CN1062374A - The liquid detergent composition that contains lipase and proteolytic enzyme - Google Patents

The liquid detergent composition that contains lipase and proteolytic enzyme Download PDF

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Publication number
CN1062374A
CN1062374A CN 91111550 CN91111550A CN1062374A CN 1062374 A CN1062374 A CN 1062374A CN 91111550 CN91111550 CN 91111550 CN 91111550 A CN91111550 A CN 91111550A CN 1062374 A CN1062374 A CN 1062374A
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China
Prior art keywords
detergent composition
proteolytic enzyme
enzyme
lipase
mixture
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Pending
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CN 91111550
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Chinese (zh)
Inventor
P·J·约翰斯顿
P·M·A·勒努瓦
C·A·J·K·特恩
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Procter and Gamble Co
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Procter and Gamble Co
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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

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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)

Abstract

The invention discloses liquid detergent composition, this detergent composition contains cleaning ingredients commonly used and enzyme system, and wherein enzyme system contains the bacterial serine proteolytic enzyme of lipase or its mixture and modification or the mixture of said proteolytic enzyme.

Description

The liquid detergent composition that contains lipase and proteolytic enzyme
The present invention relates to contain the liquid detergent composition of enzyme system.This enzyme system is the proteolytic enzyme of modification and the mixture of lipase.
As everyone knows, in the art, detergent composition can contain enzyme system expediently.This class enzyme system comprises cellulase, proteolytic enzyme, lipase and amylase.Purpose of the present invention particularly is to provide liquid detergent composition, and the enzyme system in this liquid detergent composition contains the mixture of proteolytic enzyme and lipase.
Prepare this class granular detergent composition and can not cause special problem, because these two kinds of enzymes can separate physically.Otherwise, prepare the special technique problem that this class I liquid I detergent mixture causes and be that proteolytic enzyme is counted as a kind of any proteinic Substrate that is present in this detergent composition probably.
Particularly, as can be seen, also may reside in the Degradation that lipase in the detergent composition is easier to take place this proteinoid hydrolysis.The result, the residual activity of the lipase in detergent composition will the very fast minimizing along with the storage time of this detergent composition, so that till now, the liquid detergent composition that preparation contains lipase and proteolytic enzyme simultaneously is impossible, and utilize for commodity, above-mentioned detergent composition but is enough stablizing.
Therefore, the purpose of this invention is to provide a kind of liquid detergent composition that contains the enzyme system that comprises lipase and proteolytic enzyme, wherein said enzyme system is stable.The stable meaning is meant the proteoclastic Degradation that has reduced this lipase basically.
Find now, it is by using the mixture of any lipase or its mixture and bacterial serine proteolytic enzyme or this proteinoid enzyme that this purpose can be implemented, in this proteolytic enzyme, the methionine(Met) adjacent with the Serine of reactive site replaced by other amino acid.In fact, have been found that this special composition will provide the enzyme system that contains proteolytic enzyme and lipase, and lipase will be stable in liquid detergent composition.
The advantage that this solution has is simple, because it only needs commercially available composition.Really, the various lipase that not only are suitable for using in detergent composition are commercially available, and the bacterial serine proteolytic enzyme that is suitable for the various modifications of purpose of the present invention also is commercially available.In addition, detergent composition of the present invention does not need to add special lipase stablizer, and therefore, with regard to the price of product with to the adaptability of environment, detergent composition of the present invention is attractive especially.
The bacterial serine proteolytic enzyme that comprises the modification of the proteolytic enzyme that not only is used for detergent composition but also is suitable for using in composition of the present invention for example is disclosed among the EP-A-0328229.The bacterial serine proteolytic enzyme of modification has especially been described in this patent application, and this kind proteolytic enzyme is commercially available (from GISTBROCADES), and its trade mark is called MAXAPEM15 R
At in March, 1988 the 6th page of disclosed Biotechnology Newswatch() and EP-A-0258 268 a kind of lipase has been described, this lipase is commercially available (from NOVO NORDISKA/S), its trade mark is called LIPOLASE RThis european patent application has been mentioned LIPOLASE RCan combine with proteolytic enzyme to form particle enzyme detergent additives.
EP-A-0 381262 has described and has contained proteolytic enzyme and lipase (is preferably LIPOLASE R) have the detergent composition of stabilising system simultaneously.Disclosed proteolytic enzyme comprises bacteria protease in this reference.
Therefore, the present invention is the liquid detergent composition that contains enzyme system, it is characterized in that this enzyme system contains bacterial serine proteolytic enzyme or its mixture of modification, and lipase or its mixture.The modification of this bacterial serine proteolytic enzyme is to be replaced by other amino acid adjacent to the methionine(Met) of the Serine of avtive spot.
Enzyme system of the present invention contains lipase and proteolytic enzyme.As described in EP0381262 or EP271152, any lipase that is suitable for using in detergent composition can both use in composition of the present invention.As described in the EP-A-0258068 that authorizes NOVO INDUSTRIA/S, the preferred lipase that uses in the present composition is the lipase that is obtained by Humicolalanuginosa.This patent application describes how to obtain said special lipase, but said special lipase also is that commercially available (from NOVO NORDISKA/S, trade(brand)name is LIPOLASE R).Be applicable to that other commercially available lipase of the present invention are Amono-P Lipase R, Amono-B Lipase R, Amono CES Lipase R, Amono AKG Lipase R, these lipase are all from Amono pharma-ceuticals(Japan); Toyo Jozo Co(Japan) and US biochemical Corp.(USA) and Diosynth Co.(NL) also become the lipase commodity that are fit to that are used for the present composition.
The general every gram finished product of composition of the present invention contains 0.1 to 10000 steatolysis unit, and preferably every gram finished product contains 10 to 2500 steatolysis units.Steatolysis unit is defined for example at EP0258268(page 5 38 row) in.
Proteolytic enzyme used in the present invention is the bacterial serine proteolytic enzyme of modification.All natural bacteria serine proteases are characterised in that its avtive spot always contains three seed amino acids, and this three seed amino acid is Serine, Histidine and aspartic acid.These amino acid are with the natural form of enzyme and with a kind of like this method location, so that the interior peptide bond of their catalysis split proteins.Another common ground between these bacterial serine proteolytic enzyme is always to have the methionine(Met) adjacent to the Serine of avtive spot that exists with natural order.Be applicable to that those bacterial serine proteolytic enzyme of the present invention are wherein to be replaced by other amino acid adjacent to the methionine(Met) of the Serine of avtive spot.The Serine of avtive spot also can be defined as such Serine, and promptly it is the Serine on 221 that come from together in the amino-acid sequence of the bacterium subtilisin that is produced by Bacillus subtilus (Bacillus Subtilis).Said order is listed among hereinafter Fig. 1.
In the order of this bacterium subtilisin that is produced by Bacillus subtilus, methionine(Met) is right after after the Serine on 221, thus it be need be by other amino acid the methionine(Met) on displaced 222.Possible is, in other the order of bacterial serine proteolytic enzyme, this methionine(Met) always is not right after the back at the Serine of avtive spot.Under these circumstances, it is the methionine(Met) on 222 that come from together in the order of this bacterium subtilisin that is produced by Bacillus subtilus, and this kind methionine(Met) need be replaced by other amino acid.
Certainly, the present invention does not lie in the proteolytic enzyme, opposite of these modifications itself, should be the proteolytic enzyme of these modifications is applied to also contain in the liquid detergent composition of lipase especially.Therefore.Describing in detail and how accessing these modified protein enzymes is not purpose of the present invention.This modification is can be by site-directed mutagenesis or by finishing at for this purpose known any other gene engineering in the art.For example, EP-A-0328229(authorizes GIST-BROCADES N.V.) described how to obtain this proteinoid enzyme.The method of Shi Heing is described among the EP130756 in addition, and the document has also been described the bacterial serine proteolytic enzyme of the modification that is applicable in the composition of the present invention.
In addition, be applicable to that the bacterial serine proteolytic enzyme of some modification in the present composition is commercially available, for example DURAZYM R(from NOVO), it is SAVINASE RThe methionine(Met) of modified form.The examples of proteases of another kind of available modification is that MAXAPEM15(is from GIST-BROCADES), it is MAXACAL RModified form, wherein the methionine(Met) on 216 is replaced.The OPTICLEAN of modification RAnd OPTIMASE RThe test sample of (from the SOLVAY enzyme) also is available, and both modifications are that the methionine(Met) on 222 is replaced by Gelucystine.The bacterial serine proteolytic enzyme of the preferred modification of the present invention is MAXAPEM15 R(from GIST BROCADES) and DURAZYM R(from NOVO).
The general every gram finished product of composition of the present invention contains 0.005 to 10mg active protease, and preferably every gram finished product contains 0.01 to 5.0mg active protease.The mixture of the bacterial serine proteolytic enzyme of the modification that this paper is above-mentioned also is applicable to the present composition.
The remainder of liquid detergent composition of the present invention is by cleaning ingredients commonly used, promptly water, tensio-active agent, help washing and other materials to form.Following narration for these compositions is to have integrity in order to make to narrate, and can not think composition of the present invention is restricted on described those compositions commonly used.
Liquid detergent composition of the present invention contains 5% to 60% of liquid detergent composition gross weight, the organic surface active agent of preferred 10% to 40% weight, this organic surface active agent are selected from non-ionic, anionic, cationic and zwitterionic tensio-active agent and its mixture.
The anion surface activity salt that is fit to is selected from sulfonate and vitriol.Similarly anion surfactant is known in the washing composition technical field, and has been found and is widely used in the commercially available detergent.Preferred anionic surfactants water-soluble sulfonate or vitriol have in their molecular structure and contain about 8 alkyl to about 22 carbon atoms.
The example of this class preferred anionic surfactants surfactant salt is by Sulfated C 6-C 16The reaction product that fatty alcohol (from for example tallow oil, plam oil, palm-kernel oil and Oleum Cocois) obtains; Alkylbenzene sulfonate (alkyl wherein contain have an appointment 9) to about 15 carbon atoms; The alkyl glycerylether sodium sulfonate; The ether sulfate of the fatty alcohol that obtains by tallow oil and Oleum Cocois; Coconut fatty acid monoglyceride vitriol and sulfonate; With in alkyl chain, have about 8 water-soluble salts to the sulfonated alkane of about 22 carbon atoms.Just as U.S.3, in 332,880 the patent specification more fully as described in, sulfonated olefin sheet surface-active agent also is spendable.For example sodium, potassium or alkanol ammonium provide to be used for positively charged ion commonly used that the neutralizing cation of negatively charged ion synthetic sulfonate and/or vitriol can be by being widely used in the washing composition technology.
The negatively charged ion synthetic surfactant composition that is fit among the present invention is that the water-soluble salt preferred alkyl benzene sulfonic acid sodium salt by alkyl benzene sulphonate (ABS) provides, and preferably has the sodium alkyl benzene sulfonate of about 10 to 13 carbon atoms in alkyl.Another kind of preferred anionic surfactants surfactant component is the sodium alkyl sulfate that has about 10 to 15 carbon atoms in alkyl among the present invention.
Be applicable to that ionic surfactant pack of the present invention draws together, by in the presence of acidity or basic catalyst, oxyethane with have an active hydrogen atom, for example the hydrocarbon of hydroxyl, carboxyl or amido carries out condensation and those materials of producing, and comprises that having general formula is RA(CH 2CH 2O) nThe compound of H, in this general formula, R represents hydrophobic part, the A representative has the group of active hydrogen atom, n represents the mean number of ethylene oxide moiety, and R contains 8 to 22 carbon atoms of having an appointment usually, and they also can be by 1,2-propylene oxide and low-molecular weight compound carry out condensation and form, n usually about 2 to about 24 variations.
The condensation product of the fatty alcohol that the nonionic ethoxylate of preferred class can be by having 12 to 15 carbon atoms and about 4 to 10 moles oxyethane (every mole of fatty alcohol) provides.The ethoxylate that this class is fit to comprises C 12-C 15The condensation of pure and mild 3 to the 9 moles oxyethane (every mol of alcohol) of oxo process produce; Narrow fraction C 14-C 15The condensation product of pure and mild 3 to the 9 moles oxyethane (every mole of aliphatics (oxo process) alcohol) of oxo process; Narrow fraction C 12-C 13The condensation product of pure and mild 6.5 moles of ethylene oxide of aliphatics (oxo process) (every mole of fatty alcohol); C with the ethoxylation degree (moles of ethylene oxide/mole Fatty Alcohol(C12-C14 and C12-C18)) in 4 to 8 scopes 10-C 14The condensation product of coconut Fatty Alcohol(C12-C14 and C12-C18).Although the aliphatics oxo alcohol is mainly straight chain, branching to a certain degree, particularly short chain such as methyl-branched are also arranged, this depends on processing condition and raw material olefin.The degree of branching common in the commodity oxo alcohol is at 15% to 50%(weight %) scope in.
The cats product that is fit to comprises formula R 1R 2R 3R 4N +Quaternary ammonium compound, in the formula, R 1, R 2And R 3Be methyl, R 4Be C 12-15Alkyl, or R 1Be ethyl or hydroxyethyl, R 2And R 3Be methyl, R 4Be C 12-15Alkyl.
Zwitterionics comprises the quaternary ammonium, Phosphonium of aliphatic series and the derivative of blunderbuss compound, in this derivative, aliphatic series part can be straight chain or side chain, one of them aliphatic substituting group contains has an appointment 8 to about 24 carbon atoms, another substituting group contains the anionic water-soluble group at least.Ammonium sulphonate that particularly preferred zwitter-ion material is ethoxylation and ammonium sulfate [be disclosed in U, S patent 3,925, people such as 262(Laughlin, on December 9th, 1975 published) and 3,929, people such as 678(Laughlin, on December 30th, 1975 published) in].
Semi-polar ionic surfactant pack is drawn together water-soluble amine oxides, and this water-soluble amine oxides contains an alkyl or hydroxyalkyl (contain and have an appointment 8 to about 28 carbon atoms) part and is selected from two portions (can be connected to ring texture arbitrarily) of alkyl and hydroxyalkyl (containing 1 to about 3 carbon atoms).
Has formula
Figure 911115501_IMG1
The tensio-active agent of polyhydroxy fatty acid amide also be fit to, in following formula, R 1Be H, C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-31Alkyl, Z are to have linear hydrocarbyl chain and have at least 3 hydroxyls directly to be connected in polyhydroxy alkyl or its alkoxy derivative on this chain.Preferred R 1Be methyl, R 2Be the C of straight chain 11-15Alkyl chain or alkenyl chain, or its mixture, and Z be in reductive amination process by reducing sugar, deriving as glucose, fructose, maltose, lactones obtains.
Composition of the present invention can further contain builder system.Any builder system commonly used all is fit to, but the mixture of the succsinic acid of citric acid and replacement preferably.
Employed citric acid washing assistant will be present in the finished product with the form of any water-soluble salt of citric acid in enforcement of the present invention.This class salt comprises, for example sodium, potassium, ammonium or alkanol ammonium salts.In fact, using citric acid monohydrate compound slurry is very easily as starting raw material, and it will be neutralized on the spot, so that form above-mentioned salt.
It is R-CH(COOH that the succsinic acid washing assistant of replacement of the present invention has general formula) CH 2(COOH), i.e. the derivative of succsinic acid, in following formula, R is C 10-C 16Alkyl or alkenyl, preferably C 12-C 14Alkenyl.
The succsinic acid washing assistant of these replacements preferably comprises that with their water-soluble salt the form of sodium, potassium, ammonium and alkanol ammonium salts (for example, two or triethanol ammonium) is present in the finished product.
As raw material, preferably use their derivative with the form of two acid or anhydrides of these succsinic acids.Diacid can be neutralized on the spot, and acid anhydride then passes through hydrolysis/N-process.
The specific examples of the succsinic acid washing assistant that replaces comprises lauryl succsinic acid, myristyl succsinic acid, palmityl succsinic acid, 2-dodecenyl succinic succsinic acid (preferably), 2-tetradecene base succsinic acid, or the like.
Preferred builder system includes 4 to 12% citric acid of the succsinic acid washing assistant of 4 to 12% above-mentioned replacement of composition total weight and composition total weight.As another kind of washing assistant, composition of the present invention also can contain lipid acid, preferably oleic acid and Zoomeric acid.
The personnel that are skilled in technique in the art are known to be the performance that the pH value of composition can greatly influence enzyme system.Therefore, composition of the present invention preferably has the pH value that is adjusted in 6 to 10 scopes, is preferably 7.5 to 8.0.
Composition of the present invention also can comprise the enzyme stabilising system.In fact, the invention provides a wherein system of the not obvious destruction native lipase of proteolytic enzyme, but because the existence of other cleaning ingredients, problem of unstable still may take place in this enzyme system or its component easily.Therefore, stablizer may need, these stablizers be use always and be that the present technique field is known.Preferred enzyme stabilising system is selected from boric acid, 1,2-propylene glycol, carboxylic acid and its mixture.The general amount that exists of these enzyme stabilising systems is 0.01% to 5% of a composition total weight.
Composition of the present invention also can contain other enzymes, for example cellulase or amylase.Particularly, under the situation that proteolytic enzyme exists, amylase is seemingly stable, and therefore, composition of the present invention preferably contains amylase.
Composition of the present invention can contain a series of other selectable compositions.The example of the additive of this class comprises: foaming regulator, opalizer, for improving additive for the machine consistency on enamel coating surface, sterilant, dyestuff, spices, the SYNTHETIC OPTICAL WHITNER that comprises perborate and percarbonate, whitening agent, soil release agent, softening agent etc.
The amount that liquid composition of the present invention can contain other additive is generally 0.05 to 5%.These additives comprise the polyamino carboxylate, for example the amino tetraacethyl of ethylene, diethylidene triamino pentaacetic acid, the amino disuccinic acid of ethylene or its water-soluble alkali metal salts.Other additive comprises organic phospho acid, particularly preferably is the amino tetramethylene phosphonic acid of ethylene, hexa-methylene diamino tetramethylene phosphonic acid, diethylidene triamino pentamethylene phosphonic acids and Amino Trimethylene Phosphonic Acid.
Embodiment
Following composition of the present invention be in the table in ratio with the composition of listing mixed.
1 2 3 4 5
Linear alkylbenzene sulfonate 12 7678
C 12-15Sodium alkyl sulfate 22332
C 14-15The vitriol 00220 of alkyl 2.5 ethoxylations
C 12Grape glucamide 00660
The C of 7 ethoxylations 12-15Alcohol 80000
5 ethoxylations 12-15Alcohol 08008
Oleic acid 20000
Citric acid 399 13 15
C 12-14The succsinic acid 10 5576 that alkenyl replaces
Ethanol 44345
1,2-propylene glycol 23312
NaOH 6 8 8 11 11
Diethylenetriamine five (methylene phosphonic acid) 0.5 0.7 0.7 11
Amylase (143KNU/g) 0.1 0.1 0.05 0.2 0.1
Lipolase R(100KLU/g commercial solution) 0.4 0.2 0.3 0.3 0.3
The PEM15R(50mg/g commercial solution) 0.3 000 0.4
Durazym R(39mg/g commercial solution) 0 0.2 000
Opticlean M222C R(test sample) 0 0.1 0 0.4 0
Optimase M222C R(test sample) 00 0.3 00
CaCl2 0.01 0 0.01 0.01 0.02
Sodium metaborate 2.2 2243
Trolamine 00000
Sodium formiate 00000
Lipid acid 00000
Water and subsidiary-balance are to 100%-
Embodiment
Following composition of the present invention be in the table in ratio with the composition of listing mixed.
6 7 8 9 10
The alkylbenzene sulfonate 5798 10 of straight chain
C 12-15Sodium alkyl sulfate 52 1.75 03
C 14-15The vitriol 20200 of alkyl 2.5 ethoxylations
C 12Grape glucamide 60700
The C of 7 ethoxylations 12-15Alcohol 00 0.5 0 11.6
The C of 5 ethoxylations 12-15Alcohol 0808
Oleic acid 000 3.5 2.5
Citric acid 10 9 9.5 41
C 12-14The succsinic acid 11 0 11.5 00 that alkenyl replaces
Tripoly phosphate sodium STPP 0 20 000
Zeolite 000 26 0
Ethanol 64436
1,2-propylene glycol 3222 1.5
NaOH 9 9 9.8 9 3.5
Diethylenetriamine five (methylene phosphonic acid) 1.0 1.0 1.0 0.5 0.8
Amylase (143KNU/g) 0.2 0.1 0.2 0.05 1
Lipolase R(100KLU/g commercial solution) 0.5 0.5 0.3 0.2 0.3
The PEM15R(50mg/g commercial solution) 0.4 000 0.2
The DurazymR(39mg/g commercial solution) 00 0.5 0 0.2
Opticlean M222C R(test sample) 000 0.3 0
Optimase M222C R(test sample) 0 0.5 000
CaCl2 0.01 0.01 0.02 0.02 0.01
Sodium metaborate 42430
Trolamine 00006
Sodium formiate 00001
Lipid acid 0000 12
Water and subsidiary-balance are to 100%-
Embodiment
Following composition of the present invention be in the table in ratio with the composition of listing mixed.
11 12 13 14 15
The alkylbenzene sulfonate 5798 10 of straight chain
C 12-15Sodium alkyl sulfate 52 1.75 03
C 14-15The vitriol 20200 of alkyl 2.5 ethoxylations
C 12Grape glucamide 60700
The C of 7 ethoxylations 12-15Alcohol 00 0.5 0 11.6
The C of 5 ethoxylations 12-15Alcohol 0808
Oleic acid 000 3.5 2.5
Citric acid 10 9 9.5 41
C 12-14The succsinic acid 11 0 11.5 00 that alkenyl replaces
Tartrate monosuccinic acid salt 0 15 0 17 20
Diethoxyization is gathered (propylene terephthalate) 1.0 0.5 0.7 0 0.5
Ethanol 64436
1,2-propylene glycol 3222 1.5
NaOH 9 9 9.8 9 3.5
Diethylenetriamine five (methylene phosphonic acid) 1.0 1.0 1.0 0.5 0.8
Amylase (143KNU/g) 0.2 0.1 0.2 0.05 1
Lipolase R(100KLU/g commercial solution) 0.5 0.5 0.3 0.2 0.3
PEM15 R(50mg/g commercial solution) 0.4 000 0.2
Durazym R(39mg/g commercial solution) 00 0.5 0 0.2
Opticlean M222C R(test sample) 000 0.3 0
Optimase M222C R(test sample) 0 0.5 000
CaCl2 0.01 0.01 0.02 0.02 0.01
Sodium metaborate 42430
Trolamine 00006
Sodium formiate 00001
Lipid acid 0000 12
Water and subsidiary-balance are to 100%-

Claims (11)

1, a kind of liquid detergent composition, this detergent composition contains cleaning ingredients commonly used, it is characterized in that containing lipase or its mixture and proteolytic enzyme, wherein proteolytic enzyme is the mixture of bacterial serine proteolytic enzyme or said proteolytic enzyme, in proteolytic enzyme, replaced by other amino acid adjacent to the methionine(Met) of the Serine of avtive spot.
2, according to the detergent composition of claim 1, wherein fat is that the fat enzyme is LIPOLASE R
3, according to the detergent composition of claim 1, this detergent composition contains lipase, and its content makes it every gram finished product and has 0.1 to 10000 steatolysis unit.
4, according to the detergent composition of claim 1, this detergent composition contains the described proteolytic enzyme of claim 1 or its mixture, and its content makes it every gram finished product and has 0.005 to 10mg active protease.
5, according to the detergent composition of claim 1, wherein the bacterial serine proteolytic enzyme of modification is selected from MAXAPEM15 R, DURAZYM R, M222C OPTICLEAN RWith M222C OPTIMASE R, or its mixture.
6, according to the detergent composition of claim 1, this detergent composition contains amylase in addition.
7, according to the detergent composition of claim 1, this detergent composition contains the enzyme stabilising system in addition.
8, according to the detergent composition of claim 7, wherein the enzyme stabilising system is made up of 0.01 to 5% boric acid for composition total weight.
9, according to the detergent composition of claim 7, wherein the enzyme stabilising system contains 1,2-propylene glycol and/or carboxylic acid and its mixture.
10, according to the detergent composition of claim 1, this detergent composition has pH value in 6 to 10 scope.
11, according to the detergent composition of claim 10, it is 7.0 to 8.5 that this detergent composition has pH value.
CN 91111550 1990-11-14 1991-11-14 The liquid detergent composition that contains lipase and proteolytic enzyme Pending CN1062374A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP90870212.9 1990-11-14
EP90870212 1990-11-14
EP19910200149 EP0486073B1 (en) 1990-11-14 1991-01-25 Liquid detergent composition containing lipase and protease
EP91200149.2 1991-01-25

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CN (1) CN1062374A (en)
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CA (1) CA2096256C (en)
DE (1) DE69121059T2 (en)
DK (1) DK0486073T3 (en)
ES (1) ES2091280T3 (en)
IE (1) IE913951A1 (en)
MX (1) MX9102022A (en)
NZ (1) NZ240571A (en)
TR (1) TR27423A (en)
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CN1072718C (en) * 1993-08-30 2001-10-10 诺沃·诺迪斯克A/S Novel lipase, microorganism producing the lipase, process for producing the lipase and use of the lipase
CN102444018A (en) * 2011-10-26 2012-05-09 芜湖南翔羽绒有限公司 Biochemical combination precision washing technology for eiderdown
CN102604754A (en) * 2012-02-03 2012-07-25 深圳市绿微康生物工程有限公司 Biological enzyme cleaning agent and method for preparing same
CN101925669B (en) * 2008-01-28 2013-08-14 埃科莱布有限公司 Multiple enzyme cleaner for surgical instruments and endoscopes
CN107810260A (en) * 2015-06-26 2018-03-16 荷兰联合利华有限公司 Laundry detergent composition
CN107922935A (en) * 2015-08-28 2018-04-17 荷兰联合利华有限公司 Liquid detergent compositions comprising lipase and protease

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2109526C (en) * 1991-04-30 1998-01-20 Dwight M. Peterson Liquid detergents with an aryl boroic acid
HUT66846A (en) * 1991-10-16 1995-01-30 Unilever Nv Aqueous enzymatic detergent compositions
US5442100A (en) * 1992-08-14 1995-08-15 The Procter & Gamble Company β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids
EP1707624A3 (en) 1993-10-08 2007-01-03 Novozymes A/S Amylase variants
DE4344154A1 (en) * 1993-12-23 1995-06-29 Henkel Kgaa Liquid detergent containing enzymes
JP4733861B2 (en) * 2001-06-20 2011-07-27 花王株式会社 Enzyme particles
MX2012007168A (en) * 2009-12-21 2012-07-23 Danisco Us Inc Detergent compositions containing thermobifida fusca lipase and methods of use thereof.
DE102013224250A1 (en) 2013-11-27 2015-05-28 Henkel Ag & Co. Kgaa Lipase stabilization in dishwashing detergents

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4760025A (en) * 1984-05-29 1988-07-26 Genencor, Inc. Modified enzymes and methods for making same
US4980288A (en) * 1986-02-12 1990-12-25 Genex Corporation Subtilisin with increased thermal stability
US4810414A (en) * 1986-08-29 1989-03-07 Novo Industri A/S Enzymatic detergent additive
DK571587D0 (en) * 1987-11-02 1987-11-02 Novo Industri As ENZYMATIC DETERGENT COMPOSITION
CN1056187C (en) * 1988-02-11 2000-09-06 金克克国际有限公司 Proteolytic enzymes and their use in detergents
CA2006527A1 (en) * 1988-12-30 1990-06-30 Martin S. Cardinali Enzymatic liquid detergent compositions
US4959179A (en) * 1989-01-30 1990-09-25 Lever Brothers Company Stabilized enzymes liquid detergent composition containing lipase and protease
US5030378A (en) * 1990-01-02 1991-07-09 The Procter & Gamble Company Liquid detergents containing anionic surfactant, builder and proteolytic enzyme

Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN1072718C (en) * 1993-08-30 2001-10-10 诺沃·诺迪斯克A/S Novel lipase, microorganism producing the lipase, process for producing the lipase and use of the lipase
CN101925669B (en) * 2008-01-28 2013-08-14 埃科莱布有限公司 Multiple enzyme cleaner for surgical instruments and endoscopes
CN102444018A (en) * 2011-10-26 2012-05-09 芜湖南翔羽绒有限公司 Biochemical combination precision washing technology for eiderdown
CN102604754A (en) * 2012-02-03 2012-07-25 深圳市绿微康生物工程有限公司 Biological enzyme cleaning agent and method for preparing same
CN102604754B (en) * 2012-02-03 2013-07-03 深圳市绿微康生物工程有限公司 Biological enzyme cleaning agent and method for preparing same
CN107810260A (en) * 2015-06-26 2018-03-16 荷兰联合利华有限公司 Laundry detergent composition
CN107810260B (en) * 2015-06-26 2020-07-17 荷兰联合利华有限公司 Laundry detergent compositions
CN107922935A (en) * 2015-08-28 2018-04-17 荷兰联合利华有限公司 Liquid detergent compositions comprising lipase and protease

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WO1992008779A1 (en) 1992-05-29
ES2091280T3 (en) 1996-11-01
JPH06504555A (en) 1994-05-26
DK0486073T3 (en) 1996-12-09
CA2096256A1 (en) 1992-05-15
IE913951A1 (en) 1992-05-20
EP0486073A2 (en) 1992-05-20
TR27423A (en) 1995-04-21
DE69121059D1 (en) 1996-08-29
TW215108B (en) 1993-10-21
NZ240571A (en) 1994-11-25
MX9102022A (en) 1992-07-08
CA2096256C (en) 1999-05-11
DE69121059T2 (en) 1997-03-06
EP0486073B1 (en) 1996-07-24
EP0486073A3 (en) 1993-06-23
AU9041691A (en) 1992-06-11

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