EP0486073B1 - Liquid detergent composition containing lipase and protease - Google Patents

Liquid detergent composition containing lipase and protease Download PDF

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Publication number
EP0486073B1
EP0486073B1 EP19910200149 EP91200149A EP0486073B1 EP 0486073 B1 EP0486073 B1 EP 0486073B1 EP 19910200149 EP19910200149 EP 19910200149 EP 91200149 A EP91200149 A EP 91200149A EP 0486073 B1 EP0486073 B1 EP 0486073B1
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EP
European Patent Office
Prior art keywords
detergent composition
composition according
protease
lipase
acid
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP19910200149
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German (de)
English (en)
French (fr)
Other versions
EP0486073A3 (en
EP0486073A2 (en
Inventor
James Pyott Johnston
Pierre Marie Alain Lenoir
Christiaan Arthur Jacques Kamiel Thoen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
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Procter and Gamble Co
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
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE1991621059 priority Critical patent/DE69121059T2/de
Priority to DK91200149T priority patent/DK0486073T3/da
Priority to EP19910200149 priority patent/EP0486073B1/en
Priority to ES91200149T priority patent/ES2091280T3/es
Priority to CA002096256A priority patent/CA2096256C/en
Priority to JP4500878A priority patent/JPH06504555A/ja
Priority to PCT/US1991/008041 priority patent/WO1992008779A1/en
Priority to AU90416/91A priority patent/AU9041691A/en
Priority to MX9102022A priority patent/MX9102022A/es
Priority to IE395191A priority patent/IE913951A1/en
Priority to NZ24057191A priority patent/NZ240571A/en
Priority to CN 91111550 priority patent/CN1062374A/zh
Priority to TR106991A priority patent/TR27423A/xx
Priority to TW81100525A priority patent/TW215108B/zh
Publication of EP0486073A2 publication Critical patent/EP0486073A2/en
Publication of EP0486073A3 publication Critical patent/EP0486073A3/en
Priority to US08/322,965 priority patent/US5733473A/en
Publication of EP0486073B1 publication Critical patent/EP0486073B1/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C11D3/38663—Stabilised liquid enzyme compositions
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to liquid detergent compositions which contain an enzyme system.
  • the enzyme system is a combination of a modified protease and a lipase.
  • detergent compositions may advantageously comprise enzyme systems.
  • enzyme systems include cellulase, protease, lipase and amylases.
  • the present invention is specifically aiming at providing liquid detergent compositions in which the enzyme system comprises a mixture of protease and lipase.
  • Formulating such a combination in a granular detergent raises no specific issue, since both enzymes can be physically separated. On the contrary, formulating such a combination in a liquid detergent raises a specific technical issue in that the protease is likely to take as a substrate any protein present in the detergent composition.
  • lipases which may also be present in the detergent composition are particularly subject to such proteolytic degradation; as a consequence, the residual activity of the lipase in the detergent composition will rapidly diminish with the storage time of the detergent composition, so that it was up to now impossible to formulate liquid detergent compositions comprising at the same time a lipase and a protease, said detergent compositions being sufficiently stable for a commercial exploitation.
  • liquid detergent composition comprising an enzyme system comprising a lipase and a protease, wherein said enzyme system is stable; by stable, it is meant that the proteolytic degradation of the lipase is substantially reduced.
  • Modified bacterial serine proteases including proteases suitable for use in the compositions according to the invention are disclosed for instance in EP-A-0 328 229 as well as their use in detergent compositions.
  • This patent application describes among others a modified bacterial serine protease which is commercially available from GIST-BROCADES under the name MAXAPEM 15 R
  • LIPOLASE R can be combined with proteases to form a granular enzymatic detergent additive.
  • EP-A-0 381 262 describes detergent compositions comprising a protease and a lipase, preferably LIPOLASE R , together with a stabilizing system.
  • the proteases disclosed in this reference include bacterial proteases.
  • WO-A-8904361 discloses enzymatic detergent compositions comprising lipases from Pseudomonas and a certain group of proteases showing lipase stability in said composition.
  • EP 376,705 discloses Humicola-derived lipase and protease of the Subtilisin-type in detergents showing an enhanced storage stability of the lipase by inclusion of lower aliphatic alcohol and lower carboxylic acid.
  • the present invention is a liquid detergent composition
  • a liquid detergent composition comprising an enzyme system, characterized in that the enzyme system comprises a modified bacterial serine protease or mixtures thereof, and a lipase or mixtures thereof.
  • the bacterial serine protease is modified in that the methionine adjacent to the serine of the active site is substituted by another amino acid.
  • the enzyme system according to the present invention comprises a lipase and a protease.
  • the lipase to be used in the compositions according to the present invention is a lipase derived from Humicola lanuginosa, as described in EP-A-0 258 068 to NOVO INDUSTRI A/S. This patent application describes how to obtain said specific lipase, but said specific lipase is also commercially available from NOVO NORDISK A/S under the trade name LIPOLASE R .
  • compositions according to the present invention typically comprise from 0.1 to 10000 Lipolytic Units per gram of finished product, preferably from 10 to 2500 Lipolytic Units per gram of finished product.
  • Lipolytic units are defined for instance in EP 0 258 068, page 5 lines 38-40.1 LU is the amount of enzyme which liberates 1 ⁇ mol titratable butyric acid per minute at 30°C, pH 7 with gum arabic as an emulsifier. Further details are given in Novo analytical Method AF95/5.
  • the proteases to be used according to the present invention are modified bacterial serine proteases. All native bacterial serine proteases are characterized in that the active site invariably comprises a triade of amino acids which are serine, histidine and aspartic acid. These amino acids are positioned in the native form of the enzyme in such a way that they catalyse the cleavage of internal peptide bonds of proteins. Another common point between these bacterial serine proteases is that there always is a methionine adjacent to the serine of the active site, in the native sequence.
  • the bacterial serine proteases suitable for use according to the present invention are those wherein the methionine adjacent to the serine of the active site has been substituted by another amino acid.
  • the serine of the active site can also be defined as the serine which is homologuous to the serine in position 221 in the amino acid sequence of the bacterial subtilisin protease produced by Bacillus Subtilis ; said sequence is listed herein after in figure 1.
  • this bacterial subtilisin protease is immediately after the serine in position 221 and therefore it is the methionine in position 222 which needs to be substituted by another amino acid. It is possible that, in the sequence of other bacterial serine proteases, this methionine would not be immediately following the serine of the active site; in such a case, it is the methionine homologuous to the methionine in position 222 in the sequence of this bacterial subtilisin protease produced by Bacillus Subtilis which needs to be substituted by another amino acid.
  • modified bacterial serine proteases suitable for use in the compositions according to the invention are commercially available, such as DURAZYM R from NOVO, which is the methionine modified version of SAVINASE R ; another example of available modified protease is MAXAPEM 15 from GIST-BROCADES, which is the modified version of MAXACAL R wherein the methionine in position 216 has been substituted. Also available are experimental samples of modified OPTICLEAN R and OPTIMASE R , from SOLVAY enzymes; both are modified in that the methionine in position 222 is substituted by a cysteine.
  • Preferred modified bacterial serine protease according to the present invention are MAXAPEM 15 R from GIST BROCADES and DURAZYM R from NOVO.
  • compositions according to the present invention typically will contain from 0.005 to 10 mg of active protease per gram of finished product, preferably from 0.01 to 5.0 mg of active protease per gram of finished product. Mixtures of the modified bacterial serine protease described herein above are also suitable for use in the compositions according to the invention.
  • the rest of the liquid detergent composition according to the present invention is made of conventional detergency ingredients, i.e. water, surfactants, builders and others.
  • detergency ingredients i.e. water, surfactants, builders and others.
  • the following description of these ingredients is for the sake of completeness of the description and is not to be construed as limiting the compositions of the present invention to those conventional ingredients described.
  • the liquid detergent compositions herein comprises from 5% to 60% by weight of the total liquid detergent composition, preferably from 10% by weight to 40% by weight of an organic surface-active agent selected from nonionic, anionic, cationic and zwitterionic surface-active agents and mixtures thereof.
  • Suitable anionic surface-active salts are selected from the group of sulfonates and sulfates.
  • the like anionic surfactants are well-known in the detergent arts and have found wide application in commercial detergents.
  • Preferred anionic water-soluble sulfonate or sulfate salts have in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms.
  • Such preferred anionic surfactant salts are the reaction products obtained by sulfating C 8 -C 18 fatty alcohols derived from e.g. tallow oil, palm oil, palm kernel oil and coconut oil; alkylbenzene sulfonates wherein the alkyl group contains from about 9 to about 15 carbon atoms; sodium alkylglyceryl ether sulfonates; ether sulfates of fatty alcohols derived from tallow and coconut oils; coconut fatty acid monoglyceride sulfates and sulfonates; and water-soluble salts of paraffin sulfonates having from about 8 to about 22 carbon atoms in the alkyl chain.
  • Sulfonated olefin surfactants as more fully described in e.g. U.S. Patent Specification 3,332,880 can also be used.
  • the neutralizing cation for the anionic synthetic sulfonates and/or sulfates is represented by conventional cations which are widely used in detergent technology such as sodium, potassium or alkanolammonium.
  • a suitable anionic synthetic surfactant component herein is represented by the water-soluble salts of an alkylbenzene sulfonic acid, preferably sodium alkylbenzene sulfonates, preferably sodium alkylbenzene sulfonates having from about 10 to 13 carbon atoms in the alkyl group.
  • Another preferred anionic surfactant component herein is sodium alkyl sulfates having from about 10 to 15 carbon atoms in the alkyl group.
  • nonionic surfactants suitable for use herein include those produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, or amido group, in the presence of an acidic or basic catalyst, and include compounds having the general formula RA(CH 2 CH 2 O) n H wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom and n represents the average number of ethylene oxide moieties. R typically contains from about 8 to 22 carbon atoms They can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from about 2 to about 24.
  • a preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from about 4 to 10 moles of ethylene oxide per mole or fatty - alcohol.
  • Suitable species of this class of ethoxylates include : the condensation product of C 12 -C 15 oxo-alcohols and 3 to 9 moles of ethylene oxide per mole of alcohol; the condensation product or narrow cut C 14 -C 15 oxo-alcohols and 3 to 9 moles of ethylene oxide per mole of fatty(oxo)alcohol; the condensation product of a narrow cut C 12 -C 13 fatty(oxo)alcohol and 6,5 moles of ethylene oxide per mole of fatty alcohol; and the condensation products of a C 10 -C 14 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty alcohol) in the range from 4 to 8.
  • the fatty oxo alcohols while mainly linear can have, depending upon the processing conditions and raw material olefins, a certain degree of branching, particularly short chain such as methyl branching.
  • a degree of branching in the range from 15% to 50% (weight%) is frequently found in commercial oxo alcohols.
  • Suitable cationic surfactants include quaternary ammonium compounds of the formula R 1 R 2 R 3 R 4 N + where R 1 ,R 2 and R 3 are methyl groups, and R 4 is a C 12-15 alkyl group, or where R 1 is an ethyl or hydroxy ethyl group, R 2 and R 3 are methyl groups and R 4 is a C 12-15 alkyl group.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and another substituent contains, at least, an anionic water-solubilizing group.
  • Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al., issued December 9, 1975 and 3,929,678, Laughlin et al., issued December 30, 1975.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl or hydroxy alkyl moiety of from about 8 to about 28 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from 1 to about 3 carbon atoms which can optionally be joined into ring structures.
  • Poly hydroxy fatty acid amide surfactants of the formula wherein R 1 is H, C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C 11-15 alkyl or alkenyl chain or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable, but preferred is a mixture of citric acid and a substituted succinic acid.
  • the citric acid builder employed in the practice of this invention will be present in the finished product in the form of any water-soluble salt of citric acid.
  • Such salts include, for example, sodium, potassium, ammonium or alkanolammonium salts.
  • a citric acid monohydrate slurry as a starting material, which will be neutralized in situ, so as to form the above mentioned salts.
  • substituted succinic acid builders herein are of the general formula R-CH(COOH)CH 2 (COOH), i.e., derivatives of succinic acid, wherein R is C 10 -C 16 alkyl or alkenyl, preferably C 12 -C 14 alkenyl.
  • substituted succinic acid builders are preferably in the finished product in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts (e.g., mono-, di-, or tri-ethanolammonium).
  • succinic acid derivatives As raw materials, it is preferred to use these succinic acid derivatives in their diacid or anhydride form.
  • the diacid will be neutralized in situ, while the anhydride will undergo a hydrolysis/neutralization process.
  • substituted succinic acid builders include : lauryl succinic acid, myristyl succinic acid, palmityl succinic acid, 2-dodecenyl succinic acid (preferred), 2-tetradecenyl succinic acid, and the like.
  • a preferred builder system comprises from 4% to 12% by weight of the total composition of the above substituted succinic acid builders, and from 4% to 12% by weight of the total composition of citric acid.
  • the compositions according to the invention may also contain a fatty acid. Preferred are oleic and palmitoleic acid.
  • compositions according to the invention may also comprise an enzyme stabilizing system.
  • an enzyme stabilizing system provides a system wherein the protease does not significantly attack the native lipase, but the enzyme system or components thereof may still be subject to unstability problem due to the other detergency ingredients. Therefore, stabilizing agents may be needed, which are conventional and well known in the art.
  • a preferred enzyme stabilizing system is selected from boric acid, 1,2-propanediol, carboxylic acids, and mixtures thereof. These enzyme stabilizing systems are typically present in amounts of from 0.01% to 5% by weight of the total composition.
  • compositions of the invention may also comprise other enzymes.
  • enzymes such as cellulases or amylases.
  • Amylases particularly, seem to be stable in the presence of protease, and the compositions of the invention therefore preferably comprise an amylase.
  • compositions herein can contain a series of further optional ingredients.
  • the like additives include : suds regulants, opacifiers, agents to improve the machine compatibility in relation to enamel-coated surfaces, bactericides, dyes, perfumes, bleaches including perborate and percarbonate, brighteners, soil release agents, softening agents and the like.
  • the liquid compositions herein can contain further additives, typically at levels of from 0.05 to 5%.
  • additives include polyaminocarboxylates such as ethylenediaminotetracetic acid, diethylenetriaminopentacetic acid, ethylenediamino disuccinic acid or water-soluble alkali metals thereof.
  • Other additives include organo-phosphonic acids; particularly preferred are ethylenediamino tetramethylenephosphonic acid, hexamethylenediamino tetramethylenephosphonic acid, diethylenetriamino pentamethylenephosphonic acid and aminotrimethylenephosphonic acid.
  • compositions according to the invention are made by mixing the listed ingredients in the listed proportions.
  • compositions according to the invention are made by mixing the listed ingredients in the listed proportions 6 7 8 9 10 - Linear alkyl benzene sulfonate 5 7 9 8 10 - Sodium C 12-15 alkyl sulfate 5 2 1.75 0 3 - C 14-15 alkyl 2.5 times ethoxylated sulfate 2 0 2 0 0 - C 12 glucose amide 6 0 7 0 0 - C 12-15 alcohol 7 times ethoxylated 0 0 0.5 0 11.6 - C 12-15 alcohol 5 times ethoxylated 0 8 0 8 - Oleic Acid 0 0 0 3.5 2.5 - Citric Acid 10 9 9.5 4 1 - C 12-14 alkenyl substituted succinic acid 11 0 11.5 0 0 - STPP 0 20 0 0 0 - Zeolite 0 0 0 26 0 - Ethanol 6 4 4 3 6 - 1,2-propanedio
  • compositions according to the invention are made by mixing the listed ingredients in the listed proportions 11 12 13 14 15 - Linear alkyl benzene sulfonate 5 7 9 8 10 - Sodium C 12-15 alkyl sulfate 5 2 1.75 0 3 - C 14-15 alkyl 2.5 times ethoxylated sulfate 2 0 2 0 0 - C 12 glucose amide 6 0 7 0 0 - C 12-15 alcohol 7 times ethoxylated 0 0 0.5 0 11.6 - C 12-15 alcohol 5 times ethoxylated 0 8 0 8 - Oleic Acid 0 0 0 3.5 2.5 - Citric Acid 10 9 9.5 4 1 - C 12-14 alkenyl substituted succinic acid 11 0 11.5 0 0 - Tartrate monosuccinate 0 15 0 17 20 - Diethoxylated poly (1,2 propylene terephtalate) 1.0 0.5 0.7 0 0.5
EP19910200149 1990-11-14 1991-01-25 Liquid detergent composition containing lipase and protease Expired - Lifetime EP0486073B1 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
DE1991621059 DE69121059T2 (de) 1990-11-14 1991-01-25 Lipase- und proteasehaltige flüssige Waschmittelzusammensetzung
DK91200149T DK0486073T3 (da) 1990-11-14 1991-01-25 Væskeformig detergentsammensætning, der indeholder lipase og protease
EP19910200149 EP0486073B1 (en) 1990-11-14 1991-01-25 Liquid detergent composition containing lipase and protease
ES91200149T ES2091280T3 (es) 1990-11-14 1991-01-25 Composicion detergente liquida que contiene lipasa y proteasa.
CA002096256A CA2096256C (en) 1990-11-14 1991-11-04 Liquid detergent composition containing lipase and protease
JP4500878A JPH06504555A (ja) 1990-11-14 1991-11-04 リパーゼおよびプロテアーゼを含有する液状洗剤組成物
PCT/US1991/008041 WO1992008779A1 (en) 1990-11-14 1991-11-04 Liquid detergent composition containing lipase and protease
AU90416/91A AU9041691A (en) 1990-11-14 1991-11-04 Liquid detergent composition containing lipase and protease
MX9102022A MX9102022A (es) 1990-11-14 1991-11-12 Composicion detergente liquida que contiene lipasa y proteasa
IE395191A IE913951A1 (en) 1990-11-14 1991-11-13 Liquid detergent composition containing lipase and protease
NZ24057191A NZ240571A (en) 1990-11-14 1991-11-13 Liquid detergents containing an enzyme system of lipase and modified protease
CN 91111550 CN1062374A (zh) 1990-11-14 1991-11-14 含有脂肪酶和蛋白酶的液体洗涤剂组合物
TR106991A TR27423A (tr) 1990-11-14 1991-12-04 Lipaz ve proteazi ihtiva eden sivi deterjan.
TW81100525A TW215108B (xx) 1990-11-14 1992-01-25
US08/322,965 US5733473A (en) 1990-11-14 1994-10-13 Liquid detergent composition containing lipase and protease

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP90870212 1990-11-14
EP90870212 1990-11-14
EP19910200149 EP0486073B1 (en) 1990-11-14 1991-01-25 Liquid detergent composition containing lipase and protease

Publications (3)

Publication Number Publication Date
EP0486073A2 EP0486073A2 (en) 1992-05-20
EP0486073A3 EP0486073A3 (en) 1993-06-23
EP0486073B1 true EP0486073B1 (en) 1996-07-24

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Application Number Title Priority Date Filing Date
EP19910200149 Expired - Lifetime EP0486073B1 (en) 1990-11-14 1991-01-25 Liquid detergent composition containing lipase and protease

Country Status (14)

Country Link
EP (1) EP0486073B1 (xx)
JP (1) JPH06504555A (xx)
CN (1) CN1062374A (xx)
AU (1) AU9041691A (xx)
CA (1) CA2096256C (xx)
DE (1) DE69121059T2 (xx)
DK (1) DK0486073T3 (xx)
ES (1) ES2091280T3 (xx)
IE (1) IE913951A1 (xx)
MX (1) MX9102022A (xx)
NZ (1) NZ240571A (xx)
TR (1) TR27423A (xx)
TW (1) TW215108B (xx)
WO (1) WO1992008779A1 (xx)

Families Citing this family (14)

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Publication number Priority date Publication date Assignee Title
JPH06507198A (ja) * 1991-04-30 1994-08-11 ザ、プロクター、エンド、ギャンブル、カンパニー アリールボロン酸を含有する液体洗浄剤
BR9206636A (pt) * 1991-10-16 1995-10-24 Unilever Nv Composição detergente enzimática e processo para a preparação de uma composição detergente enzimática aquosa
US5442100A (en) * 1992-08-14 1995-08-15 The Procter & Gamble Company β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids
JP2859520B2 (ja) * 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ リパーゼ及びそれを生産する微生物及びリパーゼ製造方法及びリパーゼ含有洗剤組成物
ATE318304T1 (de) 1993-10-08 2006-03-15 Novozymes As Amylasevarianten
DE4344154A1 (de) * 1993-12-23 1995-06-29 Henkel Kgaa Enzymhaltiges Flüssigwaschmittel
JP4733861B2 (ja) * 2001-06-20 2011-07-27 花王株式会社 酵素粒子
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WO2011084412A1 (en) * 2009-12-21 2011-07-14 Danisco Us Inc. Detergent compositions containing thermobifida fusca lipase and methods of use thereof
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NZ240571A (en) 1994-11-25
TR27423A (tr) 1995-04-21
MX9102022A (es) 1992-07-08
CA2096256C (en) 1999-05-11
CN1062374A (zh) 1992-07-01
JPH06504555A (ja) 1994-05-26
DK0486073T3 (da) 1996-12-09
WO1992008779A1 (en) 1992-05-29
DE69121059T2 (de) 1997-03-06
TW215108B (xx) 1993-10-21
EP0486073A3 (en) 1993-06-23
DE69121059D1 (de) 1996-08-29
IE913951A1 (en) 1992-05-20
ES2091280T3 (es) 1996-11-01
CA2096256A1 (en) 1992-05-15
EP0486073A2 (en) 1992-05-20
AU9041691A (en) 1992-06-11

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