WO1994024258A1 - Agent de lavage enzymatique - Google Patents

Agent de lavage enzymatique Download PDF

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Publication number
WO1994024258A1
WO1994024258A1 PCT/EP1994/001049 EP9401049W WO9424258A1 WO 1994024258 A1 WO1994024258 A1 WO 1994024258A1 EP 9401049 W EP9401049 W EP 9401049W WO 9424258 A1 WO9424258 A1 WO 9424258A1
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WO
WIPO (PCT)
Prior art keywords
weight
composition according
activity
washing
detergents
Prior art date
Application number
PCT/EP1994/001049
Other languages
German (de)
English (en)
Inventor
Heidi Andexer
Horst Upadek
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59404831T priority Critical patent/DE59404831D1/de
Priority to JP6522693A priority patent/JPH08508775A/ja
Priority to EP94913117A priority patent/EP0694060B1/fr
Publication of WO1994024258A1 publication Critical patent/WO1994024258A1/fr

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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 auxiliary washing agents which 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 stains.
  • Detergents which, in addition to protease, additionally contain amylase as an active ingredient for removing soils based on starch are known, for example, from German Offenlegungsschrift DE 27 27 463.
  • Cellulase-containing detergents are, for example, from European patent applications EP 120528, 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 A ins and contains a cellulase, EP 177 165, relating to a fabric softening detergent which contains a clay mineral and cellulase, EP 173398, relating to a detergent containing cellulase and a mono- or di-long-chain, primary or secondary amine, EP 173397, concerning 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
  • Detergents which contain a combination of up to three 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 .-% amylase from European patent application EP 365 103 and the combination of protease, amylase and lipase or cellulase from European patent application EP 425214.
  • the invention accordingly relates to an enzymatic detergent which contains protease, lipase, amylase and cellulase and optionally surfactant and / or builder.
  • Another object of the invention is the use of an enzymatic washing aid which has a proteolytic activity of preferably 10,000 PU / g to 75,000 PU / g, a lipolytic activity of preferably 10,000 LU / g to 90000 LU / g, has an amylolytic activity of preferably 1 KNU / g to 20 KNU / g and a cellulolytic activity of preferably 5 IU / g to 150 IU / g, as a cleaning-enhancing additive to detergents or bleaches or aqueous liquors, the detergents or contain bleach.
  • an enzymatic washing aid which has a proteolytic activity of preferably 10,000 PU / g to 75,000 PU / g, a lipolytic activity of preferably 10,000 LU / g to 90000 LU / g, has an amylolytic activity of preferably 1 KNU / g to 20 KNU / g and a cellulolytic activity of preferably 5
  • 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 a pH optimum in the alkaline range.
  • Suitable proteases are known, for example, from the 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 416967 or EP 394352.
  • Protease is preferably used in the agent according to the invention in amounts such that the finished agent is 10,000 PU / g to 75,000 PU / g (protease units per gram, determined according to the method described in Tideside 7, 125 (1970)), in particular 12500 PE / g to 65000 PE / g and particularly preferably 15000 PE / g to 45000 PE / g.
  • Useful proteases are commercially available, for example under the names Savinase ( R ), Esperase ( R ), Maxatase ( R ), 0ptimase ( R ) or Alcalase ( R ).
  • 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 the European patent applications EP 204208, EP 214761, EP 258068, EP 407225 or the international patent application WO 87/859.
  • Useful commercially available lipases are, for example, Lipolase ( R ) and Lipozym'R).
  • Lipase is used in Agents according to the invention are preferably used in amounts such that the finished agent 10,000 LU / g to 90000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 according to that in EP 258068 mentioned method), 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 are, for example, Termamyl ( R ) and Maxamyl ( R ).
  • 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 ("Klo-Novo-Um ' ts" per gram according to the Novo standard method, 1 KNU the Is the amount of enzyme that breaks down 5.26 g of 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 patent applications DE 31 17 250, DE 3207825, DE 3207847, DE 3322950 or European patent applications EP 265832, EP 269977, EP 270974, EP 273 125 and EP 339 550.
  • 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) 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 preferred 12 IU / g to 130 IU / g.
  • Suitable commercial products are, for example, Celluzyme ( R ) from Novo Industri or KAC ( R ) from Kao.
  • the agents according to the invention can be in the form of liquid, paste-like or solid preparations, in particular in the case of liquid or paste-like detergents 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.
  • 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
  • the detergents according to the invention are in particle form.
  • the enzymes mentioned are embedded in the form adsorbed on carrier substances, in coating substances or in the form of customary granules with inorganic and / or organic carrier materials, as described, for example, in German patent DE 16 17 232, the German Published documents DT 20 32766 or DE 4041 752 or the European patent applications EP 168526, EP 170360, EP 270608 or EP 304331 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 the 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 therefore preferably 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 from the washing aids according to the invention.
  • the contingent components mentioned below and their amounts are to be understood exclusively as the amounts of such ingredients which may be present in the enzyme particles.
  • 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, hexcdecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • alkoxylation products especially the ethoxylation products, of mono- or polyunsaturated fatty alcohols, for example oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and Eruca. heard ge, can be used.
  • alkoxylation products especially the ethoxylation products, of mono- or polyunsaturated fatty alcohols, for example oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and Eruca. heard ge
  • Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl moiety can also be used.
  • the ethoxylation and / or Propcxyl ists- products of fatty acid Ci-bis-CTJ alkyl esters, Ahren as f by the method described in International Patent Application WO 90/13533 Ver her ⁇ can be provided, and / or fatty acid polyhydroxyamides, they wia can be produced in accordance with 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 Cg to Ci5 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 also belong, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms -Atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as 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 counter cation.
  • 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 octa-decyl radicals.
  • the alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating agent, 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 a carboxylic acid functionality in copolymerized form.
  • the acids mentioned are usually in the form of their alkali salts, in particular special of their sodium or potassium salts used.
  • Organic builder substances of this type 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. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing, detergents according to the invention.
  • crystalline or amorphous alkali alumosilicates 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, are used as water-insoluble, water-dispersible inorganic builder materials.
  • 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 at least 80% by weight of particles 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 mixtures thereof.
  • The- Like acidic substances are contained in the agents according to the invention preferably in amounts of not more than 5% by weight, in particular from 0.1% by weight to 3% by weight.
  • the agents according to the invention can contain further constituents customary in detergents, in particular complexing agents for heavy metals, for example amino polycarboxylic acids and / or polyphosphonic acids or their salts, graying inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinylpyrrolidone, foam inhibitors, for example organopolysiloxanes or Paraffins, and another enzyme, especially oxidase, peroxidase and / or collagenase, belong.
  • Such ingredients can be contained in the agents according to the invention in amounts of up to 5% by weight, in particular from 0.1% by weight 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, with optional other powdery constituents and, if desired, also liquid or liquefied constituents which in particular include nonionic surfactants, but also colorants and fragrances, can be mixed in by spraying.
  • a conventional mixer in particular a drum, roller, belt or free-fall mixer
  • optional other powdery constituents and, if desired, also liquid or liquefied constituents which in particular include nonionic surfactants, but also colorants and fragrances, can be mixed in by spraying.
  • the detergent according to the invention is to contain other 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 convert this with the enzymes active ingredients and optionally other thermally sensitive constituents, to which bleaching agents in particular, for example alkali perborates or alkali percarbonate, are to be counted.
  • the incorporation of the other constituents by admixing a granulate or extrudate containing them with the enzymatic constituents 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 / 1 to 900 g / 1.
  • the detergents according to the invention are gentle on the dye and fabric, have excellent cleaning performance, possess, probably in particular due to their lipase content, graying-inhibiting action and, probably in particular due to their cellulase content, give soft laundry. It is noteworthy that these positive effects already occur at doses which are significantly below the dosage of about 6 g / 1 to 8 g / 1 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 quantities indicated.
  • Amylase ⁇ 25 10 12 25
  • Cotton textile pieces provided with standardized stains were washed in a launderometer with the washing liquors listed in Table 2 (WL: 0.32 g / 1 sodium lauryl sulfate, 0.16 g / 1 7-fold ethoxylated Ci2-18 ⁇ alcohol, 1, 2 g / 1 zeolite Na-A; W2: Wl and 1.6 g / 1 enzyme mixture Ml; W3: 0.64 g / 1 sodium lauryl sulfate, 0.32 g / 1 7-fold ethoxylated Ci2-l8 _alcohol , 1 , 2 g / 1 zeolite Na-A; W4: W3 and 1.6 g / 1 enzyme mixture Ml) 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 duration including heating-up time 30 minutes; Evaluation by remission measurement at 460
  • Example 1 (colored washing program normal, amount of water 20 l, Düsseldorf city water).
  • the evaluation of the primary washing result was carried out as indicated in Example 1 by means of the remission (average of 3 determinations).
  • the dosage was 1.5 g / 1 of the liquid detergent and 1.6 g / 1 of the agent M4 from Example 1.
  • the washing performance using the washing aid according to the invention was in all cases significantly better than that of the liquid detergent alone, even if 0.1% by weight of amylase (Termamyl ( R ) LDX 300) and 2% by weight of water were added to it. -% protease (alkali se () 2.5 LDX) and then used the resulting enzymatic liquid detergent in a significantly higher dosage (4.6 g / 1).

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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

L'invention a pour but l'obtention d'un agent de lavage qui, tout en étant uniquement à base d'enzymes, à l'exclusion dans la plus large mesure possible, des autres composants d'agents de lavage habituels, présente un pouvoir détersif au moins égal à celui des agents de lavage courants à composition hautement optimisée. L'agent de lavage enzymatique selon l'invention renferme de la protéase, de la lipase, de l'amylase et de la cellulase, et, le cas échéant, de faibles quantités d'agents tensioactifs et/ou d'adjuvants. Des agents ainsi constitués peuvent être utilisés comme produits de lavage employés seuls ou comme auxiliaires de lavage ajoutés à des agents de lavage de type courant.
PCT/EP1994/001049 1993-04-13 1994-04-05 Agent de lavage enzymatique WO1994024258A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE59404831T DE59404831D1 (de) 1993-04-13 1994-04-05 Enzymatisches waschmittel
JP6522693A JPH08508775A (ja) 1993-04-13 1994-04-05 酵素洗剤
EP94913117A EP0694060B1 (fr) 1993-04-13 1994-04-05 Agent de lavage enzymatique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4312010A DE4312010A1 (de) 1993-04-13 1993-04-13 Enzymatisches Waschmittel
DEP4312010.5 1993-04-13

Publications (1)

Publication Number Publication Date
WO1994024258A1 true WO1994024258A1 (fr) 1994-10-27

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ID=6485353

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Application Number Title Priority Date Filing Date
PCT/EP1994/001049 WO1994024258A1 (fr) 1993-04-13 1994-04-05 Agent de lavage enzymatique

Country Status (6)

Country Link
EP (1) EP0694060B1 (fr)
JP (1) JPH08508775A (fr)
AT (1) ATE161284T1 (fr)
DE (2) DE4312010A1 (fr)
ES (1) ES2110744T3 (fr)
WO (1) WO1994024258A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19738625C1 (de) * 1997-09-04 1999-02-04 Henkel Kgaa Waschverfahren für Strickwaren
DE19752844A1 (de) * 1997-11-28 1999-06-02 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln
WO2013000927A1 (fr) * 2011-06-29 2013-01-03 Dsm Ip Assets B.V. Procédé de traitement d'une boue ou d'une autre matière organique
DE102014226293A1 (de) * 2014-12-17 2016-06-23 Henkel Ag & Co. Kgaa Waschmittel mit verbesserter Fleckentfernung

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US4566985A (en) * 1984-09-19 1986-01-28 Applied Biochemists, Inc. Method of cleaning using liquid compositions comprising stabilized mixtures of enzymes
JPS62269684A (ja) * 1986-05-15 1987-11-24 Showa Denko Kk 酵素粒剤の製造方法
EP0425214A2 (fr) * 1989-10-23 1991-05-02 Unilever Plc Compositions détergentes contenant un enzyme et leur utilisation
WO1992018597A1 (fr) * 1991-04-12 1992-10-29 The Procter & Gamble Company Composition detersive compacte contenant de la polyvinylpyrrolidone
JPH0525776A (ja) * 1991-07-09 1993-02-02 Toyobo Co Ltd 自己洗濯性繊維製品
JPH0610274A (ja) * 1992-06-24 1994-01-18 Toyobo Co Ltd 自己洗濯性繊維製品

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US3919107A (en) * 1973-03-23 1975-11-11 Procter & Gamble Built detergent compositions containing dextrin esters of poly carboxylic acids
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NZ230842A (en) * 1988-10-21 1992-05-26 Colgate Palmolive Co Nonionic heavy duty particulate detergent containing protease, amylase and cellulase
JPH0343073A (ja) * 1989-02-27 1991-02-25 Occidental Chem Corp 種々の温度で活性を有する特異な微生物リパーゼ及び該リパーゼを含有する洗剤
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Publication number Priority date Publication date Assignee Title
DE2033822A1 (de) * 1969-07-09 1971-04-15 Astra Lakemedel AB, Sodertalje (Schweden) Hydrolytisches Enzymgemisch und Ver fahren zu dessen Herstellung
US4566985A (en) * 1984-09-19 1986-01-28 Applied Biochemists, Inc. Method of cleaning using liquid compositions comprising stabilized mixtures of enzymes
JPS62269684A (ja) * 1986-05-15 1987-11-24 Showa Denko Kk 酵素粒剤の製造方法
EP0425214A2 (fr) * 1989-10-23 1991-05-02 Unilever Plc Compositions détergentes contenant un enzyme et leur utilisation
WO1992018597A1 (fr) * 1991-04-12 1992-10-29 The Procter & Gamble Company Composition detersive compacte contenant de la polyvinylpyrrolidone
JPH0525776A (ja) * 1991-07-09 1993-02-02 Toyobo Co Ltd 自己洗濯性繊維製品
JPH0610274A (ja) * 1992-06-24 1994-01-18 Toyobo Co Ltd 自己洗濯性繊維製品

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DATABASE WPI Section Ch Week 8801, Derwent World Patents Index; Class D16, AN 88-004538 *
DATABASE WPI Section Ch Week 9310, Derwent World Patents Index; Class D16, AN 93-080888 *
DATABASE WPI Section Ch Week 9409, Derwent World Patents Index; Class A94, AN 94-068389 *

Also Published As

Publication number Publication date
ATE161284T1 (de) 1998-01-15
ES2110744T3 (es) 1998-02-16
JPH08508775A (ja) 1996-09-17
DE4312010A1 (de) 1994-10-20
EP0694060B1 (fr) 1997-12-17
EP0694060A1 (fr) 1996-01-31
DE59404831D1 (de) 1998-01-29

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