CN1066193C - Double coated protease compatible with lipase in dry concentrated bleach compositions - Google Patents
Double coated protease compatible with lipase in dry concentrated bleach compositions Download PDFInfo
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- CN1066193C CN1066193C CN94192823A CN94192823A CN1066193C CN 1066193 C CN1066193 C CN 1066193C CN 94192823 A CN94192823 A CN 94192823A CN 94192823 A CN94192823 A CN 94192823A CN 1066193 C CN1066193 C CN 1066193C
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- composition
- detergent composition
- acid
- lipase
- additive
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Abstract
The invention relates to a detergent composition or additive comprising a high level of bleach, a lipase and a double coated protease (e.g. Savinase 4.0 CT +). Also the use of said composition or additive wherein the lipolytic activity in the presence of protease remains unchanged is part of this invention.
Description
For strengthening the total cleaning action of clothing, in laundry detergent, use SYNTHETIC OPTICAL WHITNER for a long time.
The use SYNTHETIC OPTICAL WHITNER can be with color spot on fabric, textiles and the stiff dough and dirt oxidation.Render a service because peroxy bleaching compounds (peroxygenbleaching compound) such as hydrogen peroxide, Sodium peroxoborate or SPC-D have oxidation, therefore found that these compounds are applicable to the SYNTHETIC OPTICAL WHITNER preparation very much.
Some organic compound is added in the SYNTHETIC OPTICAL WHITNER as perborate can generates peracid, thereby improve bleachability, such organic compound comprises such as tetra acetyl ethylene diamine activators such as (TAED).
But the performance for lipid dirt and enzyme dirt is limited, therefore causes not satisfying to greatest extent the human consumer.So still need to improve such whitener composition.
Enzyme has the use prospect in this case, and it has in very effective mode removes for example greasy certain benefits.
Although lipase also shows good active in exsiccant has the matrix of high-content SYNTHETIC OPTICAL WHITNER, be added with proteolytic enzyme (Savinase for example
R4.0T Novo produces) time, the attack (attack) that as if lipase activity become and be subject to very much proteolytic enzyme.
Consequently lipase activity descends greatly in washing soln.
Also known under some condition of storage, the stability decreases of enzyme in detergent composition or additive.
For overcoming the problems referred to above, Novo Industri A/S provides a kind of solution in patent application Wo 87/07292 (this application is incorporated this paper into as a reference): the enzyme material that shows high stability under unfavourable condition is carried out coating and do not bring any undesirable side effect.
But in composition, add standard protein enzyme (Savinase
R4.0T Novo produces) lipase activity in washing soln is reduced greatly.
In the solution with high-content SYNTHETIC OPTICAL WHITNER, the avtive spot of lipase may directly not be subjected to the attack of proteolytic enzyme, and can continue to work.But also may be that in the quaternary structure of lipase part or all can be partly or sex change (denatured) fully, cause lipase active sites under the attack that is exposed to proteolytic enzyme to a greater extent.
In composition, add proteolytic enzyme (Savinase with high-content SYNTHETIC OPTICAL WHITNER
R4.0T Novo produces) time, find no matter be that lipase all shows tangible lipolysis activity and descends in washing soln in performance or in the analysis experiment.
Our invention is, has high-load SYNTHETIC OPTICAL WHITNER, lipase and two coating (doublecoated) proteolytic enzyme (Savinase for example
R4.0 CT
+, Novo produces) detergent composition or additive be provided at the good especially performance in lipolysis activity aspect.It is shocking that as if lipolysis activity keep more or less and do not exist the situation of proteolytic enzyme the same in composition or additive.This clearly is embodied in spot and cleans and can bleach on the removal performance of color spot, and the discolor obvious advantage of spot of the enzymatic of having kept protease simultaneously.
Therefore, in such composition or additive, producing from having fabulous consistency between lipase and the proteolytic enzyme in the dissolved environment that highly concentrates (drying) SYNTHETIC OPTICAL WHITNER.
In drying, spissated SYNTHETIC OPTICAL WHITNER, use double coated protease (Savinage
R4.0 CT
+, Novo produces), rather than use other proteolytic enzyme more commonly used (for example Savinase4.0T, Novo produces), make that the stability of lipase is extremely excellent, in our invention, lipase is not subjected to the strong attack of proteolytic enzyme, and works with maximum capacity.
Therefore, even can use the lipase of lower aq to be used for the removal of spot cleaning and/or triglycerin class color spot satisfactorily, so need not to replenish the loss of enzyme activity that causes owing to uncompatibility with proteolytic enzyme.This saving of obviously having guaranteed during products production, to pay wages, better industrial hygiene condition, and consider from the human security angle, product between the usage period danger also lower.
Equally, the SYNTHETIC OPTICAL WHITNER activating mechanism of realizing by for example toxilic acid acrylic copolymer or acid anhydrides and lipase also continues to work with very high efficient.
Activation system will replenish the effect of known activator of bleaching agent; these activators are organic complex class, quaternary ammonium or the quaternary phosphine bleach precursor of TAED, NOBS, BOBS, different NOBS, PAG, TAGU, sulfimide class, metalloporphyrin class, manganese for example, (for example trimethyl ammonium toluene acyloxy benzene sulfonate) or ethanoyl glycerol fatty acid ester.They also replenish preformed peracid, for example effect of DPDA, NAPAA, PAP (N, the N phlhalimide base is crossed caproic acid), list and dicarboxylic acid.
Self contain hydrogen peroxide cource (perborate, percarbonate etc.) if drying composition or the liquid composition that contains hydrogen peroxide also contain acid anhydrides and lipase, then they can have the bleach activation of obvious reinforcement.
The acid anhydrides that can buy, for example succinyl oxide and maleic anhydride can be contained in the dry whitener composition of band lipase.But, also can include other acid anhydrides that do not have ring-type even also do not have symmetrical structure.
Polymkeric substance acid anhydrides class and to comprise the multipolymer of anhydride monomers also very suitable.Preferred in this respect vinylformic acid and copolymer-maleic anhydride.
Exemplary formulations of the present invention comprises: anhydrous SODIUM PERCARBONATE 25-60% tetra acetyl ethylene diamine; (TAED) 0-20% anhydrous citric acid 5-20% natrium citricum 0-10% silicate SKS-6 0-20% sodium sulphate 0-40%Lipolase 100T; (Novo) 0.1-10%Savinase 4.0CT+; (Novo) 0.05-10% maleic acid acrylic copolymer 2-10%; (granular Sokalan CP5) spices 0.10-0.20%FWA; the BH-base 0.02-0.06% that (Tynopal CBS-X) 0.04-0.10% seals
Illustrate instantiation of the present invention be typical laundry bleaching agent formulation (A1) and (A2) anhydrous SODIUM PERCARBONATE 46.00 46.00TAED, the 10.22 10.22Savinase 4.0T of A1 A2 % % (4.0 KNPU/g) 0.5-Savinase 4.0CT+ (5.1 KNPU/g)-0.4 maleic acid acrylic copolymers (Sokalan CP5) 4.00 4.00Lipolase 100T (100 LU/g) 0.50 0.50 anhydrous citric acid 7.00 7.00 Carbon Dioxide hydrogen receive 13.00 13.00Brightener 49.BH base, spices is until 100% until 100%
Illustrate that other examples of the present invention are the typical automatic bowl preparation with high-content SYNTHETIC OPTICAL WHITNER.
Lipase
The used lipase of the present invention is included in washing composition and the bleaching composition, and its consumption makes the steatolysis enzymic activity that has 10～0.005LU/mg in the final composition, preferred 5～0.05LU/mg composition.
It is the emulsion of a kind of 3.3wt% of containing sweet oil and 3.3% Sudan Gum-arabic that one lipase unit (LU) is defined as at 30 ℃ of temperature, pH=9.0, substrate, at 13mmol/l Ca
++And the existence condition of the 20mmol/l NaCl in 5mmol/l Tris-buffer reagent under, per minute generates the amount of the lipase of 1/ little titratable lipid acid that rubs in stablizing pH value system.EP0258068 (Novo) is seen in the another kind definition of lipase unit, and this patent (inter alia) is mentioned operable lipase in actually operating of the present invention, quotes for referencial use herein.
Certainly can use the mixture of above-mentioned lipase and other known lipase.Can use the not purified lipase or the lipase of purifying, purification process can adopt similar phenyl sepharose adsorption technology variously knows adsorption method.
Detergent composition of the present invention or additive can be mixed with any form easily, wherein preferred powder form.Composition has various purposes and can be used in anhydrous bleaching preparation and the detergent formulations, comprising above-mentioned clothing and automatic dishwasher detergent formulations.
Composition of the present invention can be used for machine-washing or the cloth drying SYNTHETIC OPTICAL WHITNER hand-washed in.Dosage mostly is each washing 5gr-80gr, and washing lotion can be with geographical condition changing, and can change at 20-60 liter/time washing room.
The machinery that composition of the present invention also the can be used for general type process that washes the dishes, used dishwasher can be selected from market.More particularly, this machinery process of washing the dishes comprises with the dissolving or the aqueous solution that is dispersed with the said detergent composition of significant quantity and handles the article that dirt is arranged, for example pottery, glassware, hollow ware and cutter etc.The significant quantity of detergent composition is as the wash the dishes dosage of process product commonly used of standard machinery, and each washing adds 8g～60g detergent composition, makes it dissolving or is dispersed in 3 to 10 liters of washing solns.The washing process temperature is generally in 40～65 ℃ of scopes.Also can add the rinse aid composition if desired.
Can contain other used components of aforementioned present technique field in detergent composition of the present invention or the additive; Deposition agent, flavouring agent, tensio-active agent, anti-pigment shift component, white dyes, other enzymes (as proteolytic enzyme and amylase) etc. again as washing assistant, anti-soil dirt.
In addition, detergent composition also can comprise tensio-active agent, they can be anion surfactant, nonionogenic tenside, amphoterics, cats product or zwitterionics, also can be these surfactant mixtures.
These commonly used tensio-active agents are authorized on May 23rd, 1972 in the United States Patent (USP) 3,664,961 of Norris and are listed.
The mixture of anion surfactant is particularly suitable in this, the mixture of sulfosalt surfactant and sulfate surfactant especially, and wherein the weight ratio of the two was generally 5: 1 to 1: 2, was preferably 3: 1 to 2: 3, more preferably 3: 1 to 1: 1.Preferred sulfonate comprises alkylbenzene sulfonate and α-sulfonation fatty acid methyl ester, and the alkyl chain carbon number of alkylbenzene sulfonate is from 9 to 15, and the alkyl chain that contains 11 to 13 carbon atoms is more suitable, and α-the used lipid acid of sulfonation fatty acid methyl ester can be from C
12～C
18Fat source is derived, wherein C
16～C
18Fat source more preferably.Negatively charged ion separately all is a basic metal, wherein preferred sodium.Preferred sulfate surfactant is the alkyl-sulphate of alkyl chain carbon number from 12 to 18, optionally mixes ethoxy sulfate during use, and the alkyl chain carbon number of ethoxy sulfate is 10 to 20, more preferably 10 to 16, and average degree of ethoxylation from 1 to 6.The example of preferred alkyl-sulphate has tallow alkyl sulfate, coconut palm fat alkyl-sulphate and C
14～15Alkyl-sulphate.The example of preferred ethoxy sulfate is usually said AE3S (C
12～15The vitriol of 3 ethoxylations of alkyl), the positively charged ion under the various situations is alkali metal cation, preferred sodium.
Can be used for a class nonionogenic tenside of the present invention is the condenses of oxyethane and hydrophobic part, is 8-17 to form average hydrophile-lipophile balance value (HLB), preferred 9.5-13.5, the more preferably tensio-active agent of 10-12.5.Hydrophobic (oleophylic) part can be aliphatic or aromatic with regard to character, can regulate easily with the length of the polyoxyethylene group of specific hydrophobic group condensation, to generate the water-soluble cpds of required hydrophile-lipophile balance value.For bringing into play the activity of lipase to greatest extent, the present invention preferably uses a kind of so-called nil-LAS that contains detergent composition or additive.
Particularly preferred this class nonionogenic tenside is the C that every mol of alcohol contains the 3-8 moles of ethylene oxide
9-C
15Primary alcohol ethoxylate, especially those every mol of alcohol contain the C of 6～8 moles of ethylene oxide
14～C
15Primary alconol and every mol of alcohol contain the C of 3-5 moles of ethylene oxide
12～C
14Primary alconol.
Another kind of ionic surfactant pack is drawn together alkyl polyglucoside (alkyl polyglucoside) compound of following general formula,
RO (C
nH
2nO)
tZx wherein Z represents by glucose deutero-part; R is the saturated hydrophobic alkyl group that contains 12 to 18 carbon atoms; T represents 0 to 10; N represents 2 or 3; X represents 1.3 to 4.Also comprise unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the short-chain alkyl polyglucoside that is less than 50% in this compound.This compounds is open being applied among the EP-B0070077,0075996 and 0094118 of washing composition with them.
Suc as formula
Polyhydroxy fatty acid amide surfactant also be suitable for and make nonionogenic tenside, wherein R
1Represent H, C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture; R
2Represent C
5-31Alkyl, Z representative comprise one and bring to few 3 polyhydroxy alkyls that directly are connected to the linear alkyl of the hydroxyl on the chain, or its alkoxy derivative; Wherein preferential is R
1Represent methylidene, R
2Represent straight chain C
11～17Alkyl or alkenyl chain, for example coconut alkyl or their mixture, Z is derived from the reducing sugar in the reductive amination process, for example glucose, fructose, maltose and lactose.
According to the present invention, it is anion surfactant and nonionogenic tenside between 1: 1 to 10: 1 that detergent composition or additive preferably comprise ratio.
Another kind of tensio-active agent is the semi-polarity tensio-active agent as amine oxide.The amine oxide that is suitable for is selected from single C
8～C
20(preferred C
10～C
14) N-alkyl or alkenyl amine oxide compound and 1,3-propylene diamine dioxide, wherein remaining nitrogen bonding position can be replaced by methyl, hydroxyethyl or hydroxypropyl.
Another kind of tensio-active agent is an amphoterics, as being the tensio-active agent of principal constituent with the polyamine.
Cats product also can be used in the detergent composition of the present invention, and the quaternary surfactant that is fit to is selected from single C
8～C
16(preferred C
10～C
14) N-alkyl or alkenyl ammonium surfactant, wherein residual nitrogen bonding position can be replaced by methyl, hydroxyethyl or hydroxypropyl group.
The mixture of various surfactants, particularly cloudy release-non-ionic type and anionic-non-ionic type-cationic mixture are preferred.Particularly preferred surfactant mixture is described in British Patent NO.2040987 and EuropeanPublished Application NO.0087914.The tensio-active agent that can contain 1%～70% weight in the detergent composition, but the content of tensio-active agent is generally 1%～30% (weight) in detergent composition of the present invention, more preferably 2～25%.Too much tensio-active agent is harmful to lipase activity.
Washing assistant
Help washing matter content in detergent composition of the present invention to be generally 0%～90%; Preferred 0%～30%.
Detergent composition of the present invention should preferably not contain or not phosphatic substantially washing assistant (herein do not contain substantially mean help at total washing composition its content is less than 1% in the system of washing).The system of washing that helps of the present invention can be made up of water soluble detergency promoter, water-insoluble washing assistant or their mixture.Certainly, when detergent composition was used for the automatic bowl process, washing assistant was preferably water miscible.
Water-insoluble washing assistant can be a kind of mineral ion exchange material, selects the inorganic silicon-aluminum hydrochloride hydrates usually for use, especially as synthetic zeolite hydrates such as hydration Zeolite A, X, B, P, MAP or HS.
Preferred silico-aluminate ion exchange material has following structure cell formula:
M
z[(AlO
2) z (SiO
2) y] xH
2O wherein M represents the calcium exchange cation; Z and Y are at least 6, and the mol ratio of Z and Y is 1.0 to 0.5; X is at least 5, and is preferred 7.5～276, and more preferably 10～264.The silico-aluminate material is a hydrated form, and the crystal of preferably moisture 10%～28% (more preferably 18%～22%).
The feature of above-mentioned silico-aluminate ion exchange material is that also its particle diameter is between 0.1 to 10 micron, preferred 0.2～4 micron; " particle diameter " vocabulary shows the average particle diameter of the given ion exchange material that the analysis means commonly used such as microscopy that adopt scanning electronic microscope are for example measured herein.The feature of silico-aluminate ion exchange material is that also its calcium ion-exchanged capacity should be at least the normal CaCO of 200mg in anhydride
3The water hardness/g silico-aluminate, generally at the 300mg equivalent between 352mg equivalent/g.The feature of silico-aluminate ion exchange material of the present invention also is their calcium ion exchange rate, sees GB-1 for details, 429,143.
The silico-aluminate ion exchange material that the present invention can actual use is commercially available product, can be natural goods, but synthetics preferably., discussed in 985,669 at US Patent NO.3 about the method for preparing the silico-aluminate ion exchange material.The synthetic crystallization shape silico-aluminate ion exchange material that can preferably use can Zeolite A, with Zeolite B, with ZeoliteX, obtain with the trades mark such as Zeolite HS and their mixtures.In a particularly preferred embodiment, the crystal aluminosilicate ion exchange material is Zeolite A, and molecular formula is:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein X is 20～30, especially 27.Molecular formula is
Na
86[(AlO
2)
86(SiO
2)
106]-10.276H
2The Zeolite X of O and molecular formula are Na
6[(AlO
2)
6(SiO
2)
6] 7.5H
2O) Zeolite HS also is fit to.
The another kind of water-insoluble no machine aided washing matter that is fit to is stratification silicate (Layeredsilicate), as SKS-6 (Hoechst).SKS-6 is a kind of by water glass (Na
2Si
2O
5) the crystallization stratification silicate formed.High Ca
++/ mg
++Binding ability mainly is a cationic exchange mechanism.This substance dissolves improves in hot water.
Water soluble detergency promoter can be monomer or oligomeric carboxylate sequestrant.
The carboxylate that contains a carboxyl that is fit to comprises lactic acid, glycolic acid and their ether derivant, and this is at Belgian Patent Nos.831, and is open in 368,821369 and 821370.The many carboxylates that contain two carboxyls comprise the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) diacetic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid, and German OffenlegenSchrift 2,446,686 and 2,446,687 and U.S.Patent NO.3,935, the ether carboxylate of describing in 257, Belgian PatentNO.840, the sulfinyl carboxylate of describing in 623.The many carboxylates that contain three carboxyls comprise water-soluble citrate, aconitate and citraconate, and succinate derivative, as British Patent NO.1,379, the newborn oxygen base succinate (lactoxysuccinate) and the British Patent NO.1 that describe among the carboxy methoxy-succinic acid salt of describing in 241, the Netherlands Application 7205873,387, oxygen Quito carboxylate such as the 2-oxa--1 described in 447,1,3-propane three carboxylate (2-oxa-1,1,3 propane-tricarboxylate).
The many carboxylates that contain four carboxyls comprise British Patent NO.1, disclosed oxygen base disuccinate, 1,1,2 in 261,829,2-ethane tetracarboxylic acid thing, 1,1,3,3-propane tetramethyl acidulants and 1,1,2,3-propane tetramethyl acidulants.Contain the substituent many carboxylates of sulfo group and comprise British Patent Nos.1,398,421,1,398, disclosed sulfo-succinic acid salt derivative in 422 and U.S.PatentNO.3,936,448, with British PatentNO.1, the sulfonation pyrolysis Citrate trianion of describing in 082,179, and contain the substituent many carboxylates of phosphine at British Patent NO.1, open in 439,000.
The many carboxylates of alicyclic ring and heterocycle comprise pentamethylene-suitable, suitable, suitable-tetramethyl acidulants, cyclopentadiene five first acidulants, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetramethyl acidulants, 2,5-tetrahydrofuran (THF)-suitable-diformazan acidulants, 2,2,5,5-tetrahydrofuran (THF)-tetramethyl acidulants, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane-pregnancy acidulants and polyhydroxy-alcohol, these polyhydroxy-alcohol examples such as sorbyl alcohol, mannitol and Xylitol.The many carboxylates of aromatics comprise mellitic acid, 1,2,4,5-pyromellitic acid and British Patent NO.1, disclosed phthalic acid derivative in 425,343.
In above-mentioned many carboxylates, preferred many carboxylates are the hydroxyl carboxylate, particularly Citrate trianion that per molecule contains three carboxyls at the most.Used preferred builder system comprises as water-insoluble silico-aluminate washing assistant such as Zeolite A or stratification silicate (SKS/6) and mixture as water-soluble carboxylation thing sequestrants such as citric acids in the present composition.
Other washings that help that can be configured for builder system of the present invention comprise as inorganicss such as alkaline carbonate, supercarbonate and silicate.
Other water-soluble organic salts that are fit to are homopolymerization or co-polymeric acids or their salt.Wherein poly carboxylic acid comprises at least two each other for the carboxyl of no more than two carbon atoms separate.
This base polymer is at GB-A-1, and is open in 596,756.The example of this class salt is that molecular weight is the multipolymer of the polyacrylate of 2000-5000 and it and maleic anhydride, the molecular weight of this analog copolymer in 20,000 to 70,000 scopes, especially about 40,000.
Composition of the present invention can fully contain the sequestrant (heavy metal sequestering agent) that accounts for composition weight 0.05% to 5%, and is preferred 0.05%～1%, and most preferably 0.1%～0.5%.
The sequestrant that can suit to comprise in the detergent composition of the present invention is quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its an alkali metal salt, alkaline earth salt, ammonium salt, replacement or their mixture.Preferred EDDS compound is free acid and its sodium salt or magnesium salts.The example of these preferred EDDS sodium salts comprises Na
2EDDS and Na
4EDDS.The example of these preferred EDDS magnesium salts comprises MgEDDS and Mg
2EDDS.Most preferably contain the EDDS magnesium salts in the detergent composition of the present invention.
Other sequestrants include organic phosphonates, and amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxy-diphosphonic acid salt, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt are wherein arranged.Phosphonate compounds can they sour form or exist with the form of the title complex of alkalimetal ion or alkaline metal ions, the molar ratio of described metal ion and described phosphonate compounds was at least 1: 1.These title complexs are at US-A-4, describe in 259,200.
The organic phospho acid compound that exists is preferably the magnesium salts form.The content of phosphorated chelating agent should be the least possible in the detergent composition of the present invention, gets rid of them fully in the most preferred group compound.The suitable sequestrant of other that can comprise comprises as amino many carboxylates sequestrants such as EDTA and HEDTA.
Optional components
Generally also comprise optional components in the composition of the present invention, these components often constitute the part of detergent composition.The for example anti-redeposition of these optional compositions and soil-suspending agent, white dyes, SYNTHETIC OPTICAL WHITNER, activator of bleaching agent, suds suppressor, anti-hard caking agent, dyestuff and pigment, they can add different amounts as required.
Suitable anti-redeposition and soil-suspending agent comprise as derivatived celluloses such as methylcellulose gum, carboxymethyl cellulose and Natvosols, and homopolymerization or copolymerization poly carboxylic acid or their salt.Such polymkeric substance comprises that the front mentions polyacrylate and the copolymer of maleic anhydride and acrylic acid as washing assistant, also have the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, the maleic anhydride composition accounts for 20% (mole) at least in the multipolymer.The consumption of these materials is generally 0.5～10% of composition weight, and is preferred 0.75～8%, and most preferably 1%～6%.
Preferred white dyes is an anionic property, these examples have 4,4 '-two-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) Stilbene-2,2 '-the disulfonic acid disodium, 4,-4 '-two-(2-morpholino-4-anilino-S-triazine-6-base is amino) Stilbene-2: 2 '-the disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-S-triazine-6-base is amino) Stilbene-2: 2 '-the disulfonic acid disodium, 4 ', 4 " two-(2,4-hexichol amido-S-triazine-6-base is amino) Stilbene-2-sodium sulfonate; 4; 4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-S-triazine-6-base is amino) Stilbene-2; 2 '-the disulfonic acid disodium; 4,4 '-two-(4-phenyl-2,1; 3-triazole-2-yl)-Stilbene-2,2 ' disulfonic acid disodium, 4,4 '-two (2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-triazine-6-base is amino) Stilbene-2,2 ' disulfonic acid disodium and 2 (Stilbene base-4 " (naphtho--1 '; 2 ': 4; 5)-1,2,3-triazoles-2 " sodium sulfonate.
The inorganic perhydrate SYNTHETIC OPTICAL WHITNER of any particulate (perhydrate bleach) all can be used.When using in the SYNTHETIC OPTICAL WHITNER additive, the consumption of inorganic perhydrate is for providing 3～11% (weight) in composition, and is preferred 4～8.5%, more preferably 4～7% active oxygen.The preferred example of these SYNTHETIC OPTICAL WHITNER is the monohydrate and the tetrahydrate of Sodium peroxoborate, SPC-D and their mixture.
The component of another kind of preferred additionally mixed is a kind of peroxycarboxylic acid SYNTHETIC OPTICAL WHITNER and its salt, preferably adds with form granular or as a form of gel during use.
Peroxygen bleach preferably mixes use with activator of bleaching agent, (just in the washing process corresponding to the peroxy acid of bleach-activating agent) can produce resultant on the spot in the aqueous solution like this.Disclose the suitable example of this compounds among the British Patent Nos.1586769 and 2143231, in European PublishedPatent Application NO.0062 523, be described about making them generate globular method.The preferred example of these compounds is tetra acetyl ethylene diamines, 3; 5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt, diperoxy dodecylic acid, peroxide hexanodioic acid pelargonamide, positive nonanoly acyloxy benzene sulfonate (NOBS) and acetyl triethyl citrate (ATC) as describing among the EuropeanPatent Application 91870207.7 as describing among the US 4 259 201 as in US 4 818 425, describing.
The consumption of activator of bleaching agent be generally for instance composition heavy 1%～24%, more commonly used 1%～18%, preferred 2%～14%.
Another kind of optional components is a suds suppressor, for example siloxanes and silicon-dioxide one mixture of siloxanes.Siloxanes is generally the alkylation polysiloxane, and silicon-dioxide is generally selected its chip form for use, as aerosil and xerogel and dissimilar hydrophobic silicas.These materials can fine-grained form add, but wherein suds suppressor advantageously is added on a kind of non-surface active basically washing composition opacity carrier of water-soluble or water dispersible with releasing pattern.In addition, suds suppressor also solubilized or be dispersed in a kind of liquid vehicle and with spray method it is added on one or more other components.
As described above, the silicone foam control agent that is suitable for can comprise above the alkylation siloxanes of the kind of carrying and a kind of mixture of silica solid.This mixture is by making the method for siloxanes attached to the surface of solid silica.A kind of preferred silicone foam control agent be a kind of size of particles between 10 millimicrons to 20 millimicrons, specific surface area is greater than 50m
2The hydrophobic silaneization of/g (most preferably trimethylammonium-silanization) silicon-dioxide and molecular weight are greatly about 500～200, the intimately admixing thing of the dimethyl silicone fluids between 000, wherein siloxanes to the weight ratio of silanized silica greatly between 1: 1 to 1: 2.
A kind of preferred silicone foam control agent is disclosed among the U.S.Patent 3,933,672 of Bartollota etc.Other useful especially froth suppressor are self-emulsifying siloxane foams inhibitor, and this described in the German Patent ApplicationDTOS 2,646,126 that published on April 28th, 1977.An example of this compound is the DC-544 that commercially available DowCorning makes, and it is a kind of siloxanes/glycol multipolymer.
The consumption of above-mentioned suds suppressor is generally 0.001%～2% of composition weight, and preferred 0.01%～1%.Independent particle is preferably made in the adding of foam properties-correcting agent, so just can make wherein including other foam inhibition things, as C
20～C
24The high molecular weight copolymer of lipid acid, Microcrystalline Wax and oxyethane and propylene oxide, if not so, then these materials will have a negative impact to the dispersiveness of substrate.The U.S.Patent NO.3 for preparing Bartolotta that the technology of this foam modified particle formerly mentions etc., open in 933,672.
Other useful polymkeric substance are polyoxyethylene glycol, and particularly molecular weight is at 1000～10000 polyoxyethylene glycol, wherein molecular weight 2000～8000 more preferred, molecular weight be approximately 4000 the most preferred.Its consumption be composition heavy 0.2% to 5%, preferred 0.25% to 2.5%.These polymkeric substance and previously mentioned homopolymerization or copolymerization multi-carboxylate are for promoting whiteness to keep in the presence of transition metal impurity, and fabric dust deposition and the scourability that improves clay, protein and oxidable dirt all are favourable.
Used stain remover is the conventional terephthalic acid and ethylene glycol and/or the unitary multipolymer of propylene glycol or the terpolymer of different arrangements in the present composition.The example of these polymkeric substance is in the common US Patent Nos 4116885 that transfers the possession of and 4711730 and EuropeanPublished Patent Application NO.0, and is open in 272,033.The expression formula of a kind of special preferred polymers of EP-A-0 272 033 is: (CH
3(PEG)
43)
0.75(POH)
0.25(T-PO)
2.8(T-PEG)
0.4] T (PO-H)
0.25((PEG)
43CH
3)
0.75PEG is-(OC in the formula
2H
4) O-, PO is (OC
3H
6O) and T be (PCOC
6H
4CO).
Modified poly ester also is well-adapted, this modified poly ester is dimethyl terephthalate, dimethyl sulfo group isophthalic ester, ethylene glycol and 1, the random copolymers of 2-propylene glycol, and its end group mainly is made up of the sulfosalicylic acid ester, secondly is made up of ethylene glycol and/or propylene glycol monoester.Target be obtain two ends all " mainly " by the polymkeric substance of sulfo group benzene methyl group end capping, be among the present invention most of multipolymers all by sulfosalicylic acid ester end-blocking, but the inwhole end-blockings of some multipolymer, so the end group of these multipolymers just may be by ethylene glycol and/or 1, the monoesters group of 2-propylene glycol is formed, and therefore " secondly " is just by these species compositions.
The dimethyl terephthalic acid that contains about 46% (weight) herein in the selected polyester, about 16% (weight) 1, the 2-propylene glycol, the ethylene glycol of about 10% (weight), the dimethyl methyl yl benzoic acid of about 13% (weight), with the sulfoisophthalic acid of about 15% (weight), and molecular weight is about 3,000.About polyester and preparation method thereof, in EPA 311 342, be explained in detail.
5000 to 20,000, some polymkeric substance such as polyvinylpyrrolidone of preferred 10000-15000 also can be used as effective auxiliary agent and are used for the transfer that washing process stops unstable tinting material between fabric as molecular weight.
Also can add fabric softener in the detergent composition of the present invention.These auxiliary agents can be inorganic or organic on kind.The example of inorganic softening agent has GB-A-1, disclosed montmorillonitic clay in 400,898.The organic fabric softening agent is included among GB-A-1514276 and the EP-B-0011340 disclosed water-insoluble tertiary amine and disclosed these water-insoluble tertiary amines and single C in EP-B-0 026 527 and EP-B-0 026 528
12～C
14Disclosed pair of long-chain acid amides among the mixture of quaternary ammonium salt and the EP-B-0 242 919.The useful organic constituent of other of fabric sofetening system comprises as EP-A-0 299 575 and 0,313, disclosed high molecular weight polyethylene oxide material in 146.
When montmorillonitic clay was added to the rest part of preparation as a kind of dry blending component, consumption was 5% to 20% of a composition weight, preferred 8% to 15%.The consumption of organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides be composition heavy 0.5% to 5%, be generally 1% to 3%; And the add-on of high molecular weight polyethylene oxide class and water-soluble cationic material is 0.1% to 2% (weight), is generally 0.15% to 1.5%.Though can the dry mixed particulate forms add easily at these materials of some occasions, these materials are to be added in the spray-dired part of composition generally speaking, perhaps their liquid forms with fusing are sprayed onto in other solid ingredients of composition.
Manufacture method
Composition of the present invention can do mix by comprising, the whole bag of tricks manufacturing in being combined in of spraying drying, agglomeration and granulating and these technology.Composition of the present invention can be made into the product with different stacking densities, from the plain particles product to so-called " concentrating " product (being that the product tap density is greater than 600g/l).Example 1
At 40 ℃, (14g/US gallon) experimentizes in the European washing machine with medium-hard water.In each cycles of washing, on 170g powder washing composition basis, add the various preparations of 70g.Result separately carries out 6 multiple mean values with each experiment product.All results all represent and the common contrast relatively, with the wash result that A1 or A2 (as above-mentioned) obtain, contrast is that what to sell in southern Europe is the commonly used dry whitener composition (Ace Color) of principal constituent with the perborate.
By this experimental technique, the result of 0～0.5 unit shows with contrast and the removal effect that the experiment product reaches does not have observable difference.0.6-1.0 showing with having little between contrast and the removal effect that reaches of experiment product, the result of unit is the visible difference.1.1-2.0 the result of unit shows that two kinds of products provide obvious difference and removal effect that can easy-to-use visual difference.Positive result shows that with respect to contrast better removal effect is arranged.
With scourability experimental result (this test used detergent composition be liquid Regular Dash) the Ace Color A* A1 A2 of the preparation of being with enzyme with respect to ACe Color acquisition
*[preparation A refers to the preparation identical with A1 and A2, but does not have the Savinase (4.0CT+) of Savinase (4.0T) and two coatings respectively]
These results show that adding standard Savinase 4.0T in product causes the active decline of Lipolase.This clearly shows total spot cleaning performance (with the object evaluation that tarnishes of human consumer's family, comprising the dirt of triglyceride level base, as the body dirt) and can bleach in the removal effect decline of dirt.Back one effect is derived from the bleach activation of undesirably removing by lipase and toxilic acid and acrylic copolymer.Clean and can bleach dirt with Savinase 4.0CT+ spot and remove performance and all be restored, and keep the obvious advantage of the enzyme dirt removal effect that protease provides simultaneously.Example 2
To the matrix that does not contain SYNTHETIC OPTICAL WHITNER (100% sodium sulfate) with have and add Lipolase 100T and/or different types of Savinase in the matrix (for example A1 and A2) of high-content SYNTHETIC OPTICAL WHITNER.The result is as follows:
These results are the average of three parallel detections of each sample, and prove that lipolysis activity is subjected to having a strong impact on of Savinase 4.0T when dissolving has the matrix of high-load SYNTHETIC OPTICAL WHITNER.And when using 4.0CT+, lipolysis activity maintains very high level, also is like this in the matrix of high-load SYNTHETIC OPTICAL WHITNER is arranged.
Possible is that consistency and coated material fairly obvious and good between Savinase 4.0 CT+ and the Lipolase are closely related with its concentration in granular enzyme.Coating generally uses Macrogol 4000 (PEG) and/or polyvinylpyrrolidone (PVP) and derivatived cellulose to constitute.Coating also can contain other components as filler, Liniment or granulating agent, oxidation inhibitor (as Na
2SO
4, CaCO
3, NaCl, talcum, TiO
2, Magnesium Silicate q-agent, sorbyl alcohol, acrylic or methacrylic acid and other unitary multipolymers etc.).
Savinase 4.0 CT+ and the good consistency of Lipolase may be attributable to the content height of PEG in the coating and/or PVP.What it should be noted that is, PEG and PVP are the materials that can play reversible inhibition under specific situation to Savinase, and therefore strengthens the consistency with Lipolase.
In addition, being added with proteolytic enzyme when suppressing composition (as PEG and/or PVP) in the coating of Lipolase itself rather than in the coating of proteolytic enzyme, also is a part of the present invention to the effect of Lipolase stabilization.
Claims (8)
1. detergent composition or additive; the proteolytic enzyme that contains high-load SYNTHETIC OPTICAL WHITNER, lipase and two coatings, the proteolytic enzyme of wherein said pair of coating contain and are selected from following application substance: Macrogol 4000, polyvinylpyrrolidone, derivatived cellulose, filler, Liniment, granulating agent, oxidation inhibitor and composition thereof.
2. by the detergent composition or the additive of claim 1, wherein effective active oxygen is 3.0-11 weight % in the composition.
3. by the detergent composition or the additive of claim 1, wherein SYNTHETIC OPTICAL WHITNER is anhydrous SPC-D.
4. by the detergent composition or the additive of claim 3, wherein composition also contains activator of bleaching agent.
5. press the detergent composition or the additive of claim 1, wherein the proteolytic enzyme of two coatings polyoxyethylene glycol and/or polyvinylpyrrolidone and a kind of derivatived cellulose coating.
6. by the detergent composition or the additive of claim 5, wherein proteolytic enzyme is NOVO system Savinase 4.0 CT+.
7. the detergent composition of claim 1 or Application of Additives, wherein lipolysis activity remains unchanged in washing soln.
8. by the detergent composition or the Application of Additives of claim 7, be used for removing grease and/or can bleaching and/or the protein dirt at washing soln.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93870099A EP0628625B1 (en) | 1993-06-07 | 1993-06-07 | Protease compatible with lipase in dry, concentrated bleach compositions |
| EP93870099.4 | 1993-06-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1127522A CN1127522A (en) | 1996-07-24 |
| CN1066193C true CN1066193C (en) | 2001-05-23 |
Family
ID=8215348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94192823A Expired - Fee Related CN1066193C (en) | 1993-06-07 | 1994-06-02 | Double coated protease compatible with lipase in dry concentrated bleach compositions |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0628625B1 (en) |
| JP (1) | JPH09501451A (en) |
| CN (1) | CN1066193C (en) |
| AU (1) | AU678027B2 (en) |
| BR (1) | BR9406791A (en) |
| CA (1) | CA2164587A1 (en) |
| DE (1) | DE69324802T2 (en) |
| ES (1) | ES2131103T3 (en) |
| GR (1) | GR3030162T3 (en) |
| WO (1) | WO1994029423A1 (en) |
| ZA (1) | ZA943979B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9407534D0 (en) * | 1994-04-13 | 1994-06-08 | Procter & Gamble | Detergent compositions |
| DE19501120A1 (en) * | 1995-01-17 | 1996-07-18 | Henkel Kgaa | Enzyme-containing bleaching detergent |
| EP0846155B1 (en) * | 1995-08-25 | 2000-02-09 | Henkel Kommanditgesellschaft auf Aktien | Use of lipases in low-alkaline mechanical dishwashing agents |
| CA2665521C (en) * | 2006-10-06 | 2016-10-18 | Danisco Us, Inc., Genencor Division | Cellulase-free enzyme compositions and host cells for producing the same |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1590432A (en) * | 1976-07-07 | 1981-06-03 | Novo Industri As | Process for the production of an enzyme granulate and the enzyme granuate thus produced |
| GB8514707D0 (en) * | 1985-06-11 | 1985-07-10 | Unilever Plc | Enzymatic detergent composition |
| US5167854A (en) * | 1985-08-21 | 1992-12-01 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
| US4863626A (en) * | 1985-08-21 | 1989-09-05 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
| JPS63503390A (en) * | 1986-05-21 | 1988-12-08 | ノボ インダストリ アクテイ−ゼルスカブ | coated detergent enzyme products |
| ATE110768T1 (en) * | 1986-08-29 | 1994-09-15 | Novo Nordisk As | ENZYMATIC DETERGENT ADDITIVE. |
| US4965012A (en) * | 1987-04-17 | 1990-10-23 | Olson Keith E | Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches |
| DK571587D0 (en) * | 1987-11-02 | 1987-11-02 | Novo Industri As | ENZYMATIC DETERGENT COMPOSITION |
| JPH02208400A (en) * | 1989-02-07 | 1990-08-17 | Lion Corp | Bleaching agent composition |
| US5107854A (en) * | 1989-05-19 | 1992-04-28 | Boulder Impact Monitors, Inc. | Orthopedic limb load monitor |
| ATE94206T1 (en) * | 1989-12-21 | 1993-09-15 | Novo Nordisk As | ENZYME-CONTAINING PREPARATION AND DETERGENTS CONTAINING SUCH PREPARATION. |
| US5281356A (en) * | 1993-03-25 | 1994-01-25 | Lever Brothers Company | Heavy duty liquid detergent compositions containing non-proteolytic enzymes comprising capsules comprising proteolytic enzyme and composite polymer |
-
1993
- 1993-06-07 DE DE69324802T patent/DE69324802T2/en not_active Expired - Fee Related
- 1993-06-07 EP EP93870099A patent/EP0628625B1/en not_active Expired - Lifetime
- 1993-06-07 ES ES93870099T patent/ES2131103T3/en not_active Expired - Lifetime
-
1994
- 1994-06-02 BR BR9406791A patent/BR9406791A/en not_active Application Discontinuation
- 1994-06-02 JP JP7501929A patent/JPH09501451A/en not_active Ceased
- 1994-06-02 WO PCT/US1994/006189 patent/WO1994029423A1/en active Application Filing
- 1994-06-02 CN CN94192823A patent/CN1066193C/en not_active Expired - Fee Related
- 1994-06-02 CA CA002164587A patent/CA2164587A1/en not_active Abandoned
- 1994-06-02 AU AU70507/94A patent/AU678027B2/en not_active Ceased
- 1994-06-07 ZA ZA943979A patent/ZA943979B/en unknown
-
1999
- 1999-05-07 GR GR990401142T patent/GR3030162T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0628625A1 (en) | 1994-12-14 |
| ES2131103T3 (en) | 1999-07-16 |
| CA2164587A1 (en) | 1994-12-22 |
| WO1994029423A1 (en) | 1994-12-22 |
| GR3030162T3 (en) | 1999-08-31 |
| DE69324802T2 (en) | 1999-12-09 |
| AU678027B2 (en) | 1997-05-15 |
| AU7050794A (en) | 1995-01-03 |
| DE69324802D1 (en) | 1999-06-10 |
| BR9406791A (en) | 1996-01-30 |
| CN1127522A (en) | 1996-07-24 |
| EP0628625B1 (en) | 1999-05-06 |
| ZA943979B (en) | 1995-02-02 |
| JPH09501451A (en) | 1997-02-10 |
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