CN1380900A - Transparent/translucent liquid enzyme compositions in clear bottles comprising antioxidants - Google Patents

Transparent/translucent liquid enzyme compositions in clear bottles comprising antioxidants Download PDF

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Publication number
CN1380900A
CN1380900A CN99814495.9A CN99814495A CN1380900A CN 1380900 A CN1380900 A CN 1380900A CN 99814495 A CN99814495 A CN 99814495A CN 1380900 A CN1380900 A CN 1380900A
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CN
China
Prior art keywords
composition
enzyme
lipase
antioxidant
alkyl
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CN99814495.9A
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Chinese (zh)
Inventor
M·贝-李
F·L·G·苏
D·S·穆菲
K·M·纽泽
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Unilever NV
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Unilever NV
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/2034Monohydric alcohols aromatic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2058Dihydric alcohols aromatic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663Stabilised liquid enzyme compositions

Abstract

An enzyme containing transparent/translucent liquid heavy duty detergent in a clear bottle wherein the liquid comprises antioxidant.

Description

The transparent/translucent liquid enzyme compositions that contains antioxidant in clear bottles
Invention field
The present invention relates to containing antioxidant, contain the moisture transparent or semitransparent heavy-filth liquid detergent for washing clothes of enzyme in clear bottles.The enzyme that this oxygenant protection is present in heavy-filth liquid (HDL) composition is avoided harmful UV radiating infringement, keeps the activity of enzyme thus.
Background of invention
Traditional liquid washing agent is sold in opaque bottle.Yet, use the transparent bottle can be from the aesthetic interest that causes the human consumer, because they can see the denseness and the particles suspended (if present) of product., use transparent bottle to be caused undesirable enzymic activity (promptly being present in the enzyme in the liquid composition) loss by UV light.The light that only refers to the about 250-460 nanometer of wavelength (nm) about UV.Particularly, in the scope of 320-400nm, UVB is at about 290-320nm usually for UVA, and UVC is lower than 290nm, and is low to about 250nm.
Well known in the prior art is can be during the manufacturing of clear bottles the UV absorption agent to be joined in the bottle material to protect it so as to not make to become fragile and to protect the component in the bottle.For example, in GB2228940, described in the polyester bottle and to use dicarboxylic ester with protection vial-mainly be food-the avoid infringement of 320-360nm light.
In EU0361537A2, described use film formation thing and passed through vial so that stop the UV radiation.Although use such component can stop that the UV light transmission crosses clear vial, the UV absorption agent that is included in the bottle material is expensive, and must add and have scald operator's danger when bottle material is heat and fusion.
(Colgate's) WO 97/26315 discloses the transparent vessel with the specific chlorination degree that is limited by x and y value.In liquid, use specific dyestuff so that be complementary with container.This reference had not both had instruction not advise using the transparent liquid with antioxidant of the present invention and enzyme capsule particular combinations yet.
GB1303810 discloses limpid liquid medium and has seen component clearly with the naked eyes that are suspended in this medium.Openly do not contain the capsular detergent composition of antioxidant and enzyme.
The US3812042 of Verdier discloses the transparent container that contains liquid and the viscosity and the transparency hierarchy of control, and this hierarchy of control contains urea, the pure and mild optional hydrotropic agent of lower aliphatic.
Summary of the invention
We have made us unexpectedly finding: the antioxidant of relatively small amount when it being joined in the liquid that contains enzyme, has the ability of the loss of activity that very big reduction causes by UV light.It is unexpected to be that the amount that adds is very little and to be dispersed in the whole liquid matrix.The advantage of using antioxidant is that it can add in the safety temperature lower than usefulness fusion bottle material.Therefore, the present invention relates to a kind of transparent or semitransparent heavy-dirt liquid composition in clear bottles, it contains:
(a) tensio-active agent of 10-85% weight, it is selected from negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics and its mixture;
(b) enzyme of 0.001-5% weight, it is selected from proteolytic enzyme, lipase, cellulase, oxydase, amylase and its mixture; With
(c) antioxidant of 0.001-3% weight;
Wherein said composition has about 50% or higher transparence (use the cuvette of 1cm, measure) under wavelength 410-800nm; With
Wherein this bottle has the transparence greater than 25% under about 410-800nm wavelength.
Detailed Description Of The Invention
The present invention relates to the transparent/translucent liquid heavy-filth liquid that contains enzyme in clear bottles, it contains the loss (for example, by rayed enzyme by clear bottles caused) of antioxidant to prevent enzymic activity.
Antioxidant
In operable preferred anti-oxidants class, comprise: tocopherol, thiodipropionate, quinhydrones, diphenylamine, hindered phenol and cresols.Antioxidant is limited to these kinds by no means.
Comprise for the useful especially antioxidant of the application: metal chelator, xitix, list or polyphenol be tocopherol for example, butylated hydroxyl fennel phenol (BHA), butylated hydroxytoluene (BHT), tertiary butylated hydroquinone (TBHQ), propyl group training acid esters (PG), 2,4,5-trihydroxy-butyl benzophenone (THBP) and 4-hydroxymethyl-2, the 6-di-tert-butylphenol.Particularly preferred antioxidant comprises: xitix, BHA, BHT and its mixture.Although without being limited by theory, antioxidant has postponed oxidizing reaction by the formation that suppresses free radical in the initiation step.This can suppress the chain reaction of radical transfer by playing hydrogen donor or free-radical acceptor.
Defined other operable antioxidant in the 2nd volume " functional materials " (North American edits, and is published in 1997 by Manufacturing Confectioner publishing company) of McCutcheon, the document is introduced the application as a reference.
Antioxidant can use with the amount of 0.001-3%, preferred 0.005-2%, more preferably 0.01-1%.
Detergent composition
Detergent active
Composition of the present invention contains one or more surface-active agents (tensio-active agent), and it is selected from: negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics or its mixture.The preferred surfactants that is used for the present invention is the mixture of negatively charged ion and nonionogenic tenside, but should understand that any tensio-active agent can use separately or with other combinations-of surfactants.Tensio-active agent should account at least 10% weight of composition, and 11-85% for example preferably is at least the 15-70% of total composition, more preferably 16-65%, most preferably 20-65%.
Nonionogenic tenside
Can separately or be used for the synthetic organic detergent of nonionic of the present invention with other combinations-of surfactants ground is described below.
As well known, nonionic detergent is characterised in that and has organic hydrophobic group and organic hydrophilic base and generally by organic aliphatic series or alkyl aromatic hydrophobic compound and oxyethane (hydrophilic) condensation prepared.Typical suitable nonionogenic tenside is those tensio-active agents of describing in US4316812 and US3630929.
Nonionic detergent is the oleophilic substance of poly-alkoxylation normally, and wherein the ideal hydrophile-lipophile balance value obtains from hydrophilic poly-lower alkoxy is added to oleophilic moiety.The preferred nonionic detergent of one class is oxyalkylated alkanol, wherein this alkanol be the alkanol of 9-18 carbon atom and wherein the mole number of oxirane (2 or 3 carbon atoms) be 3-12.Preferably using wherein in such material, alkanol is Fatty Alcohol(C12-C14 and C12-C18) and every mole of those materials that contain 5-8 or 5-9 alkoxy grp of 9-11 or 12-15 carbon atom.
The example of compound is that wherein alkanol is that 12-15 carbon atom and every mole contain those of 7 ethylene oxide groups of having an appointment like this, for example Neodol 25-7 and Neodol 23-6.5, and they are by Shell Chemical Company, the product that Inc makes.The former is the mixture of high fatty alcohol of on average about 12-15 carbon atom and the condensation product of about 7 moles of ethylene oxide, and the latter is that the carbonatoms of wherein high fatty alcohol is that the respective mixtures of 12-13 and oxyethane mean number are 6.5 condensation product.This high fatty alcohol is a primary alkanol.Other useful nonionic is to be represented by a commercial class nonionic of knowing of selling with trade(brand)name Plurafac.This Plurafac is the reaction product of the mixture of senior straight chain alcohol and oxyethane and propylene oxide, and it contains the combination chain of oxyethane and propylene oxide, is ended by hydroxyl.Example comprises the C with 6 moles of ethylene oxide and 3 moles of propylene oxide condensations 13-15Fatty Alcohol(C12-C14 and C12-C18) is with the C of 7 moles of propylene oxide and 4 moles of ethylene oxide condensations 13-15Fatty Alcohol(C12-C14 and C12-C18) is with the C of 5 moles of propylene oxide and 10 moles of ethylene oxide condensations 13-15Fatty Alcohol(C12-C14 and C12-C18), or above-mentioned any mixture.
Another kind of liquid nonionic is that Inc buys with trade(brand)name Dobanol from Shell Chemical Company: Dobanol 91-5 is the C with ethoxylation of average 5 moles of ethylene oxide 9-C 11Fatty Alcohol(C12-C14 and C12-C18), Dobanol 23-7 are the C that every mole of Fatty Alcohol(C12-C14 and C12-C18) has the ethoxylation of average 7 moles of ethylene oxide 12-C 15Fatty Alcohol(C12-C14 and C12-C18).
In composition of the present invention, preferred nonionic comprises the C that has at the narrow relatively content epoxy ethane of about 7-9 scope 12-C 15Uncle's Fatty Alcohol(C12-C14 and C12-C18) and with the C of about 5-6 moles of ethylene oxide ethoxylation 9-C 11Fatty Alcohol(C12-C14 and C12-C18).
The another kind of nonionogenic tenside that can be used for the present invention is the polyglycoside surfactant promoting agent.Be applicable to that polyglycoside surfactant promoting agent among the present invention comprises those materials of following general formula:
RO-R’O- y(Z) x
Wherein R is any monovalent organic radical group that contains the individual carbon atom of the 6-30 that has an appointment (preferably about 8-18); R ' is the bivalent hydrocarbon radical that contains 2-4 the carbon atom of having an appointment; O is a Sauerstoffatom; Y is that mean value is the number of 0-about 12, but most preferably is 0; Z is from containing 5 or 6 carbon atom reducing sugar deutero-parts; X is that mean value is the number of about 1-10 (preferably about 1.5-10).
Be used for the particularly preferred class polyglycoside surfactant promoting agent of the present invention practice and be included in that R is any monovalent organic radical group (straight or branched) that contains the individual carbon atom of the 6-18 that has an appointment (particularly about 8-18) in the following formula; Y is 0; Z is a glucose or from its deutero-part; X is that mean value is those materials of the number of about 1-about 4 (preferably about 1-4).
Draw together for the useful especially ionic surfactant pack of the present invention, but be not limited to: alcohol ethoxylate (for example deriving from the Neodol 25-9 of Shell Chemical Co.), alkylphenol ethoxylate (for example deriving from the Tergitol NP-9 of Union Carbide Corp.), alkyl poly glucoside (for example deriving from the Glucapon 600CS of Henkel Corp.), the polyoxy propylene glycol of polyoxyethyleneization (for example deriving from the Pluronic L-65 of BASF Corp.), sorbitol ester (for example deriving from the Emsorb 2515 of Henkel Corp.), the sorbitol ester of polyoxyethyleneization (for example deriving from the Emsorb 6900 of Henkel Corp.), alkanolamide (for example deriving from the Alkamide DC212/SE of Rhone-Poulenc Co.) and N-alkyl pyrrolidone (for example deriving from the Surfadone LP-100 of ISP Technologies Inc).
By weight, the consumption of nonionogenic tenside in prescription is about 0-70%, preferably between 5-50%, and more preferably 10-40%.
Can use the mixture of two or more nonionogenic tensides.
The anion surfactant washing composition
The anion surfactant that can be used for the present invention is that to contain long chain hydrocarbon hydrophobic grouping and hydrophilic radical in its molecular structure be for example those surface active cpds of sulfonate radical or sulfate radical of water solubilizing group.This anion surfactant comprises: basic metal (for example sodium or potassium) water-soluble senior alkyl benzene sulfonate, alkylsulfonate, alkyl-sulphate and alkyl, polyether vitriol.They also can comprise lipid acid or fatty acid soaps.The preferred anionic surfactants tensio-active agent is basic metal, ammonium or the alkanolamide salt of senior alkyl Phenylsulfonic acid and basic metal, ammonium or the alkanolamide salt of senior alkyl sulfonic acid.Preferred senior alkyl sulfonate is that wherein alkyl contains 8-26 carbon atom, preferred 12-22 carbon atom, more preferably those materials of 14-18 carbon atom.Alkyl in alkylbenzene sulfonate contains 8-16 carbon atom, more preferably 10-15 carbon atom.Particularly preferred alkylbenzene sulfonate is Sodium dodecylbenzene sulfonate or potassium, for example linear alkyl benzene sulphonate.Can by with long-chain alpha-olefin and sulphite or inferior hydrosulphuric acid salt for example sodium bisulfite react and prepare uncle or secondary alkyl sulfonate.Also can pass through the positive paraffinic hydrocarbon of long-chain and sulfurous gas and oxygen prepared in reaction alkylsulfonate, thereby obtain being suitable for do the tensio-active agent washing composition just or secondary senior alkyl sulfonate, as described in US2503280, US2507088, US3372188 and the US3260741.
This alkyl substituent is straight chain preferably, promptly positive alkyl, yet, also can use branched-chain alkyl sulfonate, but they are not so good aspect biological degradation.This alkane is that alkyl substituent can be uncle's sulfonated, perhaps can be connected on the carbon atom of chain for example, and promptly can be secondary sulfonate.Should understand that in this area this substituting group can be connected on any carbon on the alkyl chain.This senior alkyl sulfonate can be used as an alkali metal salt for example sodium and potassium use.Preferred salt is sodium salt.Preferred alkylsulfonate is C 10-C 18The primary, positive alkyl sodium sulfonate and potassium, C 10-C 15The primary, just alkylsulfonate is preferred.
Can use the mixture of senior alkyl benzene sulfonate and senior alkyl sulfonate and the mixture of senior alkyl benzene sulfonate and senior alkyl polyether thiourea hydrochlorate.
By weight, can use this basic metal alkylbenzene sulfonate, preferred 10-50%, more preferably 10-20% with the amount of 0-70%.
This alkali metal sulfonate can be used for the mixture of alkylbenzene sulfonate, and by weight, its amount is 0-70%, preferred 10-50%.
Just also can be used as anionic group with branched-chain alkyl vitriol (for example primary alkyl sulphates).
The senior alkyl polyether thiourea hydrochlorate that is used for the present invention can be just or branched-chain alkyl and contain lower alkoxy (it can contain 2 or 3 carbon atoms) group.The reason of preferred positive senior alkyl polyether thiourea hydrochlorate is that they have the biological degradability higher than branched-chain alkyl, and this lower alkoxy groups is oxyethyl group preferably.
The preferred senior alkyl polyethoxye vitriol that is used for the present invention is expressed from the next:
R’-O(CH 2CH 2O) p-SO 3M
Wherein R ' is C 8-C 20Alkyl, preferred C 10-C 18, more preferably C 12-C 15P is 2-8, preferred 2-6, more preferably 2-4; M is for example sodium and potassium or an ammonium cation of basic metal.
Sodium and sylvite are preferred.
The vitriol of preferred senior alkyl polyethoxylated is the triethoxy C with following formula 12-C 15The alcohol sodium sulfate salt:
C 12-15-O-(CH 2CH 2O) 3-SO 3Na
The example that can be used for the present invention's suitable alkyl ethoxy sulfate is C 12-15Just or primary alkyl tetraethoxy sodium sulfate; Positive decyl diethoxy sodium sulfate; C 12Primary alkyl diethoxy ammonium sulfate; C 12Primary alkyl triethoxy sodium sulfate; C 15Primary alkyl tetraethoxy sodium sulfate; Blended C 14-15Positive primary alkyl mixing three and tetraethoxy sodium sulfate; Stearyl five oxyethyl group sodium sulfate; With blended C 10-18Positive primary alkyl triethoxy vitriolate of tartar.
Positive alkyl ethoxy sulfate is biodegradable easily and is preferred.The poly-lower alkoxy vitriol of this alkyl can be used for mixture each other and/or be used for the mixture of senior alkyl benzene sulfonate discussed above, alkylsulfonate or alkyl-sulphate.
This basic metal senior alkyl polyethoxye vitriol can use with alkylbenzene sulfonate and/or with alkylsulfonate or vitriol, and by composition total weight, its amount is 0-70%, preferred 10-50%, more preferably 10-20%.
The anion surfactant useful especially for the application comprises, but be not limited to: linear alkylbenzene sulfonate (for example deriving from the Vista C-500 of Vista Chemical Co.), alkyl-sulphate (for example deriving from the Polystep B-5 of Stepan Co.), the alkyl-sulphate of polyoxyethyleneization (for example deriving from the Standapol ES-3 of Stepan Co.), alhpa olefin sulfonate (for example deriving from the Witconate AOS of Witco Corp.), α sulfo group methyl ester (for example deriving from the α Step MC-48 of Stepan Co.) and isethionate (for example deriving from the JordaponCI of PPG industries Inc.).
By weight, the consumption of anion surfactant in prescription is about 0-60%, preferably between 5-40%, and more preferably 8-25%.
Cats product
A lot of cats products are known in this area, and any cats product that almost has a chain alkyl of at least one about 10-24 carbon atom all is suitable among the present invention.Such compound is described in " cats product " of Jungermann in 1970, and the document is incorporated by reference.
The cats product that specifically can be used as tensio-active agent in the present invention is described among the US4497718, and the document is incorporated by reference.
The same with anion surfactant as nonionic, composition of the present invention can perhaps use cats product with any other combinations-of surfactants ground known in the art individually.Certainly, said composition also can not contain cats product.
Amphoterics
The both sexes synthetic detergent can briefly be described as the derivative of aliphatic series or heterocycle is secondary and the aliphatic derivatives of tertiary amine, wherein this aliphatic group can be straight or branched and one of them aliphatic substituting group contain have an appointment 8-18 carbon atom and at least one and contain for example carboxyl of anionic water solubilizing group, sulfonate radical, sulfate radical.The example that drops on the compound in this definition is 3 (dodecyl amino) Sodium Propionate, 3-(dodecyl amino) propane-1-sodium sulfonate, 2-(dodecyl amino) sodium ethyl sulfate, 2-(dimethylamino) sodium stearate, 3-(N-carboxyl methyl dodecyl amino) propane-1-disodium sulfonate, octadecyl Iminodiacetic acid sodium salt, 1-carboxyl methyl-2-undecyl imidazole sodium, and N, two (2-the hydroxyethyl)-2-sulfatos of N--3-dodecyloxy propylamine sodium.3-(dodecyl amino) propane-the 1-sodium sulfonate is preferred.
Zwitterionics can briefly be described as the derivative of secondary and tertiary amine, the derivative of the heterocycle second month in a season and tertiary amine, perhaps quaternary ammonium, season rattle or the derivative of uncle's sulfonium compound.Cation atom in quaternary compound can be the part of heterocyclic ring.In all these compounds, there is at least one straight or branched aliphatic group to contain to have an appointment 3-18 carbon atom and at least one aliphatic substituting group to contain an anionic water solubilizing group for example carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical.
The example of operable zwitterionics is described among the US4062647, and the document is incorporated by reference.
The amount of the amphoterics that uses can be in the range of 0-50% weight, preferred 1-30% weight.
Should be noted that: composition of the present invention preferably isotropic (being generally understood as when the macroscopic observation about isotropy is homogeneous phase) and be transparent or semitransparent.
By weight, the total amount of the tensio-active agent of use must be 10% at least, preferably at least 15%, more preferably at least 20%.
Washing assistant/ionogen
The operable washing assistant of the present invention comprises the clean washing assistant of conventional inorganic or organic basic, presses composition weight meter, and its usage quantity can be about 0-50%, preferred 3-about 35%.
As using in this article, the term ionogen refers to water-soluble salt.
By weight, composition preferably includes at least 1.0%, and more preferably at least 5.0%, at least 10.0% ionogen most preferably.This ionogen also can be to clean for example inorganic builders tripoly phosphate sodium STPP of washing assistant, perhaps it also can the functional ionogen of right and wrong for example sodium sulfate or sodium-chlor.This inorganic builders preferably includes all or part ionogen.
By weight, composition can contain at least about 1%, preferably at least 3%, preferred 3% to about 50% ionogen.
Composition of the present invention can suspended particulate solids, but particularly preferably be those above-mentioned solids in fact be in suspended state system.This solid can be undissolved ionogen, and with identical or different in the solution, the latter is saturated ionogen.In addition, they can be water-fast basically materials.So basically, insoluble examples of material is the particle of silico-aluminate washing assistant and calcite abrasive material.
The example that operable suitable inorganic alkaline is cleaned washing assistant is a water-soluble alkali phosphoric acid salt, poly-phosphate, and borate, silicate also has carbonate.The object lesson of salt is sodium and potassium tri-polyphosphate like this, pyrophosphate salt, orthophosphoric acid salt, hempa hydrochlorate, tetraborate, silicate and carbonate.
The example that suitable organic basic is cleaned builder salt is: (1) water soluble amino multi-carboxylate is ethylenediamine tetraacetic acid (EDTA) for example, the sodium and the sylvite of triglycollamic acid and N-(2 hydroxyethyl)-nitrilo two acetic acid; (2) for example sodium phytate and potassium (seeing US2379942) of water miscible phytate; (3) water-soluble poly-phosphate comprises particularly: ethane-1-hydroxyl-1, the sodium of 1-bisphosphate, potassium and lithium salts; The sodium of Medronate, potassium and lithium salts; The sodium of ethylene phosphoric acid, potassium and lithium salts; Ethane-1,1, the sodium of 2-triphosphoric acid, potassium and lithium salts.Other example comprises: ethane-2-carboxyl-1,1-bisphosphate, hydroxyl methane bisphosphate, carboxyl bisphosphate, ethane-1-hydroxyl-1,1,2-triphosphoric acid, ethane-2-hydroxyl-1,1,2-triphosphoric acid, propane-1,1,3,3-four phosphoric acid, propane-1,1,2,3-four phosphoric acid and propane-1,2,2, an alkali metal salt of 3-four phosphoric acid; (4) water-soluble salt of multi-carboxy acid copolymer and multipolymer is as described in the US3308067.
In addition, can use the multi-carboxy acid salt washing agent satisfactorily, comprise mellitic acid, the water-soluble salt of citric acid and carboxyl methoxyl group succsinic acid, the salt of methylene-succinic acid and toxilic acid polymkeric substance, tartrate monosuccinic acid salt, tartrate disuccinate and its mixture (TMS/TPS).
Can use some zeolite and silico-aluminate.An above-mentioned silico-aluminate useful in the present composition is unformed water-insoluble formula Na x[(AlO 2) y.SiO 2) hydrated compound, wherein x is the number of 1.0-1.2, and y is 1, and the feature of described amorphous material also is its Mg ++Exchange capacity is about 50mg eq.CaCO 3/ g and its particle diameter are about 0.01-5mm.This ion-exchange washing assistant more fully is described among the GB1470250.
Second the insoluble synthetic aluminosilicate salt ion of useful herein water exchange material be crystallographic and have a formula Na z[(AlO 2) y. (SiO 2)] xH 2O, wherein z and y are at least 6 integer, and the mol ratio of z and y is in the scope of 1.0-0.5, and x is the integer of about 15-264; The particle diameter of described aluminosilicate ion exchange material is about 0.1-100mm; By moisture-free basis, calcium ion exchange capacity is about 200 milligramequivalent CaCO 3Hardness per gram; By moisture-free basis, calcium ion exchange rate is at least about 2 grains/gallon per minute/gram.These synthetic silico-aluminates more fully are described among the GB1429143.
Enzyme
Be described in more detail below the enzyme that can be used for the present invention.
If use lipase, this lipolytic enzyme can be the fungal lipase by Humicolalanuginosa and Thermomyces lanuginosus preparation so, perhaps can be the bacterium lipase that shows positive immunological cross-reaction with the antibody of the lipase of being separated fat subspecies N RRL B-3673 preparation by microorganism thickness look bacillus.This microorganism has been described in the Netherlands patent applications 154269 of ToyoJozo Kabushiki Kaisha and by Fermentation Research Institute, Agency of IndustrialScience and Technology, Ministry of International Trade andIndustry, Tokyo, the Japan preservation, joined in the permanent collection catalogue with the title of nr.KO Hatsu Ken Kin Ki137 and title that the public can nr.NRRL B-3673 at United States Department of Agriculture, AgriculturalResearch Service, Northern Utilization and DevelopmentDivision at Peoria, III., USA obtains.Lipase by this microorganism preparation can be from Toyo Jozo Co., Tagata, and Japan buys, and it is called as " TJ lipase " hereinafter.These bacterium lipase use standard and the known immunodiffusion(ID) method according to Ouchterlony (Acta.Med.Scan., 133.pages 76-79 (1930)) to demonstrate positive immunological cross-reaction with the TJ lipase antibody.
Sero-fast being prepared as follows:
Isopyknic 0.1mg/ml antigen and freund's adjuvant (completely or incomplete) are mixed up to obtaining emulsion.Give 2 female rabbit injections 45 times according to following scheme with the 2ml emulsion sample:
The 0th day: the antigen in complete Freund's adjuvant
The 4th day: the antigen in complete Freund's adjuvant
The 32nd day: the antigen in incomplete Freund's adjuvant
The 64th day: the antigen in incomplete Freund's adjuvant of booster dose
The serum that contained required antibody at the 67th day by the centrifugation preparation of the clot that condenses.
According to the Ouchteriony method, determine the sero-fast titre of anti-TJ lipase by checking the dilution sedimentation of a series of antigens and antiserum(antisera).Sero-fast extent of dilution is that the antigen concentration with 0.1mg/ml still can produce and can observe settled extent of dilution.
The bacterium lipase that all and aforesaid TJ lipase antibody demonstrate positive immunological cross-reaction all is suitable in the embodiment of the present invention.Its general example is that the lipase that derives from Pseudomonas fluorescens (Pseudomonas fluorescens) IAM 1057 is (can trade(brand)name Amano-P lipase from Amano Pharmaceutical Co., Nagoya, Japan obtains), derive from the lipase (can trade(brand)name AmanoB obtain) of Pseudomonas fragi FERM P 1339, derive from nitrogen reduction pseudomonas and separate the lipase of fat subspecies PERM 1338, derive from the lipase (can trade(brand)name Amano CES obtain) of Rhodopseudomonas kind, derive from the lipase of pseudomonas cepacia, (for example derive from thickness look bacillus, can be from Toyo Jozo Co., the thickness look bacillus that Tagata, Japan buy is separated fat subspecies N RRL B-3673) lipase; Derive from U.S.Biochemical Corp.USA and Diosynth Co. with other, the thickness look bacillus lipase of TheNetherlands and the lipase that derives from the Tang Changpu pseudomonas.
Example as fungal lipase defined above is: the lipase that derives from Humicola lanuginosa that can trade(brand)name Amano CE obtains; As at the lipase that derives from Humicola lanuginosa described in the above-mentioned EP0258068 (NOVO), and by the lipase that the clone derives from the gene of Humicola lanuginosa and this gene of expression obtains in aspergillus oryzae, it can trade(brand)name " Lipolase " be buied from NOVO industri A/S.This lipase is preferred among the present invention.
Although various concrete lipase described above should be understood and can use any lipase that needed lipolytic activity can be offered composition and the present invention not to plan to limit by any way the concrete selection of lipase.
The lipase of embodiment of the present invention is included in the liquid detergent composition with such amount, it makes that the using dosage of working as this prescription is about 0.1-10 grams per liter, more preferably 0.5-7 grams per liter, most preferably during the 1-2 grams per liter, the lipolytic enzyme activity of final composition in cycles of washing is 100-0.005LU/ml, preferred 25-0.05LU/ml.
Lipase unit (LU) be when a pH state below under the condition per minute form the amount of the lipase of the titratable lipid acid of 1/mmol: 30 ℃ of temperature; PH=9.0; Substrate is 3.3wt% sweet oil and 3.3% Sudan Gum-arabic, has 13mmol/l Ca in the 5mmol/l tris buffer 2+Emulsion with 20mmol/l NaCl.
Naturally also can use the mixture of above-mentioned lipase.Can use lipase with the form of its non-purifying or with the form (for example using known sour adsorption method such as phenyl sepharose adsorption technology purifying) of purifying.
If use proteolytic enzyme, this proteolytic enzyme can be plant, animal or microbe-derived so.Preferably originate in back one, and it comprises yeast, fungi, mould and bacterium.Particularly preferably be the bacterium subtilysin type proteolytic enzyme that obtains from the specific bacterial strain of for example subtilis and Bacillus licheniformis.Suitable commercially available examples of proteases is Alcalase, Savinase, and Esperase, they are all buied from NOVO Industri A/S; The Maxatase of Gist-Brocades and Maxacal; The Kazusase of Showa Denko; BPN and BPN ' proteolytic enzyme etc.By final composition, be included in the scope of the amount of the proteolytic enzyme in the composition, preferred 0.1-50GU/mg at 0.05-50000GU/mg.Naturally also can use the mixture of different proteolytic enzyme.
Although various concrete proteolytic enzyme described above should be understood and can use any proteolytic enzyme that needed protein decomposing activity can be offered composition and the present invention not to plan the concrete selection of limit protein enzyme by any way.
Except lipase or proteolytic enzyme, should understand other enzyme cellulase for example known in the art, oxydase, amylase, peroxidase etc. also can be used for composition of the present invention.If necessary, these enzymes can be with promoting the essential cofactor (cofactors) of enzymic activity to use, and promptly they can use with the form of enzyme system.Will also be appreciated that at all places the enzyme (for example strengthening and the enzyme of design for performance and/or stability) of sudden change being arranged also is that the present invention will consider.Example through the commercially available enzyme of design is the Durazym that derives from Novo.
Optional components
Except above-mentioned enzyme, can also use a lot of other optional components.
The alkaline buffer solution that can join in the present composition comprises monoethanolamine, trolamine, borax, water glass etc.
The hydrotropic agent that can join in the present composition comprises ethanol, sodium xylene sulfonate, cumene sodium sulfonate etc.
Other material is clay for example, and particularly the insoluble type of water can be an additive useful in the composition of the present invention.Useful especially is wilkinite.This material is montmorillonite basically, and it is a hydrated aluminium silicate, wherein about 1/6th aluminium atom can be substituted by magnesium atom and by this atom can loosely in conjunction with the hydrogen of difference amount, sodium, potassium, calcium etc.The wilkinite (promptly not having quartz sand, sand etc.) that is suitable for the purer form of washing composition contains at least 30% montmorillonite, so its cation exchange capacity (CEC) is at least about the 50-75meg/100g wilkinite.Particularly preferred wilkinite be by Georgia Kaolin Co. with Thixo-jels 1,2,3 and 4 Wyoming or the Western U.S. wilkinites of selling.As described in the GB461221 of the GB401413 of Marriott and Marriott and Guam, the known softening fabrics that is used to of these wilkinites.
In addition, various other detergent additives may reside in the Betengent product so that provide other needed character, or functional or aesthetic beauty.
By with the higher fatty acid aluminium salt of very little significant quantity for example aluminum stearate join the improvement that composition can be realized physical stability of such mixtures and resist coagulation aspect.The add-on of aluminum stearate stablizer can be 0-3%, preferred 0.1-2.0%, more preferably 0.5-1.5%.
Can also be included in the prescription is that a spot of dirt suspends or anti redeposition agent, polyvinyl alcohol for example, fatty amide, Xylo-Mucine, HYDROXY PROPYL METHYLCELLULOSE.Preferred anti redeposition agent is to be 2: 1 Xylo-Mucine with the CM/MC ratio that trade(brand)name Relatin DM 4050 sells.
Another minor consistuent is a dirt release agent, for example the deflocculate polymkeric substance.Usually the deflocculate polymkeric substance comprises hydrophilic backbone and one or more hydrophobic side chain.
Deflocculate polymkeric substance of the present invention is described in greater detail among people's such as Montague the US5147576, and the document is introduced among the application as a reference.
When using, the deflocculate polymkeric substance accounts for about 0.1-5% of composition usually, preferred 0.1-2%, most preferably from about 0.5-1.5%.
Can use the white dyes that is used for cotton, polymeric amide and polyester textile.Suitable white dyes comprises Tinopal, stilbene, the triazinyl stilbene that triazole and benzidine sulfone composition, especially sulfonated replace, sulfonated aphthotriazoles stilbene, biphenyl sulfone etc., most preferably stilbene and triazole composition.Preferred whitening agent is stilbene whitening agent N4, and it is a dimorpholine pentanoic stilbene sulphonate.
Antifoams for example silicone compounds such as Silicane L 7604 also can add with little significant quantity.
Can use sterilant for example tetrachloro salicylamide and Perchlorobenzene, mycocide, dyestuff, pigment (water-dispersion), sanitas is formalin for example, UV light absorber, anti-jaundice agent is Xylo-Mucine for example, pH regulator agent and pH buffered soln, color-safe SYNTHETIC OPTICAL WHITNER, spices and dyestuff and blue light agent be Iragon Blue L2D for example, Detergent Blue472/372 and ultramarine blue.
In addition, also can use soil release polymers and cationic softener.
The optional components of listing above be not limit and do not list but other optional components known in the art also can be included in the composition.
Randomly, the present composition can contain component below all or part: zwitterionics (for example deriving from the Miratain BET C-30 of Rhone-Poulenc Co.), cats product (for example deriving from Scher Chemicals, the SchercamoxDML of Inc.), fluorescence dye, the antiredeposition polymkeric substance, anti-dye transfer polymkeric substance, soil release polymers, proteolytic enzyme, lipase, amylase, cellulase, peroxidase, enzyme stabilizers, spices, opalizer, UV absorption agent, washing assistant and particle diameter are at the suspended particle of 300-5000 micrometer range.
Composition of the present invention has at least 50% transparence (use the cuvette of 1cm, at wavelength 410-800nm, preferred 570-690nm measures down, and wherein said composition does not have dyestuff basically).
In addition, the transparency of composition can be used as to have at visible wavelength (about 410-800nm) and is lower than 0.3 specific absorption and represents that it is equivalent at least 50% transparence of above-mentioned use cuvette and wavelength.For purpose of the present invention, as long as have transparence greater than 50% at the wavelength of visible-range, it just is considered to transparent/translucent.
When low-down uv b radiation transmission, enzyme deactivation can take place in the result as the UV-infringement.
Bottle material
The operable clear bottles material of the present invention includes, but are not limited to: polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyamide (PA) and/or polyethylene terephthalate (PETE), polyvinyl chloride (PVC), and polystyrene (PS).
Transparent or light transmission container according to the present invention preferably has the transparence greater than 25% in spectrographic visible light part (about 410-800nm), more preferably greater than 30%, more preferably greater than 40%, most preferably greater than 50%.
In addition, the light absorptive of bottle can be used as and is lower than 0.6 (being equivalent to 25% transparence approximately) mensuration, perhaps uses the light transmission measurement greater than 25%, and wherein the % transparence equals:
For purpose of the present invention, as long as have transparence greater than 50% at the wavelength of visible-range, this container just is considered to transparent/translucent or printing opacity.
When low-down uv b radiation saw through wall of container, enzyme deactivation can take place in the result as the UV-infringement.
Container of the present invention can be any form or the size that is suitable for family expenses purpose preservation and packaging liquid.For example, this container can have virtually any size, but the maximum volume of this container is 0.05-15L usually, preferred 0.1-5L, more preferably 0.2-2.5L.This container preferably is suitable for easily using.For example, this container can have a handle or have the part of such size so that can the portable or displacement with easily.This container preferably has the device that is suitable for the pouring liquid detergent composition and is used for closing again the device of upper container.This tipper can be virtually any size or form, but preferred enough wide so that metering liquid detergent composition easily.This stopping device can be any form or size, thereby but normally twists or press the pass upper container on container.This stopping device can be the lid that can pull down from container.Another kind method is no matter container is to open or cut out this lid still to be connected on the container.This stopping device also can be contained on the container.
Following embodiment is that being used for further specifying of the present invention is not to limit the present invention by any way:
Except as otherwise noted, all percentage ratios all are weight percentage.
All numerical ranges in this specification sheets and claims all are proximate.
At last, the term that uses in specification sheets and claims " comprises ", is not to get rid of term, step or the feature of specifically not addressing.
Method
The mensuration of light absorptive and transparence
Instrument: Milton Roy Spectronic 601
Method:
1. open spectrophotometer and power supply box switch and allow its preheating 30 minutes.
2. wavelength is set
-on keyboard, key in necessary wavelength (promptly 590,640, or the like)
-by [second function] key
-by " go to λ " [yes] key
So-machine is prepared in selected wavelength reading of data
3. instrument zeroing
-by [second function] key
-by " zero A " [%T/A/C]
So the reading of-instrument is " XXX NM 0.000 AT "
4. open lid, with samples vertical be placed on before the transmitter
5. close loam cake and reading of data (ex.640 NM 0.123 A T)
* annotate: all readings all read under " A " pattern (extinction pattern)
* annotate: carry out the instrument zeroing with each new wavelength change and/or fresh sample
The light absorption value of two kinds of typical plastics bottles
Wavelength nm Polyethylene (HDPE); 0.960mm it is thick Polypropylene (PP); 0.423mm it is thick
254 (invisible lights) ????1.612 ????1.886
310 (invisible lights) ????1.201 ????0.919
360 (invisible lights) ????0.980 ????0.441
590 (visible-ranges) ????0.525 ????0.190
640 (visible-ranges) ????0.477 ????0.169
Synthetic day light box
(be used to try to execute the device of example; Only be used for UVA and UVB scope)
Chest size and outward appearance:
Long 4 feet
Wide 2 feet
High 2 feet
By 3/4 " the glued board formation.Chest is placed so that the air cycle circulation for liftoff about 2 inches.One small fan is placed on covering of chest.4 lamps are installed in the long limit of chest, and 2 on every limit is separated by about 6 inches.
Comprise that fan is in order to keep internal temperature during whole test.This has guaranteed that any effect of being seen only is the result of UV-light rather than heat.
Sample is put in the container of opening and put in the chest.Using open containers is in order to limit the interference of container material to light.Also the water with open containers is added in this chest.This water remains on air constant humidity and makes and slows down from the evaporation of opening sample.After given for some time, from chest, take out sample, rethink the evaporation of moisture and the effect of test UV.
Accelerated deterioration:
According to " daylight, UV and accelerated deterioration " technical bulletin LU-0822, QUV accelerated weathering test instrument forms grade estimation panel of experts (Q-panel) laboratory product.
Daylight is to damage plastics, fabric, the major reason of coating and other organic materials.Although UV light only constitutes 5% of daylight, it is the major cause that causes most of photochemistry to damage.This is because the photochemical effect of light increases along with the reduction of wavelength.Short UV light is considered to cause most of the damage to have for a long time.The accelerated weathering test instrument is widely used in research and development, quality control, and materiology.They use various light source solar simulated and by sun-induced damage.
In order to simulate, do not need to reproduce the whole spectrum of daylight by sun-induced damage.For most of material, only need to simulate shortwave UV.For our specific purpose, select the UVA-340 lamp.Most of radiation of this lamp is in the UV-A zone, on a small quantity in the UV-B zone.This lamp simulated admirably about 370nm to sunlight by the daylight of 295nm.
Embodiment 1
The liquid washing agent sample (being set forth in the following table 1) that will contain proteolytic enzyme and lipase joins diameter 1 " glass disc in, open top cover and be exposed to 254nm, 110 microwatts/cm 2UV light in (apart from light source 28 ", 5 days).After per 24 hours, the weighing sample is also opened the water that top cover replenishes evaporation.Use suitable substrate (for example casein is as protease substrate, and the p-NP valerate is as the lipase substrate) to measure the enzymic activity of the sample that is exposed to UV light.With the initial activity before the sample UV irradiation is the percentage ratio that benchmark calculates remaining activity.These samples contain the xitix of 25mM, the BHA of 2.5mM, or the BHA of 2.5mM is as protective material.This is corresponding to the xitix of 0.044wt%, the BHA of 0.045wt% and the BHA of 0.055wt%.Control sample does not contain such protective material.Result following (table 2a):
Table 1A detergent formulation
Component as 100% actives ????Wt%
????Neodol?25-9 * ????6-8
The ethanol ethoxy sulfate ????12-15
Linear alkylbenzene sulfonate ????6-9
Trisodium Citrate, dihydrate ????3-6
Propylene glycol ????4-8
Sorbyl alcohol ????3-6
The sodium tetraborate pentahydrate ????2-4
Less important additive and water To 100%
* C 12-C 15Oxyalkylated (9EO) chain group
Table 2a antioxidant is to the effect of the enzyme stability under UV-C (254nm) irradiation
Sample Enzyme Residual enzyme % after 24 hours
Base-material+no antioxidant only is a base-material Proteolytic enzyme lipase ????62 ????67
Base-material+25mM xitix (0.044wt.%) Proteolytic enzyme lipase ????82 ????75
Base-material+2.5mM BHA (0.045wt.%) Proteolytic enzyme lipase ????74 ????76
Base-material+2.5mM BHT (0.055wt.%) Proteolytic enzyme lipase ????68 ????68
Table 2a shows that enzyme stability is higher when using antioxidant.
The liquid washing agent sample (top table 1) that embodiment 2 will contain proteolytic enzyme and lipase joins diameter 1 " glass disc in, open top cover and be exposed to 254nm, 110 microwatts/cm 2UV light in (apart from light source 28 ", 24 hours).After 24 hours, the weighing sample is also opened top cover and is replenished the weight of the water of evaporation to beginning.Use suitable substrate to measure the enzymic activity of the sample that is exposed to UV light.With the initial activity before the sample UV irradiation is the percentage ratio (% residual enzyme) that benchmark calculates remaining activity.These samples contain the xitix of 12.5mM, the BHA of 12.5mM, or the BHT of 12.5mM is as protective material.Control sample does not contain such protective material.Result following (table 2b):
Table 2b antioxidant is to the effect of the enzyme stability under UV-C (254nm) irradiation
Sample Enzyme Residual enzyme % after 24 hours
Base-material+no antioxidant (only being base-material) Proteolytic enzyme ????53
Lipase ????67
Base-material+12.5mM xitix (0.22wt.%) Proteolytic enzyme ????79
Lipase ????70
Base-material+12.5mM BHT (0.23wt.%) Proteolytic enzyme ????77
Lipase ????70
Base-material+12.5mM BHT (0.28wt.%) Proteolytic enzyme ????77
Lipase ????70
This has shown the effect of the composition protective enzyme under the UV irradiation with antioxidant again.
Embodiment 3
With embodiment 1 and 2 similar conditions under similarly test, but use UV-A/B chamber (UVA=1.01mW/cm in the lamp 2, UVB=6.17mW/cm 2).In this case, the HDL that will contain enzyme and antioxidant protection agent was exposed to UV light following 4 days.Result's following (table 3):
Table 3 antioxidant is to the effect of the enzyme stability under the UV-A/B irradiation
Sample Enzyme Residual enzyme % after 4 days
Base-material+no antioxidant (only being base-material) Proteolytic enzyme ????22
Lipase ????0
Base-material+12.5mM xitix (0.22wt.%) Proteolytic enzyme ????87
Lipase ????21
Base-material+12.5mM BHA (0.23wt.%) Proteolytic enzyme ????73
Lipase ????48
Base-material+6.25mM xitix (0.11wt.%)+6.25mM BHA (0.12wt.%) Proteolytic enzyme ????90
Lipase ????43
Last table explanation: as indicated in the % residual enzyme, have xitix, BHA, the stability of proteolytic enzyme and lipase under the BHT raising UV-A/B light.The result has also confirmed the synergy between two kinds of antioxidants, as contains shown in the example of xitix and BHA.

Claims (5)

1, a kind of transparent or semitransparent heavy-dirt liquid composition in clear bottles, it contains:
(a) tensio-active agent of 10-85% weight, it is selected from negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics and its mixture;
(b) enzyme of 0.001-5% weight, it is selected from proteolytic enzyme, lipase, cellulase, oxydase, amylase and its mixture; With
(c) antioxidant of 0.001-3% weight;
Wherein said composition has about 50% or higher transparence, and this transparence is used the cuvette of 1cm, measures under wavelength 410-800nm; With
Wherein this bottle has the transparence greater than 25% under about 410-800nm wavelength.
2, according to the composition of claim 1, wherein this antioxidant is BHT.
3, according to the composition of claim 2, wherein this antioxidant is an xitix.
4, according to the composition of claim 1, wherein this antioxidant is BHA.
5, a kind ofly prevent in clear bottles the method for the enzyme liberating of enzyme in the transparent or semitransparent liquid composition, this method comprises antioxidant is joined in the described composition.
CN99814495.9A 1998-12-16 1999-11-30 Transparent/translucent liquid enzyme compositions in clear bottles comprising antioxidants Pending CN1380900A (en)

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US7074581B2 (en) * 2002-08-09 2006-07-11 Sysmex Corporation Reagent for assaying lipid
WO2005080540A1 (en) * 2004-02-24 2005-09-01 Novozymes A/S Enzyme stabilization in liquid detergents
EP1700904A1 (en) * 2005-03-11 2006-09-13 Unilever N.V. Liquid detergent composition
US20070267444A1 (en) * 2006-05-05 2007-11-22 De Buzzaccarini Francesco Concentrated compositions contained in bottom dispensing containers
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Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2136913B1 (en) * 1971-05-07 1973-05-11 Colgate Palmolive Co
JPS5438605B2 (en) * 1974-06-07 1979-11-22
US4238345A (en) * 1978-05-22 1980-12-09 Economics Laboratory, Inc. Stabilized liquid enzyme-containing detergent compositions
US4243543A (en) * 1979-05-11 1981-01-06 Economics Laboratory, Inc. Stabilized liquid enzyme-containing detergent compositions
US4462922A (en) * 1981-11-19 1984-07-31 Lever Brothers Company Enzymatic liquid detergent composition
GB8311314D0 (en) * 1983-04-26 1983-06-02 Unilever Plc Aqueous enzyme-containing compositions
GB8520550D0 (en) * 1985-08-16 1985-09-25 Unilever Plc Detergent compositions
DE68923398T2 (en) * 1988-05-12 1996-01-25 Procter & Gamble Liquid universal detergents containing anionic and non-ionic surfactants, builders and proteolytic enzyme.
GB2232420A (en) * 1989-05-30 1990-12-12 Unilever Plc Liquid detergent compositions
US5789364A (en) * 1993-02-17 1998-08-04 The Clorox Company High water liquid enzyme prewash composition
US5466394A (en) * 1994-04-25 1995-11-14 The Procter & Gamble Co. Stable, aqueous laundry detergent composition having improved softening properties
AU2399295A (en) * 1994-04-29 1995-11-29 Procter & Gamble Company, The Cellulase fabric-conditioning compositions
CA2189544C (en) * 1994-05-06 2000-06-13 Kenneth Michael Kemen Liquid detergent containing polyhydroxy fatty acid amide and toluene sulfonate salt
WO1997026315A1 (en) * 1996-01-18 1997-07-24 Colgate-Palmolive Company Filled package of light duty liquid cleaning composition
BR9713487A (en) * 1996-10-21 2002-11-26 Procter & Gamble Processes for the preparation of an active compound and a premixed fabric softener and fabric softener composition
WO1999053008A1 (en) * 1998-04-09 1999-10-21 The Procter & Gamble Company Dishwashing detergent product having a ultraviolet light resistant bottle

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