CN1027080C - Liquid detergent composition contg. enzyme and enzyme stabilization system - Google Patents
Liquid detergent composition contg. enzyme and enzyme stabilization system Download PDFInfo
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- CN1027080C CN1027080C CN90100768.4A CN90100768A CN1027080C CN 1027080 C CN1027080 C CN 1027080C CN 90100768 A CN90100768 A CN 90100768A CN 1027080 C CN1027080 C CN 1027080C
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- enzyme
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
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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
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Stabilization systems for aqueous liquid detergent compositions containing detergent enzymes and peroxygen bleaches are disclosed. The detergent compositions contain a carboxylic acid or a mixture of carboxylic acids as an enzyme stabilizing system.
Description
The present invention relates to a stable system about detergent enzyme.Particularly relate in aqueous liquid detergent composition as the stable system of detergent enzyme, said composition also comprises peroxygen bleach.
EP88-201009.3 discloses the aqueous liquid detergent composition that contains peroxygen bleach.Said composition is to be used for being limited in the amount that can utilize oxygen in the solution.This patent also discloses the composition that contains enzyme.But this patent documentation does not have open stable system about enzyme.EP88-201009.3 is also not open in the time of present patent application.
EP28865 discloses in the liquid detergent composition that contains formic acid or its salt and calcium ion the stable system about enzyme.The composition of the disclosure has pH value from 6.5 to 8.5.
Unless otherwise prescribed, all following per-cents are all used the weight meter.
The present invention relates to the organic tensio-active agent of a kind of 5%-60% of containing; A kind of peralcohol of from 1% to 40%; A kind of aqueous liquid detergent composition of detergent enzyme is characterized in that it comprises that also molecular formula is the enzyme stabilization system of 0.01% to 15% the carboxylic acid of X-R-COOH, and wherein X is H, and OH or COOH, R are unsubstituted or the C that replaces of hydroxyl
1To C
9Alkyl, alkenyl, alkynyl or aromatic yl group; Said composition also comprises the mixture of above-mentioned acid.
The pH value of the composition of preferentially selecting for use is at least 8.5, and the pH value is at least 9.0 preferably, and best pH value is at least 9.5.Peralcohol is preferably perborate, and best is the tetrahydrate of perborate.
Composition comprises water solubleness organic solvent, for example ethanol preferably.Reduced molten Jie's degree of any dispersed peralcohol like this, its result makes that available oxygen is controlled at below 0.5% usually in liquid phase under lower concentration, and more better is to be controlled to be lower than 0.1%.
The amount of carboxylic acid enzyme stabilizers better is from 0.5% to 10%, preferably from 1% to 7.5%.The enzyme stabilizers of preferentially selecting for use is an acetate, propionic acid and hexanodioic acid.Best is hexanodioic acid.According to the present invention, these sour mixtures that contain formate are suitable equally.
Suitable detergent enzyme comprises washing composition proteolytic enzyme, washing composition amylase, washing composition lipase and washing composition cellulase.The detergent composition of herein preferentially selecting for use is those compounds that contain washing composition proteolytic enzyme, is preferably high alkaline protease, and its amount is a benchmark from 0.01% to 5% with 8KNPU/g, preferably from 0.05% to 2.5%.
Also contain not necessarily in this detergent composition, but as the stablizer of second kind of enzyme, promptly content is 0.01% to 5% magnesium ion, its better amount be that 0.1% to 0.5% magnesium ion is as second kind of enzyme stabilizers.
Although liquid detergent composition obtains very fast ever-increasing popularizing, but available so far liquid detergent composition can't be compared with the profile performance of high quality granulous washing composition fully, particularly can not compare with those compounds that comprises peroxygen bleach and detergent enzyme.Therefore, the desirable liquid detergent composition that contains peroxygen bleach and detergent enzyme that provides.In we early stage patent application EP88-201009.3, once provided the method how to prepare.
Have now found that detergent enzyme that exists with moisture form and the peroxygen bleach that contains liquid washing agent are subjected to the domination of two types deactivation mechanism.First kind of mechanism relates to the automatic hydrolysis effect of enzyme, and can be referred to as autolysis.The washing composition of such deactivation has a lot of people all to know in detergent industry, simultaneously in order to reduce its effect, has proposed several enzyme stabilization systems.When the pH of liquid detergent composition value increased, the automatic hydrolysis effect had just become bigger problem.On the other hand, high pH value makes peroxygen bleach have good performance.
Second mechanism of enzyme deactivation relates to some the amino acid whose oxidation in enzyme.This mechanism is distinctive when storage contains the liquid washing agent of peroxygen bleach, and simultaneously this point can't be recognized before in detergent industry.
Employed enzyme stabilization system should protective enzyme neither be subjected to the influence of automatic hydrolysis effect in containing the aqueous liquid detergent compositions of peroxygen bleach.The also influence of not oxidated deactivation.Formic acid presents provide protection makes it avoid being subjected to the automatic hydrolysis effect, but can not overcome the deactivation of oxidation.
Present some carboxylic acid of beyond thought discovery, be exactly molecular formula be the carboxylic acid of X-R-COOH, can protective enzyme have both avoided being subjected to the deactivation of oxidation, avoid being subjected to the automatic hydrolysis effect again, wherein X is H, OH or COOH, R are unsubstituted or the C that replaces of hydroxyl
1To C
9Alkyl, alkenyl, alkynyl or aromatic yl group.Certainly, these carboxylic acids are understood part or whole deprotonation under the pH of detergent composition value, and particularly the pH value of working as composition just as the peroxygen bleach performance of preferentially selecting for use, is like this greater than 8.5 more.Unless otherwise mentioned, word " carboxylic acid " is the material that is used for deprotonation herein, and carboxylate salt also is the material with same effect.Percentage wherein is weight percentage, and is that calculate on the basis with protonated acid.
In practice, sour or sour water-soluble salt is added in the composition and goes, and simultaneously as the case may be, uses alkaliferous or sour material that the pH value of said composition is transferred to desired value usually.As another kind of method, narrated hereinafter and to be pre-mixed with enzyme earlier before acid or its water-soluble salt be incorporated into composition.Described be pre-mixed also can be by evaporation or lyophilize so that obtain containing for example solids of silicone oil of coating.At present, even it is to exist or add with a kind of form in its various salt, the compound of stabilized enzyme also will be considered to acid.Certainly, according to the present invention, also can use the mixture of above-mentioned acid.
Equally also can be earlier be pre-mixed acid and enzyme, and then premixture joined in the composition go; At that time, in last composition, may obtain lower acidity.
Preferred compositions comprises carboxylic acid, and it is to be selected from acetate, propionic acid, hexanodioic acid and its mixture.
Liquid detergent composition described herein all contains 5% to 60% liquid detergent composition by weight, organic surface active agent is selected from non-ionic preferably, anionic, cationic, with zwitterionics and its mixture, this organic surface active agent concentration is between 15% to 40%.
The synthetic anion surfactant can be used general formula R
1SO
3M represents, wherein R
1The expression hydrocarbon group, it is to be selected from alkyl group straight chain or side chain that contains about 8 to 24 carbon atoms and to be selected from the alkyl phenyl that contains about 9 to 15 carbon atoms in alkyl group.M is the salifiable positively charged ion of shape, is typically to be selected to contain sodium potassium, the monovalent ion or the monovalence compound radical of ammonium and its mixture.
Preferred synthetic cats product is the water-soluble salt that contains the alkyl benzene sulphonate (ABS) of 9 to 15 carbon atoms in alkyl.Another kind of preferred synthetic anion surfactant is the water-soluble salt of alkyl-sulphate, and wherein alkyl is to contain from 8 to 24 carbon atoms approximately, and better about 10 to 18 carbon atoms also contain about 1 to 20 oxyethyl group, preferably about 1 to 12 oxyethyl group group.Other suitable anion surfactant is open in the United States Patent (USP) 4,170,565 that people such as Flesher delivered on October 9th, 1979.
Under the situation that the acid basic catalyst exists, non-ionic tensio-active agent generally by oxyethane with contain one and have a reactive hydrogen atom, hydroxyl for example, carboxyl, or amino hydrocarbon polymer carries out that condensation reaction produces, and comprises that having general formula is RA(CH
2CH
2O) compound of nH, R represents the part of hydrophobic nature herein, and the A representative contains this class group of active hydrogen atom, and n represents the mean number of ethylene oxide moiety.R typically contains 8 to 22 carbon atoms.They also can be by propylene oxide and a kind of lower molecular weight the condensation reaction of compound form.N changes between being about 2 to 24 usually.
The hydrophobic part of non-ionic compound better be straight chain or side chain, have the aliphatic primary alcohol or the secondary alcohol of about 8 to 24 carbon atoms, be more preferably from the aliphatic primary alcohol or the secondary alcohol of about 12 to 20 carbon atoms.United States Patent (USP) 4,111 in 855, discloses suitable nonionogenic tenside more completely.The mixture of nonionogenic tenside may be the product that meets the requirements.
Suitable cationic surfactants comprises that molecular formula is R
1R
2R
3R
4N
+Quaternary ammonium compound, R wherein
1, R
2And R
3Be methyl and R
4Be a C
12-C
15Alkyl, perhaps R wherein
1Be ethyl or hydroxyethyl, R
2And R
3Be methyl and R
4Be a C
12-C
15Alkyl.
Zwitterionics comprises aliphatic quaternary ammonium, the derivative of phosphorus and sulfonium compound, wherein aliphatic portion may be a straight chain and side chain, and wherein one of aliphatics substituting group contains about 8 to 24 carbon atoms, and another substituting group contains the group that at least one negatively charged ion increases water-soluble.Ammonium sulphonate and ammonium sulfate that particularly preferred zwitter-ion material is ethoxylation, it be disclosed in United States Patent (USP) 3925262 that on December 9th, 1975, people such as Laughlin delivered and on December 30th, 1975 3,929,678 on.
Semi-polar nonionic surfactants comprises alkyl or the hydroxyalkyl part that contains 8 to 28 carbon atoms of having an appointment, also comprise being selected from containing alkyl and hydroxyalkyl, and contain 1 to 3 two-part water-soluble amine oxides of carbon atom that can at random be combined into ring texture.
The suitable active salt of anionic synthetic surface is selected from sulfonate or vitriol.Similar anionic detergent is well-known in washing composition technology, and is widely used in commercial washing composition.The water miscible sulfonate of preferred anionic surfactants synthetic of vitriol has an alkyl that contains about 8 to 22 carbon atoms in its molecular structure.
The example of preferred anionic surfactants surfactivity salt is the C that refines from (animal) fatty oil and Oleum Cocois like this
8-C
18The resulting reactor product of individual fatty alcohol sulphuric acidization; Alkylbenzene sulfonate wherein alkyl contains about 9 to 15 carbon atoms; Sodium sulfonate alkyl glycerylether (Sodium alkylglyceryl ether sulfonates); The glim that from (animal) fatty oil and Oleum Cocois, refines; Coconut fatty acid monoglyceride vitriol and sulfonate; Water-soluble salt with the paraffin sulfonate that in alkyl chain, has about 8 to 22 carbon atoms.The alkene sulfonic acid salt surfactant, the same just as narration more completely in US Patent specification 3,332,880 for example also can be utilized.The neutralizing cation that is used for negatively charged ion synthetic sulfonate and/or vitriol is that for example sodium and potassium are represented with the common cation that is widely used in the washing composition technology.
A particularly preferred negatively charged ion synthetic surfactant component is to represent with the water-soluble salt of alkyl benzene sulphonate (ABS) herein, and preferable is the sodium alkyl benzene sulfonate that has about 10 to 13 carbon atoms in alkyl.
In Fatty Alcohol(C12-C14 and C12-C18) that the preferred classification of non-ionic ethoxy compound can be by having 12 to 15 carbon atoms and every mole the Fatty Alcohol(C12-C14 and C12-C18) about 2 to 10, the condensation product that is more preferably the oxyethane of 3 to 7 moles is represented.The suitable material of this class ethoxy compound comprises: C
12-C
15The condensation product of about 7 moles of ethylene oxide when oxo alcohol and every mol of alcohol; The C of narrow fraction
14-C
15The condensation product of 7 to 9 moles of ethylene oxide when oxo alcohol and every mole of aliphatics (oxo process) alcohol; The C of narrow fraction
12-C
13The condensation product of aliphatics (oxo process) alcohol and every mole of fatty alcohol 6.5 moles of ethylene oxide; C
10-C
14The coconut Fatty Alcohol(C12-C14 and C12-C18) with contain the condensation product of the oxyethane of ethoxylation degree (mole number of oxyethane/mole Fatty Alcohol(C12-C14 and C12-C18)) in 5 to 8 scopes.According to the raw material of processing condition and alkene, when mainly being the aliphatics oxo alcohol of straight chain, may have branching to a certain degree, Duan chain such as methyl branch exist especially.
The 15%-50%(weight percent) product of the degree of branching of scope usually can obtain in commercial oxo alcohol.
Preferred non-ionic ethoxylation composition also can with have two of ethoxylation degree in various degree independently the mixture of ethoxylated non-ionic surface active agent represent.For example, every mole of hydrophobic part contains second kind of ethoxylation material that the hydrophobic of the non-ionic alcohol ethoxylate surfactant of from 3 to 7 moles of ethylene oxide and each mole partly has from 8 to 14 moles of ethylene oxide.A kind of mixture of preferred nonionic ethoxylate comprises lower ethoxylate and higher ethoxylate, and wherein lower ethoxylate is C
12-C
15Oxo alcohol with high to 50%(by weight) side chain, the condensation products that the oxyethane of every mole of about 3 to 7 moles of aliphatics oxo alcohol reacts, wherein higher ethoxylate is C
16-C
19Oxo alcohol with contain by weight above 50%() side chain, the condensation product that the oxyethane of about 8 to 14 moles reacts in every mole of oxo alcohol that contains side chain.
Suitable SYNTHETIC OPTICAL WHITNER in the present composition is a solid, water-soluble peralcohol.Preferred compound comprises perborate, persulphate, and peroxydisulfate, superphosphate and crystalline peroxyhydrate, they are formed by hydrogen peroxide and yellow soda ash or urea reaction.Preferred peroxy bleaching agent compound is the tetrahydrate and the SPC-D of the monohydrate and the Sodium peroxoborate of Sodium peroxoborate, perborate bleach in composition of the present invention can exist with short grained form, just from 0.1 to 20 micron, described particle forms by boratory crystallization at the scene.
Combine at water/anion surfactant/detergent builder under the situation of existence, described " crystallization at the scene " term relates to technological process, and the perborate particle is by bigger particle or solution and form whereby.Therefore this term is also comprising the process that contains chemical reaction, and for example Sodium peroxoborate is reacted by the hydrogen peroxide of stoichiometric quantity and sodium metaborate or borax and forms.The process that is also comprising dissolving and recrystallize when having served as the dissolving of boratory monohydrate and when then forming the tetrahydrate of perborate.Absorb crystal water by the monohydrate that makes perborate and recrystallization process may take place yet, by this process, monohydrate does not just directly recrystallize into tetrahydrate through dissolving step.
One of embodiments of the invention, with a kind of perborate compound, for example, the monohydrate of Sodium peroxoborate joins and contains in anion surfactant and detergent component liquid, aqueous.Stir resulting mud.During churning the perborate compound dissolves/treating processes of recrystallize.Since there are anion surfactant and detergent builder, this dissolving/recrystallization process, and its result has just obtained having the particle of desired particle diameter.
Because monohydrate is relatively more responsive to recrystallize, so preferentially select monohydrate in the embodiments of the invention for use.Except as otherwise noted, the average particulate diameter that is by weight of particle diameter herein.Because therefore the cause of physical stability, preferentially selects the narrower relatively particle of particle size dispersion for use; That is to say, should preferentially select for use particle diameter greater than 10 microns to be less than 10%(by weight) such particle.
Among second embodiment of the present invention, the perborate compound is to form by chemical reaction at the scene.For example, sodium metaborate is joined comprise in anion surfactant and detergent builder liquid, aqueous.Then, when stirring, add hydrogen peroxide according to stoichiometric quantity.Stirring proceeds to reaction and finishes.
Also can use another borate compound, for example borax and boric acid replace metaborate.If be used as the compound of boron, so,, for example add sodium hydroxide in order to guarantee to make borax generate the alkali that metaborate will add stoichiometric quantity by reacting with borax.Then this process just as on regard to going on of description that metaborate transforms.As described in the prior art, also can use other superoxide (for example sodium peroxide), replace hydrogen peroxide.
In preferred liquid detergent composition, except that moisture, also contain a kind of water miscible organic solution, this solvent has reduced the solubleness of the perborate in liquid phase, thereby has increased the chemical stability of said composition.
Do not need this organic solvent and water to mix fully, change the solubleness of perborate compound in liquid phase as long as there is the solvent of q.s to mix with water in the said composition.
Certainly this water miscible organic solvent must adapt with perborate compound pH value in use.Therefore, it is just not ideal to have a polyvalent alcohol (for example 1,2 propylene glycol and glycerol) of vicinal hydroxyl.
Suitable water miscible organic solvent comprises lower aliphatic single alcohol and the ether of glycol ether and lower single aliphat single-alcohol.Preferred solvent is an ethanol, Virahol, 1-methoxyl group 2-propyl alcohol, butyldiglycol ether and ethyl glycol ether ether.
Also contain detergent enzyme according to composition of the present invention; Suitable enzyme comprise washing composition proteolytic enzyme, amylase,, lipase, cellulase and its mixture.Preferred enzyme is alkaline proteolytic enzyme, for example Maxacal(R) and Savinase(R).As described, also can use enzyme with silicon coating at EP-A-0238216.
Contain a kind of fatty acid component in the preferred compositions as builder, yet the amount of lipid acid by weight, is selected preferentially to be less than 5% for use.More desirable less than 4%.Preferred saturated fatty acid has 10 to 16 carbon atoms, and preferable is the lipid acid of 12 to 14 carbon atoms.Preferred non-saturated fatty acid is oleic acid and Zoomeric acid.
Preferred compositions comprises a kind of inorganic or organic builder.The example of inorganic builder comprises alkalescence (Asia) phosphorus builder, for example, and three sodium polyphosphates, trisodium phosphate, and silico-aluminate (zeolite).
The example of organic synergistic auxiliary agent is with polyprotonic acid citric acid for example, and the mixture of nitrilotriacetic acid(NTA) and tartrate monosuccinic acid ester and tartrate disuccinate is representative.Preferred builder used herein is the succinic acid compound that citric acid and alkyl (alkene) replace, and alkyl wherein (alkene) contains 10 to 16 carbon atoms.The example of this group compound is the dodecenyl succinic succsinic acid.Also can use to comprise polyacrylic ester, poly-hydroxy acrylate and polyacrylic ester/polymaleic acid ester copolymer is at interior polycarboxylate builder.
Compositions herein may comprise a series of other supplementary components, and this composition adds with the amount of additive usually, is usually less than about 5%.Similarly the example of additive comprises foaming regulator (sudsregulants), and opalizer is in order to improve the reagent of machine for the miscibility on enamel coating surface, sterilant, dyestuff, spices, whitening agent or the like.
Liquid composition herein may comprise other additive, the amount of its adding from 0.05% to 5%.
These additives comprise polyaminocarboxylate, ethylene diamino tetraacethyl for example, diethylidene triamino pentaacetic acid, ethylene diamino two Succinic Acid or its water-soluble alkali metal salts.Other additive comprises organic phospho acid; Particularly preferably be ethylene diamino tetramethylene phosphonic acid, hexa-methylene diamino tetramethylene phosphonic acid, diethylidene triamino pentamethylene phosphonic acids and amino trimethylene methyl acid phosphate.
Bleaching stibilizer, xitix for example, pyridine dicarboxylic acid, sodium stannate and oxine also can be included in these compositions, its content from 0.01% to 1%.
Under the condition of various different application, the effective application of the composition of claim may need to use foaming regulator.Usually all detergent foam conditioning agents that can preferably use herein are the alkylation polysiloxane, and for example dimethyl polysiloxane also often is called (gathering) siloxanes.Should (gathering) siloxanes usual amounts be no more than 1.5%, preferably 0.1% to 1%.
The opalizer that utilizes as much as possible also may be desirable, and their contribution is the spissated liquid detergent composition that produces a kind of uniform state.The example of suitable opalizer comprises: polystyrene, the commercial nylon 621(LYTRON621 that is called), make by MONSANTO chemical company.The common usage quantity of this opalizer from 0.3% to 1.5%.
Liquid detergent composition of the present invention also comprises a kind of reagent that improves the miscibility on washing machine surface, particularly for the miscibility reagent on enamel coating surface.
Also require the known anti redeposition agent and/or the miscibility reagent of adding 0.1% to 5% in the said composition.The example of similar additive comprises: Xylo-Mucine; Hydroxyl-C
1-6Alkyl-Mierocrystalline cellulose, the poly carboxylic acid homopolymer-or multipolymer composition, for example polymaleic acid; Maleic anhydride and methylvinylether are to react the multipolymer of generation in 2: 1 to 1: 2 by mole ratio;
A kind of unsaturated monocarboxylic acid monomer of thiazolinyl, react resulting multipolymer with a kind of undersaturated dicarboxylic acid monomer of thiazolinyl, the unsaturated monocarboxylic acid monomer that wherein contains thiazolinyl has and is no more than 5 carbon atoms, it better is the compound of 3 or 4 carbon atoms, methylacrylic acid for example, and the unsaturated dicarboxylic acid monomer that wherein contains thiazolinyl has and is no more than 6 carbon atoms, be preferably 4 carbon atoms, according to this point, above-mentioned two kinds of monomeric mol ratios are in 1: 4 to 4: 1 scope, and above-mentioned multipolymer is reported in the EP application for patent 0066915 of application on May 17 nineteen eighty-two in more detail.
Following Example is to specify of the present invention, facilitates like this and understands the present invention.
Liquid detergent composition prepares by (composition) various compositions in the table are mixed according to a certain percentage.The pH value of these compositions is in 9.5 to 10.5 scope.
(composition) component composition (by weight percentage)
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ Ⅶ Ⅷ Ⅸ Ⅹ Ⅺ Ⅻ ⅩⅢ ⅩⅣXV XVI
Hexamethylene-diamine 4(methylene phosphonic acid) 0.7 0.7 0.7 0.7 0.7
Sodium peroxoborate-hydrate 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5
Proteinase 8 KNPU/g 0.6 0.6 0.6 0.6 0.6 0.6 0.6
Proteolytic enzyme 16KNPU/g 0.3 0.3 0.3 0.3 0.3 0.3 0.3
The mixture of proteolytic enzyme
*
Amylase 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Sodium formiate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.5 1.5 1.0 1.5
Sodium acetate 2.5 2.5 2.5 2.5 2.5 5.0 2.5 2.5
Sodium Propionate 2.5
Hexanodioic acid 2.5 2.5 2.5 2.5 2.5
Succsinic acid 2.5
Suberic acid 2.5
Toxilic acid 2.5
Magnesium acetate 4 hydrate 1.5 1.7
Sodium hydroxide 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Perfume compound and trace ingredients remainder
* contain with 8KNPU/g be benchmark 20%(by weight) the moisture protein enzyme solution of proteolytic enzyme and 5% hexanodioic acid, neutralizing with NaOH makes the pH value reach 9.5.
The ratio of * monosuccinic acid tartrate and two amber ambers acid tartrates is 80: 20 a mixture.
Claims (10)
1, a kind of aqueous liquid detergent composition comprises organic surface active agent; Peroxy bleaching agent compound; Detergent enzyme and be selected from the ether of the single pure and mild glycol ether of lower fat family and rudimentary single aliphat single-alcohol and make available oxygen content in the solution less than 0.5% water-soluble solvent; It is a kind of as enzyme stabilization system to it is characterized in that said composition also comprises, molecular formula is the carboxylic acid of X-R-COOH, and the content of carboxylic acid is 0.01% to 15%, and wherein X is H or COOH, and R is a kind of alkyl of unsubstituted 1-9 carbon atom; Said composition comprises that also the mixture of above-mentioned acid and the pH value of composition are at least 9.5.
2, a kind of aqueous liquid detergent compositions as claimed in claim 1, peralcohol wherein is a kind of perborate.
3, a kind of aqueous liquid detergent compositions as claimed in claim 1, water-soluble solvent wherein is selected from ethanol, Virahol, 1-methoxyl group-2-propyl alcohol, diethylene glycol monoethyl ether, diethylene glycol butyl ether and its mixture and peralcohol are a kind of percarbonate, and available oxygen content is less than 0.1% in the solution.
4, a kind of aqueous liquid detergent compositions as claimed in claim 1 comprises the organic solvent of the aqueous solution perborate compound being existed with solid particulate dispersive state, and makes in solution available oxygen content less than 0.1%.
5, aqueous liquid detergent compositions as claimed in claim 1, wherein the amount of carboxylic acid enzyme stabilizers from 0.01% to 10%.
6, aqueous liquid detergent compositions as claimed in claim 5, wherein the amount of carboxylic acid enzyme stabilizers is from 0.1% to 7.5%.
7, aqueous liquid detergent compositions as claimed in claim 1, wherein the carboxylic acid enzyme stabilizers is selected from acetate, propionic acid, hexanodioic acid and its mixture.
8, as the described aqueous liquid detergent compositions of above-mentioned claim 1, wherein detergent enzyme is selected from and contains washing composition proteolytic enzyme, washing composition amylase, washing composition lipase, this compounds that washing composition cellulase and its mixture are formed.
9, a kind of aqueous liquid detergent compositions as claimed in claim 8, detergent enzyme wherein is a high alkaline protease.
10, any aqueous liquid detergent compositions described in above-mentioned claim 1 comprises from 0.01% to 5% magnesium ion as second kind of enzyme stabilizers.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898900496A GB8900496D0 (en) | 1989-01-10 | 1989-01-10 | Liquid detergent composition containing enzyme and enzyme stabilization system |
| GB8900496 | 1989-01-10 | ||
| EP90870197A EP0482274A1 (en) | 1989-01-10 | 1990-10-22 | Liquid detergent compositions containing a suspended peroxygen bleach |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044294A CN1044294A (en) | 1990-08-01 |
| CN1027080C true CN1027080C (en) | 1994-12-21 |
Family
ID=40149609
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90100768.4A Expired - Fee Related CN1027080C (en) | 1989-01-10 | 1990-01-10 | Liquid detergent composition contg. enzyme and enzyme stabilization system |
| CN91111077.1A Expired - Lifetime CN1030333C (en) | 1989-01-10 | 1991-10-22 | Liquid detergent compositions containing suspeded peroxygen bleach |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111077.1A Expired - Lifetime CN1030333C (en) | 1989-01-10 | 1991-10-22 | Liquid detergent compositions containing suspeded peroxygen bleach |
Country Status (17)
| Country | Link |
|---|---|
| EP (2) | EP0378261B1 (en) |
| JP (2) | JP2749416B2 (en) |
| CN (2) | CN1027080C (en) |
| AR (1) | AR244323A1 (en) |
| AT (1) | ATE109201T1 (en) |
| AU (2) | AU638961B2 (en) |
| CA (2) | CA2007381C (en) |
| DE (1) | DE69010922T2 (en) |
| FI (1) | FI900130A (en) |
| GB (1) | GB8900496D0 (en) |
| IE (2) | IE900097L (en) |
| MX (2) | MX172149B (en) |
| MY (1) | MY108663A (en) |
| NZ (2) | NZ232055A (en) |
| PT (2) | PT92820A (en) |
| TR (1) | TR25347A (en) |
| WO (1) | WO1992007055A1 (en) |
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| ATE145424T1 (en) * | 1989-11-30 | 1996-12-15 | Clorox Co | STABLE AQUEOUS OXIDATION DETERGENT |
| BR9105999A (en) * | 1990-02-08 | 1992-10-20 | Unilever Nv | LIQUID DETERGENT COMPOSITION AND WASHING PROCESS |
| EP0476726A1 (en) * | 1990-07-27 | 1992-03-25 | Unilever N.V. | Protease-containing liquid detergent compositions |
| EP0471410A3 (en) * | 1990-08-15 | 1992-07-01 | Unilever Nv | Structured liquid detergent compositions containing subtilisin mutants |
| US5264142A (en) * | 1991-11-25 | 1993-11-23 | Lever Brothers Company, Division Of Conopco, Inc. | Stabilization of peroxygen bleach in enzyme-containing heavy duty liquids |
| ES2126743T5 (en) | 1993-02-11 | 2010-02-05 | Genencor International, Inc. | OXIDATIVELY STABLE ALFA-AMYLASE. |
| EP1707624A3 (en) | 1993-10-08 | 2007-01-03 | Novozymes A/S | Amylase variants |
| US5691295A (en) * | 1995-01-17 | 1997-11-25 | Cognis Gesellschaft Fuer Biotechnologie Mbh | Detergent compositions |
| AU2801395A (en) * | 1994-07-01 | 1996-01-25 | Warwick International Group Limited | Bleaching compositions |
| CA2194373A1 (en) * | 1994-07-21 | 1996-02-08 | Minnesota Mining And Manufacturing Company | Concentrated cleaner compositions capable of viscosity increase upon dilution |
| DE19515072A1 (en) * | 1995-04-28 | 1996-10-31 | Cognis Bio Umwelt | Detergent containing cellulase |
| DE19605688A1 (en) * | 1996-02-16 | 1997-08-21 | Henkel Kgaa | Transition metal complexes as activators for peroxygen compounds |
| US5958739A (en) * | 1996-06-06 | 1999-09-28 | Genencor International Inc. | Mutant α-amylase |
| US6548134B1 (en) | 1996-06-26 | 2003-04-15 | The Procter & Gamble Company | Vented container containing a liquid product with particulate solids |
| EP0816247B1 (en) * | 1996-06-26 | 2001-08-16 | The Procter & Gamble Company | Venting container containing a liquid product with particulate solids |
| EP0843001B1 (en) * | 1996-11-13 | 2003-04-23 | The Procter & Gamble Company | Aqueous alkaline peroxygen bleach-containing compositions |
| US6080568A (en) * | 1997-08-19 | 2000-06-27 | Genencor International, Inc. | Mutant α-amylase comprising modification at residues corresponding to A210, H405 and/or T412 in Bacillus licheniformis |
| RU2003105683A (en) | 2000-07-28 | 2004-08-20 | Хенкель Кгаа (De) | A NEW AMILOLYTIC ENZYME FROM BACILLUS SP.A7-7 (DSM12368), AND ALSO A CLEANING AND CLEANING AGENT WITH THIS NEW AMILOLYTIC ENZYME |
| JP2002129189A (en) * | 2000-10-26 | 2002-05-09 | Teepol Ltd | Solubilizing process of surfactant, surfactant solubilized solution obtained by it, liquid detergent composition using it |
| US7888104B2 (en) | 2000-11-28 | 2011-02-15 | Henkel Ag & Co. Kgaa | Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase |
| CN1575308B (en) | 2001-10-22 | 2010-04-28 | 汉高两合股份公司 | Cotton active, dirt removing urethane-based polymers |
| DE10153792A1 (en) | 2001-10-31 | 2003-05-22 | Henkel Kgaa | New alkaline protease variants and washing and cleaning agents containing these new alkaline protease variants |
| DE10162727A1 (en) | 2001-12-20 | 2003-07-10 | Henkel Kgaa | New alkaline protease from Bacillus gibsonii (DSM 14391) and washing and cleaning agents containing this new alkaline protease |
| DE10162728A1 (en) | 2001-12-20 | 2003-07-10 | Henkel Kgaa | New alkaline protease from Bacillus gibsonii (DSM 14393) and washing and cleaning agents containing this new alkaline protease |
| DE10163884A1 (en) | 2001-12-22 | 2003-07-10 | Henkel Kgaa | New alkaline protease from Bacillus sp. (DSM 14392) and detergents and cleaning agents containing this new alkaline protease |
| DE10257387A1 (en) | 2002-12-06 | 2004-06-24 | Henkel Kgaa | Dispensing bottle, used for applying toilet or hard surface cleaner, disinfectant, laundry or dish-washing detergent or corrosion inhibitor, has separate parts holding different active liquids mixing only after discharge from nozzles |
| GB2392167A (en) * | 2002-08-22 | 2004-02-25 | Reckitt Benckiser Inc | Composition containing an acid with anionic and nonionic surfactants |
| DE10303130A1 (en) * | 2003-01-28 | 2004-07-29 | Clariant Gmbh | Aqueous liquid detergent dispersion useful as a laundry detergent comprises anionic surfactant, builder and quaternary alkyl hydroxyethyl ammonium salt |
| US8071345B2 (en) | 2006-03-31 | 2011-12-06 | Novozymes A/S | Stabilized subtilisin composition |
| WO2007113241A1 (en) * | 2006-03-31 | 2007-10-11 | Novozymes A/S | A stabilized liquid enzyme composition |
| DE102007011236A1 (en) | 2007-03-06 | 2008-09-11 | Henkel Ag & Co. Kgaa | Carboxyl-bearing benzophenone or benzoic acid anilide derivatives as enzyme stabilizers |
| JP5436199B2 (en) * | 2009-12-28 | 2014-03-05 | ライオン株式会社 | Method for producing liquid detergent composition |
| CA2934519A1 (en) * | 2013-12-18 | 2015-06-25 | Arkema Inc. | Stable liquid compositions containing enzymes and peroxides |
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| FR2140822A5 (en) * | 1971-06-09 | 1973-01-19 | Air Liquide | Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers |
| CA1104451A (en) * | 1978-02-28 | 1981-07-07 | Manuel Juan De Luque | Detergent bleach composition and process |
| US4377489A (en) * | 1981-03-16 | 1983-03-22 | Ceil Clean Corporation, Inc. | Inorganic persulfate cleaning solution for acoustic materials |
| EP0086511B1 (en) * | 1982-02-03 | 1986-07-02 | THE PROCTER & GAMBLE COMPANY | Oxygen-bleach-containing liquid detergent compositions |
| US4529525A (en) * | 1982-08-30 | 1985-07-16 | Colgate-Palmolive Co. | Stabilized enzyme-containing detergent compositions |
| GB8311314D0 (en) * | 1983-04-26 | 1983-06-02 | Unilever Plc | Aqueous enzyme-containing compositions |
| US4689167A (en) * | 1985-07-11 | 1987-08-25 | The Procter & Gamble Company | Detergency builder system |
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| GB8713756D0 (en) * | 1987-06-12 | 1987-07-15 | Procter & Gamble | Liquid detergent |
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| GB8826458D0 (en) * | 1988-11-11 | 1988-12-14 | Ici Plc | Bleach formulation & aqueous detergent compositions |
| GB8900525D0 (en) * | 1989-01-10 | 1989-03-08 | Procter & Gamble | Liquid detergent composition containing enzyme and enzyme stabilization system |
-
1989
- 1989-01-10 GB GB898900496A patent/GB8900496D0/en active Pending
-
1990
- 1990-01-05 DE DE69010922T patent/DE69010922T2/en not_active Expired - Fee Related
- 1990-01-05 AT AT90200026T patent/ATE109201T1/en not_active IP Right Cessation
- 1990-01-05 EP EP90200026A patent/EP0378261B1/en not_active Expired - Lifetime
- 1990-01-09 CA CA002007381A patent/CA2007381C/en not_active Expired - Fee Related
- 1990-01-09 NZ NZ232055A patent/NZ232055A/en unknown
- 1990-01-09 TR TR90/0095A patent/TR25347A/en unknown
- 1990-01-10 IE IE900097A patent/IE900097L/en unknown
- 1990-01-10 CN CN90100768.4A patent/CN1027080C/en not_active Expired - Fee Related
- 1990-01-10 PT PT92820A patent/PT92820A/en not_active Application Discontinuation
- 1990-01-10 MX MX019083A patent/MX172149B/en unknown
- 1990-01-10 AU AU47871/90A patent/AU638961B2/en not_active Ceased
- 1990-01-10 FI FI900130A patent/FI900130A/en not_active Application Discontinuation
- 1990-01-10 JP JP2003298A patent/JP2749416B2/en not_active Expired - Fee Related
- 1990-10-22 EP EP90870197A patent/EP0482274A1/en not_active Withdrawn
-
1991
- 1991-10-15 WO PCT/US1991/007606 patent/WO1992007055A1/en active Application Filing
- 1991-10-15 AU AU89523/91A patent/AU662501B2/en not_active Ceased
- 1991-10-15 JP JP3518590A patent/JPH06502440A/en active Pending
- 1991-10-15 CA CA002094604A patent/CA2094604C/en not_active Expired - Fee Related
- 1991-10-21 NZ NZ240293A patent/NZ240293A/en unknown
- 1991-10-21 AR AR91320962A patent/AR244323A1/en active
- 1991-10-21 IE IE368591A patent/IE913685A1/en not_active Application Discontinuation
- 1991-10-21 MX MX9101678A patent/MX9101678A/en unknown
- 1991-10-22 MY MYPI91001948A patent/MY108663A/en unknown
- 1991-10-22 PT PT99296A patent/PT99296A/en not_active Application Discontinuation
- 1991-10-22 CN CN91111077.1A patent/CN1030333C/en not_active Expired - Lifetime
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