WO1996008554A1 - Agent de lavage et de blanchiment en poudre contenant des enzymes - Google Patents

Agent de lavage et de blanchiment en poudre contenant des enzymes Download PDF

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Publication number
WO1996008554A1
WO1996008554A1 PCT/EP1995/003506 EP9503506W WO9608554A1 WO 1996008554 A1 WO1996008554 A1 WO 1996008554A1 EP 9503506 W EP9503506 W EP 9503506W WO 9608554 A1 WO9608554 A1 WO 9608554A1
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WO
WIPO (PCT)
Prior art keywords
weight
bleach
detergent according
powdery
detergent
Prior art date
Application number
PCT/EP1995/003506
Other languages
German (de)
English (en)
Inventor
Heinz-Manfred Wilsberg
Günther VOGT
Georg Meine
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.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6528391&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1996008554(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP95932676A priority Critical patent/EP0781323B1/fr
Priority to JP8509875A priority patent/JPH10506135A/ja
Priority to AT95932676T priority patent/ATE201440T1/de
Priority to DE59509292T priority patent/DE59509292D1/de
Publication of WO1996008554A1 publication Critical patent/WO1996008554A1/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
    • C11D3/38645—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • the invention relates to a pulverulent, oxidizing agent and cellulase-containing bleaching agent and detergent for use in household laundry, which as an additive increases the cleaning action of a conventional detergent or can be added to the washing liquor as the sole detergent-active agent.
  • Bleach and bleach-containing additives are often used in household laundry as a supplement to the usual detergents to enhance their cleaning effect. These additives are used particularly when heavily soiled laundry is to be washed or to lighten white laundry.
  • Bleaching systems which contain a combination of an inorganic peroxide or perhydrate with a bleach activator which forms an organic peracid under washing conditions are generally used as bleaching agents. These combinations have been known for a long time.
  • the most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates.
  • activators such compounds are generally used which split off carboxylic acids or percarboxylic acids under hydrolysis or perhydrolysis conditions, the predominant use being made of compounds which deliver peracetic acid in the presence of the oxidizing agents mentioned .
  • German patent application DE 31 41 745 describes an enzyme-containing bleaching agent composition which contains an inorganic peroxide which is effective for bleaching fabrics, and 0.01 to 5% by weight, based on the total mass of the enzymes, hydrolase, transferase, oxyreductase, Lyase, isomerase, ligase, protease, lipase, cellulase or amylase with an optimal effective temperature of 10 ⁇ C to 80 ° C at an optimal pH of 4 to 12, and at least 0.1 to 20 wt .-%, based on the total mass of an anhydrous salt from the series of anhydrous sodium nitrate, anhydrous magnesium sulfate, anhydrous calcium chloride and anhydrous zinc sulfate.
  • the water content of the total mass of the composition described is less than 2% by weight.
  • European patent application EP 0 407 045 describes a stabilized sodium percarbonate composition which, in addition to sodium percarbonate, also contains 2.5 to 35% by weight of at least one compound from the group consisting of urea, urea derivatives, acetates, amino acids with no more than seven carbon atoms or contains their salts, triazine compounds and guanidine compounds as stabilizers.
  • Compositions are described which consist only of percarbonate or of a mixture of percarbonate and alkali metal carbonates, dicarbonates, sulfates and borates.
  • the European patent application EP 0 508034 describes a detergent composition which, in addition to polyvinylpyrrolidone, surfactants and builders, can also contain bleach, bleach activator and enzymes.
  • the object of the present invention was to provide a bleach and detergent composition which does not have the above disadvantages and which can also be used for washing colored textiles without losing their color even after several washes.
  • the present invention relates to a pulverulent, oxidizing agent and cellulase-containing bleaching agent and washing agent which contains 1% by weight of oxidizing agent cellulase in an activity of 0.005 CEVU to 10.5 CEVU and 1% by weight to 20% by weight .-% bleach activator contains.
  • the agent according to the invention shows an excellent washing and bleaching effect, but the color is essentially retained even after several washes.
  • the detergent and bleaching agent contains 1% by weight of cellulase oxidizing agent with an activity of 0.005 CEVU to 10.5 CEVU, (cellulose viscosity units, based on the increase in viscosity of CMC solutions in the enzymatic hydrolysis of CMC as described in Novo publication AF-253/1), in particular from 0.01 CEVU to 8.5 CEVU and particularly preferably from 0.02 CEVU to 7.0 CEVU.
  • oxidizing agents the sodium perborate tetrahydrate, the sodium perborate monohydrate and the sodium percarbonate being of particular importance.
  • Other useful oxidizing agents are, for example, peroxyprophosphates, citrate perhydrates and peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
  • the compositions according to the invention preferably contain a total of 5 to 75% by weight and in particular 15 to 60% by weight of oxidizing agent, sodium percarbonate being particularly preferably used.
  • the bleaching and washing agent according to the invention contains a bleach activator.
  • a bleach activator Any powder-formable compound that provides organic peracid under perhydrolysis conditions is suitable as bleach activator component.
  • These include, in particular, N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylene diamine, N-acylated triazines, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-phenolsulfonate,
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions.
  • TAED tetraacetylethylenediamine
  • Bleach activator can be contained in the agent according to the invention in an amount of 1% by weight to 20% by weight, in particular 2% by weight to 15% by weight.
  • the agent according to the invention further contains enzymes from the class or cellulases.
  • the cellulase used according to the invention belongs to the enzymes obtainable from bacteria or fungi, which have 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 Offenlegungsschriften DE 31 17250, DE 3207825, DE 3207847, DE 3322950 or European patent applications EP 265 832, EP 269 077, EP 270 974, EP 273 125 and EP 339 550.
  • Suitable commercial products are, for example, Celluzyme ( R ) from Novo Nordisk or AC (R) from Kao.
  • the agent according to the invention can contain surfactants which can be selected from the group of synthetic anionic and / or nonionic surfactants and soaps. They can be contained in an amount from 2% by weight to 40% by weight, preferably in amounts from 2% by weight to 30% by weight, in particular from 2% by weight to 20% by weight.
  • Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as those obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used are used.
  • the anionic surfactants are preferably used in the form of the sodium salts.
  • Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, ie of fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the Cio to C20-0x ° alcohols and those of secondary alcohols of this chain length.
  • sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or ethoxylated with 1 to 10 moles of ethylene oxide Alkylphenols into consideration.
  • Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
  • the surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with Cg to Ci5 alkyl groups, sulfosuccinic acid mono- and diesters with 6 to 22 C atoms in the alcohol parts and the esters of a-sulfofatty acids, for example the a-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • alkanesulfonates which can be obtained from C 2 -C 8 -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins
  • olefin sulfonates i.e. Mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates, e.g. from long-chain mono-olefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkali or acid hydrolysis of the sulfonation products.
  • anionic surfactants are the alkylbenzenesulfonates with linear Cg to Cjs alkyl groups, the fatty alcohol sulfates with 12 to 18 C atoms and mixtures of these surfactants.
  • Anionic surfactant can be contained in the agent according to the invention in amounts of 2% by weight to 40% by weight, in particular 3% by weight to 24% by weight.
  • Suitable surfactants are, in particular, soaps, with saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and from natural fatty acids, e.g. Ko ⁇ kos-, palm kernel or Taig fatty acids, derived soap mixtures are suitable.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 1-4 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the detergents according to the invention preferably contain the soaps in amounts of 0.1 to 4% by weight, in particular 0.1 to 3% by weight.
  • Suitable nonionic surfactants include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, especially those Ethoxylates and / or propoxylates of linear and 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 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
  • the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and their mixtures are particularly useful.
  • Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can also be used.
  • Nonionic surfactant is preferably present in amounts of up to 10% by weight, in particular from 0.5% by weight to 6% by weight, based on the finished composition.
  • the agent according to the invention can contain builders as a further constituent.
  • the builders are a water-soluble or a water-insoluble compound or a mixture of two or more such compounds.
  • Commercial builder substances can be used. Suitable builder substances are, in particular, those from the classes of polycarboxylic acids, in particular polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, phyllosilicates, in particular bentonites, aluminum silicates, in particular zeolites, alkali metal silicates, in particular sodium silicate, and alkali carbonates, in particular sodium carbonate.
  • the aforementioned polycarboxylic acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts.
  • the preferably incorporated zeolites are in particular those of the NaA or NaX type or mixtures thereof.
  • the alkali silicates those with molar ratios of S1O2 to alkali oxide in the range from 1.5 to 3.0 are preferred.
  • Such builder substances are preferably contained in the composition according to the invention in amounts of 20% by weight to 75% by weight, in particular from 10% by weight to 35% by weight.
  • the agent according to the invention can contain alkali metal salts of lower alkyl carboxylic acids with 1 to 5 carbon atoms, which may be substituted by hydroxyl groups. Examples of such lower alkyl carboxylic acids or their salts are alkali metal citrates, sodium citrate 2-hydrate being particularly preferred. These substances can be contained in an amount of 1 to 25% by weight.
  • the washing and bleaching agent according to the invention can contain, as a further powdery component, water-soluble salts which do not give off crystal water in the range from 1 ° C. to 45 ° C. and whose melting point is above 45 ° C.
  • these salts include in particular sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium sulfate and mixtures thereof.
  • Such powdery components are preferably not contained in the agents according to the invention in excess of 65% by weight, in particular from 5% by weight to 60% by weight.
  • the agent according to the invention can contain, in addition to the previously mentioned components, complexing agents for heavy metals, which increase both the storage stability, in particular the percarbonate component, and the bleaching action of the bleaching agent according to the invention under conditions of use.
  • Suitable complexing agents include aminopolycarboxylic acids, in particular nitrilotriacetic acid, ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and l-hydroxyethane-l, l-di-phosphonic acid and their alkali metal salts, in particular their sodium salts .
  • Such complex formers are preferably present in amounts of not more than 10% by weight, in particular from 0.05% by weight to 2% by weight, based on the finished composition. They can be added in any way and are preferably incorporated into the spray-dried powder of builder and surfactant, in which they can be present in particular in amounts of 0.1% by weight to 10% by weight.
  • the agent according to the invention can also contain further additives customary in bleaching and washing agents, such as enzymes, dyes, optical brighteners and / or fragrances.
  • These constituents are preferably in amounts of not more than 1% by weight, in particular from 0.05 to 0.5% by weight. based on the total mean available. They can be part of one or more powder components or more or less homogeneously distributed over all powder components.
  • the individual components of the agent according to the invention can be mixed and packaged in a manner known per se.
  • the preparation of the agents according to the invention does not require any major technical effort.
  • Simple mixing devices such as paddle or drum mixers, in which the powdery components can be mixed, are usually suitable.
  • the use of automatic belt weighers in combination with free-fall mixers is also possible and is preferred for continuous production of the agents according to the invention.
  • the mixture can be carried out with simultaneous spraying-on of colorants and / or fragrances or liquid enzyme preparations. It is also possible to prepare the agent by spray drying an aqueous suspension or slurry of the components.
  • the agent according to the invention contains nonionic surfactant, it can also be sprayed as part of the aqueous slurry or sprayed onto the powder in a known manner after the other components have been spray-dried. It is preferred that the spray-dried powder have a water content such that the water content of the finished composition is 8% by weight to 15% by weight, in particular 8% by weight to 13% by weight.
  • Vor ⁇ preferably this spray-dried product is produced so that a 30 wt .-% to about 65 wt .-% water suspension containing substances from Builder ⁇ surfactant and heated to temperatures of about 40 ⁇ C to 100 ° C and by means of nozzles under a Atomization pressure from about 20 to 120 bar, in particular from 30 to 60 bar, is sprayed into a drop space into which drying gases are introduced in cocurrent or preferably in countercurrent, the inlet temperatures from about 150 ° C. to about 350 ° C., in particular from Have 200 ° C to 250 ° C.
  • the agent according to the invention preferably has a bulk density of not more than 850 g / 1, in particular from 250 to 800 g / 1 and particularly preferably from 400 to 750 g / 1. It is preferably used as an additive to detergent-containing liquors, especially in the temperature range from 30 ° C to 60 ° C, to enhance the bleaching effect (bleach booster). However, it can also be used as the sole cleaning-active component in the wash liquor, in particular then, when soiled textiles are to be cleaned only with relatively small amounts of non-bleachable soiling.
  • the agent according to the invention contains 20% by weight to 60% by weight of alkali percarbonate, 5% by weight to 20% by weight of bleach activator, cellulase with an activity of 0.01 CEVU / g to 2, 7 CEVU / g, 5% to 10% by weight of anionic surfactant, 0.1% to 3% by weight of nonionic surfactant, 5% to 15% by weight of builder, 1 to 6% by weight of alkali citrate, up to 15% by weight of water, 10% by weight to 60% by weight of water-soluble salts, 0.01% by weight to 1% by weight of complexing agent and 0.1 % By weight to 0.5% by weight of optical brighteners.
  • Granular detergents of the compositions shown in Table 1 were produced. The effect of color refreshment on textiles by using the detergent according to the invention was tested. 3 different recipes were used.
  • bleaching agent A 3: universal detergent 1 + bleaching agent according to the invention
  • bleaching agent B 1 Persil Supra ( R ) liquid, manufacturer Henkel KGaA, Dusseldorf
  • Bleaching agent used (amount of components in% by weight):
  • Test fabric colored fabric with dots, prewashed 25 times at 60 ° C in Miele () 717, colored washing program with a long washing time, 12 liters of water, 98 g universal detergent, the prewashed fabric showed a clear loss of color and graying.
  • Washing conditions 40 ° C, Miele ( R ) W 717, colored washing program with long washing time
  • the color refreshment was determined by means of a pairwise comparison. For this purpose, two assessments were presented to the assessors, who had to assess which sample the color looked fresher.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Abstract

L'invention concerne un agent de lavage et de blanchiment en poudre, contenant un oxydant et de la cellulase. Ledit agent renferme, pour 1 % en poids d'oxydant, de la cellulase d'une activité de 0.005 CEVU à 10,5 CEVU, ainsi que 1 % à 20 % en poids d'activateur de blanchiment. Cet agent peut être utilisé pour le lavage de matières textiles teintes, sans que celles-ci perdent leur coloration même après plusieurs lavages.
PCT/EP1995/003506 1994-09-16 1995-09-07 Agent de lavage et de blanchiment en poudre contenant des enzymes WO1996008554A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP95932676A EP0781323B1 (fr) 1994-09-16 1995-09-07 Agent de lavage et de blanchiment en poudre contenant des enzymes
JP8509875A JPH10506135A (ja) 1994-09-16 1995-09-07 粉末状の酵素含有洗濯および漂白剤
AT95932676T ATE201440T1 (de) 1994-09-16 1995-09-07 Pulverförmiges, enzymhaltiges bleich- und waschmittel
DE59509292T DE59509292D1 (de) 1994-09-16 1995-09-07 Pulverförmiges, enzymhaltiges bleich- und waschmittel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4433027A DE4433027A1 (de) 1994-09-16 1994-09-16 Pulverförmiges, enzymhaltiges Bleich- und Waschmittel
DEP4433027.8 1994-09-16

Publications (1)

Publication Number Publication Date
WO1996008554A1 true WO1996008554A1 (fr) 1996-03-21

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ID=6528391

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/003506 WO1996008554A1 (fr) 1994-09-16 1995-09-07 Agent de lavage et de blanchiment en poudre contenant des enzymes

Country Status (6)

Country Link
EP (1) EP0781323B1 (fr)
JP (1) JPH10506135A (fr)
AT (1) ATE201440T1 (fr)
DE (2) DE4433027A1 (fr)
ES (1) ES2158129T3 (fr)
WO (1) WO1996008554A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2295579A1 (fr) * 1997-07-11 1999-01-21 The Procter & Gamble Company Composition detergente comportant une cellulase specifique, et un activateur hydrophobe de blanchiment

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0381397A2 (fr) * 1989-01-30 1990-08-08 Unilever Plc Compositions détergentes en particules et leur utilisation
WO1992006167A1 (fr) * 1990-10-08 1992-04-16 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage contenant du percarbonate
EP0495258A1 (fr) * 1991-01-16 1992-07-22 The Procter & Gamble Company Compositions de détergent contenant de la cellulase de haute activité et de l'argile adoucissant
EP0495554A1 (fr) * 1991-01-16 1992-07-22 The Procter & Gamble Company Compositions de détergent contenant de la cellulase de haute activité et de composés d'ammonium quaternaire
WO1993021294A1 (fr) * 1992-04-13 1993-10-28 The Procter & Gamble Company Utilisation de polyesters modifies pour le lavage de textiles contenant du coton
EP0659876A2 (fr) * 1993-12-24 1995-06-28 The Procter & Gamble Company Composition additive pour détergent
DE4344490A1 (de) * 1993-12-24 1995-06-29 Henkel Kgaa Pulverförmiges Wasch- und Reinigungsmittel

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0381397A2 (fr) * 1989-01-30 1990-08-08 Unilever Plc Compositions détergentes en particules et leur utilisation
WO1992006167A1 (fr) * 1990-10-08 1992-04-16 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage contenant du percarbonate
EP0495258A1 (fr) * 1991-01-16 1992-07-22 The Procter & Gamble Company Compositions de détergent contenant de la cellulase de haute activité et de l'argile adoucissant
EP0495554A1 (fr) * 1991-01-16 1992-07-22 The Procter & Gamble Company Compositions de détergent contenant de la cellulase de haute activité et de composés d'ammonium quaternaire
WO1993021294A1 (fr) * 1992-04-13 1993-10-28 The Procter & Gamble Company Utilisation de polyesters modifies pour le lavage de textiles contenant du coton
EP0659876A2 (fr) * 1993-12-24 1995-06-28 The Procter & Gamble Company Composition additive pour détergent
DE4344490A1 (de) * 1993-12-24 1995-06-29 Henkel Kgaa Pulverförmiges Wasch- und Reinigungsmittel

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
NOVO NORDISK, B157G-GB 3500: "Enzymes for the Detergent Industry", NOVO NORDISK, DK *
U.HOTZ: "Verwendung von Cellulasen in Waschmitteln", TENSIDE, vol. 30, no. 6, DE, pages 388 - 393 *

Also Published As

Publication number Publication date
EP0781323A1 (fr) 1997-07-02
ATE201440T1 (de) 2001-06-15
JPH10506135A (ja) 1998-06-16
ES2158129T3 (es) 2001-09-01
DE4433027A1 (de) 1996-03-21
DE59509292D1 (de) 2001-06-28
EP0781323B1 (fr) 2001-05-23

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