components, which include bleaching agents, for example alkali perborates or alkali percarbonate. The incorporation of the other ingredients by admixing a granulate or extrudate containing them with the enzymatic ingredients is also possible and is particularly preferred for the production of detergents according to the invention with a relatively high bulk density of preferably 650 g / l to 900 g / l.

Die erfindungsgemäßen Waschmittel sind farb- und gewebeschonend in der Anwendung, weisen ausgezeichnete Reinigungsleistungen auf, besitzen, wahrscheinlich insbesondere durch ihren Lipase-Gehalt, vergrauungsinhibierende Wirkung und ergeben, wahrscheinlich insbesondere durch ihren Cellulase-Gehalt, weiche Wäsche. Bemerkenswert ist, daß diese positiven Auswirkungen schon bei Dosierungen auftreten, die signifikant unterhalb der für typische europäische Haushalts-Universalwaschmittel üblichen Dosierung von etwa 6 g/l bis 8 g/l Waschflotte liegen.The detergents according to the invention are gentle on the color and fabric, have excellent cleaning performance, possess, probably particularly due to their lipase content, graying-inhibiting action and, probably particularly due to their cellulase content, give soft laundry. It is noteworthy that these positive effects already occur at doses that are significantly below the dosage of about 6 g / l to 8 g / l wash liquor customary for typical European household universal detergents.

BeispieleExamples Beispiel 1example 1

Die in der nachfolgenden Tabelle 1 durch ihre Zusammensetzung charakterisierten Mittel M1 bis M4 wurden durch einfaches Vermischen der Enzymgranulate in den angegebenen Mengenanteilen hergestellt. Tabelle 1: Zusammensetzung der Mittel [Gew.-%] M1 M2 M3 M4 Proteasea) 25 30 30 - Proteaseb) - - - 25 Lipasec) 25 54 50 25 Amylased) 25 10 12 25 Cellulasee) 25 6 8 - Cellulasef) - - - 25 a) BLAP(R)-Granulat (Hersteller Biozym), Aktivität 147 000 PE/g b) BLAP(R)-Granulat (Hersteller Biozym), Aktivität 170 000 PE/g c) Lipolase(R)-Granulat (Hersteller Novo), Aktivität 100 000 LU/g d) Termamyl(R)-Granulat (Hersteller Novo), Aktivität 60 KNU/g e) KAC(R)-Granulat (Hersteller Kao), Aktivität 500 IU/g f) Celluzyme(R)-Granulat (Hersteller Novo), Aktivität 700 IU/g The compositions M1 to M4 characterized in Table 1 below by their composition were prepared by simply mixing the enzyme granules in the stated proportions. Table 1: Composition of funds [% by weight] M1 M2 M3 M4 Protease a) 25th 30th 30th - Protease b) - - - 25th Lipase c) 25th 54 50 25th Amylase d) 25th 10th 12th 25th Cellulase e) 25th 6 8th - Cellulase f) - - - 25th a) BLAP (R) granules (manufacturer Biozym), activity 147,000 PE / g b) BLAP (R) granules (manufacturer Biozym), activity 170,000 PE / g c) Lipolase (R) granules (manufacturer Novo), activity 100,000 LU / g d) Termamyl (R) granules (manufacturer Novo), activity 60 KNU / g e) KAC (R) granules (manufacturer Kao), activity 500 IU / g f) Celluzyme (R) granules (manufacturer Novo), activity 700 IU / g

In einem Launderometer wurden mit standardisierten Anschmutzungen versehene Baumwoll-Textilstücke mit den in Tabelle 2 aufgeführten Waschflotten (W1: 0,32 g/l Natriumlaurylsulfat, 0,16 g/l 7-fach ethoxylierter C12-18-Alkohol, 1,2 g/l Zeolith Na-A; W2: W1 und 1,6 g/l Enzymmischung M1; W3: 0,64 g/l Natriumlaurylsulfat, 0,32 g/l 7-fach ethoxylierter C12-18-Alkohol, 1,2 g/l Zeolith Na-A; W4: W3 und 1,6 g/l Enzymmischung M1) gewaschen (Testbedingungen: 2 g angeschmutztes Gewebe und 6 g nicht angeschmutztes Füllgewebe, 100 ml Waschflotte, Wasserhärte 16 °d, Temperatur 40 °C, Waschdauer inkl. Aufheizzeit 30 Minuten; Auswertung mittels Remmissionsmessung bei 460 nm, ohne UV). Es ergaben sich die in Tabelle 2 angegebenen Remissionswerte. Zum Vergleich wurde unter den gleichen Bedingungen eine Waschflotte W5 mit einem handelsüblichen Flüssigwaschmittel, enthaltend 13,5 Gew.-% nichtionisches Tensid (12 Gew.-% 7-fach ethoxylierter Fettalkohol und 1,5 Gew.-% C12/14-Alkylglucosid), 5 Gew.-% Aniontensid (Na-C16/18-Alkylsulfat), 14 Gew.-% Seife, 7 Gew.-% 1,2-Propylenglykol, 5 Gew.-% Ethanol, Rest auf 100 Gew.-% Wasser, in der für dieses vorgeschriebenen Dosierung von 7,5 g/l getestet. Tabelle 2: Remission der gewaschenen Testgewebe [%] Waschflotte Remission bei Anschmutzung S/Ha) BMTb) BMRc) MRd) MKe) W1 45,9 32,3 61,5 43,7 29,2 W2 52,1 47,3 67,9 74,2 43,3 W3 49,8 32,4 63,6 51,3 32,3 W4 58,9 49,0 67,9 75,4 45,6 W5 51,1 39,4 64,7 57,9 37,7 a) Staub/Hautfett b) Blut/Milch/Tusche c) Blut/Milch/Ruß d) Milch/Ruß e) Milch/Kakao Cotton textile pieces provided with standardized soiling were washed in a launderometer using the washing liquors listed in Table 2 ( W1 : 0.32 g / l sodium lauryl sulfate, 0.16 g / l 7-fold ethoxylated C 12-18 alcohol, 1.2 g / l zeolite Na-A; W2 : W1 and 1.6 g / l enzyme mixture M1 ; W3 : 0.64 g / l sodium lauryl sulfate, 0.32 g / l 7-fold ethoxylated C 12-18 alcohol, 1.2 g / l zeolite Na-A; W4 : W3 and 1.6 g / l enzyme mixture M1 ) washed (test conditions: 2 g soiled fabric and 6 g non-soiled filler fabric, 100 ml washing liquor, water hardness 16 ° d, temperature 40 ° C, Washing time heating time 30 minutes; Evaluation by remission measurement at 460 nm, without UV). The remission values given in Table 2 resulted. For comparison, a washing liquor W5 with a commercially available liquid detergent containing 13.5% by weight of nonionic surfactant (12% by weight of 7-fold ethoxylated fatty alcohol and 1.5% by weight of C12 / 14-alkyl glucoside) was used under the same conditions. , 5% by weight anionic surfactant (Na-C 16/18 alkyl sulfate), 14% by weight soap, 7% by weight 1,2-propylene glycol, 5% by weight ethanol, balance to 100% by weight Water, tested in the prescribed dosage of 7.5 g / l. Table 2: Remission of the washed test tissue [%] Wash liquor Remission when soiled S / H a) BMT b) BMR c) MR d) MK e) W1 45.9 32.3 61.5 43.7 29.2 W2 52.1 47.3 67.9 74.2 43.3 W3 49.8 32.4 63.6 51.3 32.3 W4 58.9 49.0 67.9 75.4 45.6 W5 51.1 39.4 64.7 57.9 37.7 a) Dust / skin fat b) blood / milk / ink c) blood / milk / soot d) milk / soot e) milk / cocoa

Man erkennt, daß durch den Zusatz des erfindungsgemäßen eizymatischen Mittels in geringer Dosierung zu den lediglich geringe Konzentrationen Builder und Tensid enthaltenden Flotten W1 und W3, die als sclche erwartungsgemäß nur unzureichende Waschleistungen zeigen, Waschleistungen erreicht werden, welche diejenige eines üblichen Flüssigwaschmittels übertreffen, auch wenn dieses in deutlich höherer Dosierung angezündet wird. Bemerkenswert ist überdies, daß in einigen Fällen schon eine Waschflotte, die ausschließlich M1 (Dosierung 1,6 g/l) enthielt, eine Waschleistung aufwies, die derjenigen des höher dosierten Flüssigwaschmittels (Flotte W5 in Tabelle 2) zumindest entspricht).It can be seen that the addition of the eizymatic agent according to the invention in small doses to the fleets W1 and W3 containing only low concentrations of builder and surfactant, which, as expected, show inadequate washing performance, achieves washing performance which exceeds that of a conventional liquid detergent, even if this is lit in a significantly higher dosage. It is also noteworthy that in some cases a wash liquor containing only M1 (dosage 1.6 g / l) has a washing performance had that which at least corresponds to that of the higher-dose liquid detergent (fleet W5 in Table 2)).

Beispiel 2Example 2

Um die vorteilhafte Wirkung eines erfindungsgemäßen enzymatischen Wasch-hilfsmittels auch unter Praxisbedingungen nachzuweisen, wurde ein Flüssigwaschmittel, enthaltend 25 Gew.-% 7-fach ethoxylierten C12-18-Fettalkohol, 2 Gew.-% C12/14-Alkylglucosid, 5 Gew.-% Na-C12/14-Alkylsulfat, 16 Gew.-% Seife, 5 Gew.-% Glycerin, 7 Gew.-% Ethanol, Rest auf 100 Gew.-% Wasser, Parfum und Salze, hergestellt. In einer handelsüblichen Haushaltswaschmaschine (Miele W701) wurden die in der nachfolgenden Tabelle angegebenen künstlichen Anschmutzungen, fixiert auf Gerstenkornhandtüchern, zusammen mit 3,5 kg sauberer Haushaltswäsche bei 40 °C gewaschen (Buntwaschprogramm normal, Wassermenge 20 l, Düsseldorfer Stadtwasser). Die Auswertung des Primärwaschergebnisses erfolgte wie in Beispiel 1 angegeben über die Remission (Mittelwert aus 3 Bestimmungen). Die Dosierung betrug 1,5 g/l des Flüssigwaschmittels und 1,6 g/l des Mittels M4 aus Beispiel 1. Tabelle 3: Remission von bei Praxisbedingungen gewaschenen Testgeweben [%] Anschmutzung Remission nach Wäsche (Schwankungsbreite) Anfangswert Staub auf Baumwolle 73,3 (1,9) 36,2 Staub/Hautfett auf Baumwolle 73,0 (0,4) 26,8 Staub/Hautfett auf Polyester 74,7 (0,5) 31,4 Rotwein auf Baumwolle 47,5 (0,5) 31,6 Milch/Ruß auf Baumwolle 74,0 (1,0) 18,0 In order to demonstrate the advantageous effect of an enzymatic detergent according to the invention even under practical conditions, a liquid detergent containing 25% by weight of 7-fold ethoxylated C 12-18 fatty alcohol, 2% by weight of C 12/14 alkyl glucoside, 5% by weight was used .-% Na-C12 / 14-alkyl sulfate, 16 wt .-% soap, 5 wt .-% glycerol, 7 wt .-% ethanol, balance to 100 wt .-% water, perfume and salts. In a commercial household washing machine (Miele W701), the artificial soiling specified in the table below, fixed on barley grain towels, was washed together with 3.5 kg of clean household laundry at 40 ° C (colored washing program normal, water volume 20 l, Düsseldorf city water). The evaluation of the primary washing result was carried out as indicated in Example 1 via the remission (average of 3 determinations). The dosage was 1.5 g / l of the liquid detergent and 1.6 g / l of the agent M4 from Example 1. Table 3: Remission of test fabrics washed under practical conditions [%] Pollution Remission after washing (fluctuation range) Initial value Dust on cotton 73.3 (1.9) 36.2 Dust / skin fat on cotton 73.0 (0.4) 26.8 Dust / skin fat on polyester 74.7 (0.5) 31.4 Red wine on cotton 47.5 (0.5) 31.6 Milk / soot on cotton 74.0 (1.0) 18.0

Die Waschleistung unter Einsatz des erfindungsgemäßen Waschhilfsmittels war in allen Fällen signifikant besser als diejenige des Flüssigwaschmittels alleine, auch wenn man in dieses unter Verringerung des Wasseranteils 0,1 Gew.-% Amylase (Termamyl(R) LDX 300) und 2 Gew.-% Protease (Alkalase(R) 2.5 LDX) einarbeitete und das dann entstehende enzymatische Flüssigwaschmittel in deutlich höherer Dosierung (4,6 g/l) einsetzte.The washing performance using the washing aid according to the invention was significantly better in all cases than that of the liquid detergent alone, even if 0.1% by weight of amylase (Termamyl (R) LDX 300) and 2% by weight were reduced in it. Protease (Alkalase (R) 2.5 LDX) and incorporated the resulting enzymatic liquid detergent in a significantly higher dosage (4.6 g / l).

Claims (9)

  1. An enzyme-containing detergent containing protease, lipase, amylase and cellulase characterized in that it is present in particulate form and contains no more than 5% by weight of anionic, nonionic, cationic and/or amphoteric surfactant and/or no more than 20% by weight of builder, the enzymes being used in granular form adsorbed onto support materials.
  2. A detergent as claimed in claim 1, characterized in that it contains protease in such a quantity that it has a proteolytic activity of 10,000 PU/g to 75,000 PU/g.
  3. A detergent as claimed in claim 1 or 2, characterized in that it contains lipase in such a quantity that it has a lipolytic activity of 10,000 LU/g to 90,000 LU/g.
  4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains amylase in such a quantity that it has an amylolytic activity of 1 KNU/g to 20 KNU/g.
  5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains cellulase in such a quantity that it has a cellulolytic activity of 5 IU/g to 150 IU/g.
  6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains 0.5% by weight to 5% by weight of surfactant, more particularly nonionic surfactant.
  7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains no more than 20% by weight and, in particular, from 1% by weight to 5% by weight of water-soluble or water-dispersible builders, more particularly zeolite NaA.
  8. A detergent as claimed in claim 7, characterized in that it contains an ethoxylation product of a primary linear alcohol containing 10 to 22 carbon atoms and, more particularly, 12 to 18 carbon atoms and having an average degree of ethoxylation of 5 to 10 and, more particularly, 6 to 8 as surfactant.
  9. The use of an enzymatic washing aid which contains no more than 5% by weight of anionic, nonionic, cationic and/or amphoteric surfactant and/or no more than 20% by weight of builder and which has a proteolytic activity of, in particular, 10,000 PU/g to 75,000 PU/g, a lipolytic activity of, in particular, 10,000 LU/g to 90,000 LU/g, an amylolytic activity of, in particular, 1 KNU/g to 20 KNU/g and a cellulolytic activity of, in particular, 5 UI/g to 150 IU/g as a detergency-boosting additive in detergents or bleaching agents or in aqueous liquors containing detergents or bleaching agents.
EP94913117A 1993-04-13 1994-04-05 Enzymatic washing agent Revoked EP0694060B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4312010A DE4312010A1 (en) 1993-04-13 1993-04-13 Enzymatic detergent
DE4312010 1993-04-13
PCT/EP1994/001049 WO1994024258A1 (en) 1993-04-13 1994-04-05 Enzymatic washing agent

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EP0694060A1 EP0694060A1 (en) 1996-01-31
EP0694060B1 true EP0694060B1 (en) 1997-12-17

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DE19738625C1 (en) * 1997-09-04 1999-02-04 Henkel Kgaa Texturising and softening knitwear, especially cotton knitwear to give used look
DE19752844A1 (en) * 1997-11-28 1999-06-02 Henkel Kgaa Increasing the cleaning performance of detergents
WO2013000927A1 (en) * 2011-06-29 2013-01-03 Dsm Ip Assets B.V. Process for the treatment of sludge or other organic material
DE102014226293A1 (en) * 2014-12-17 2016-06-23 Henkel Ag & Co. Kgaa Detergent with improved stain removal

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ATE161284T1 (en) 1998-01-15
WO1994024258A1 (en) 1994-10-27
JPH08508775A (en) 1996-09-17
EP0694060A1 (en) 1996-01-31
ES2110744T3 (en) 1998-02-16
DE4312010A1 (en) 1994-10-20

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