CN101550385A - Process for the preparation of laundry soap bars with improved storage stability - Google Patents

Process for the preparation of laundry soap bars with improved storage stability Download PDF

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Publication number
CN101550385A
CN101550385A CNA2009101299293A CN200910129929A CN101550385A CN 101550385 A CN101550385 A CN 101550385A CN A2009101299293 A CNA2009101299293 A CN A2009101299293A CN 200910129929 A CN200910129929 A CN 200910129929A CN 101550385 A CN101550385 A CN 101550385A
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enzyme
soap
preblend
acid
laundry
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CN101550385B (en
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尼尔斯·H·索伦森
杰弗里·邓卡夫
李浩东
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Novo Nordisk AS
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Novo Nordisk AS
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    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/40Proteins
    • 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0069Laundry bars
    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/042Acids
    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • 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
    • 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
    • C11D3/2065Polyhydric alcohols
    • 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
    • C11D3/2075Carboxylic acids-salts thereof
    • 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
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/221Mono, di- or trisaccharides or derivatives thereof
    • 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
    • C11D3/38609Protease or amylase in solid compositions only
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/08Water-soluble 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/08Water-soluble compounds
    • C11D9/10Salts
    • C11D9/16Borates
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/26Organic compounds, e.g. vitamins containing oxygen
    • C11D9/265Organic compounds, e.g. vitamins containing oxygen containing glycerol

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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  • Detergent Compositions (AREA)

Abstract

The present invention relates to a process for the preparation of laundry soap bars comprising the steps of a) Preparing a premix by mixing an enzyme, a stabilizer, a polyol and optionally a pH controlling agent; b) Mixing the premix of step a) with a soap,- c) Refining the mixture of b) to refined soap; and d) Plodding the refined soap of step c).

Description

The laundry soap bar of improved storage stability
Invention field
The present invention relates to have the laundry bars (laundry bar) of the enzyme stability of improvement, prepare the method for described laundry bars and the purposes of this laundry bars.
Background of invention
It is well-known that enzyme is added into laundry bars.When adding enzyme in laundry bars, the stability of the enzyme of interpolation in production and storage process just becomes extremely important.Certainly wish to keep activity as much as possible.
The activity of the enzyme that adds can be subjected to for example influence of the water-content of laundry bars.High-load water causes enzyme activity in storage of being added lower usually, particularly for proteolytic enzyme.
It is 10-33% and the laundry bars that contains proteolytic enzyme that GB2186883 has described water-content, and wherein proteolytic ferment comes stabilization by following mixture: an alkali metal salt of the mineral acid of boron compound, polyvalent alcohol, organic acid or its an alkali metal salt and non-boron compound.
WO98/54285 has described the laundry bars that contains high-moisture proteolytic enzyme of the proteolytic enzyme stability with improvement.Obtain the stability of this improvement by adding stablizer, this stablizer is to be made together with polyvalent alcohol, carboxylate salt, carboxylic acid or their mixture by borate.
In WO97/36958 by providing a kind of laundry bars to improve the enzyme stability of cellulase, this laundry bars contains the synthetic detergent tensio-active agent of about 0.5%-60%, in final laundry bars component, have about 4% or moisture still less, with about 0.1% to about 10% on-liquid thixotropic adhesive (thixotropic binding agents), and cellulase.
Prior art cited above all relate to store and use in enzyme stability, yet the loss of making enzyme work in the laundry bars process when enzyme incorporated into the laundry composition of washing bars also is a major issue.It is believed that the sex change of the loss of this kind of enzyme stability, and this sex change owing to being exposed to high shear forces and high pH and/or high temperature, causes enzyme because of enzyme.Make it have acceptable physical property in order to process the laundry bars component that contains synthetic surfactant and have a relative high-moisture level, high temperature usually is essential.If enzyme adds with particle (granule) or pill (prill) form, in runner milling and/or moulding press, act on the high shear forces meeting destructive enzyme particle of laundry bars composition and the integrity of enzyme pill, and make enzyme be exposed to be subjected to opposing compound (hostile compound), for example attack of anion surfactant.
WO98/18897 has described and has a kind ofly incorporated enzyme the method for the composition of washing bars of doing washing into, and this method makes the minimization of loss of enzyme stability in the preparation process of laundry bars.This be by mill and cool off after the enzyme pill is added mold pressing then (plodding) mixture method realize.
Summary of the invention
An object of the present invention is to provide the Preblend that contains liquid enzymes that is used to prepare laundry bars.Another object of the present invention provides a kind of soap bar that comprises enzyme and acceptable enzyme stability is provided.Another object of the present invention provides the method that contains the enzyme laundry bars that a kind of preparation has the package stability of improvement.Another object of the present invention provides the laundry bars by method preparation of the present invention.
The inventor finds surprisingly: in the process of making the laundry soap bar, preparation comprises the Preblend of liquid enzymes product, stablizer and polyvalent alcohol rather than respectively each component is added in the soap, has significantly improved the package stability of enzyme in the laundry soap bar.
Therefore, another aspect of the present invention provides the Preblend that comprises enzyme, stablizer and polyvalent alcohol.
Another aspect of the present invention is the method for preparing the soap bar of doing washing, and it comprises the following steps:
A) prepare Preblend by enzyme, stablizer and the polyvalent alcohol that mixes as liquid preparation;
B) Preblend of step a) is mixed with soap;
C) with b) mixture be refined into refining soap; And
D) the refining soap of mold pressing step c).
The invention still further relates to the purposes of laundry soap bar of the present invention.
Detailed Description Of The Invention
Definition
Laundry bars:
Term laundry bars or laundry soap bar comprise soap bar (soap bar), compound (combo bar), synthetic detergent bar (syndet bar) and detergent bar (detergent bar).Laundry bars is used for hand-wash laundry (handwashing laundry).
Foreword
The present invention relates to laundry bars, it contains the enzyme of incorporating into wherein.The present invention be more particularly directed to the package stability of laundry bars.
Although enzyme stability in the production of laundry bars and the storage process improved did some trials, enzyme loses its activity and remains a significant problem during storage in process of production and in laundry bars.We find surprisingly: if enzyme with make Preblend before soap mixes, then can significantly improve in the production process of laundry bars and the enzyme stability after storing.
The invention still further relates to the improved method of enzyme being mixed laundry bars, can obtain good enzyme stability and good mixing simultaneously, thereby realize more mixing of homogeneous simultaneously by this method.
Known practice is; the dried enzyme that uses as enzyme granulate with the enzyme granulate form when the preparation laundry bars can provide protective layer around enzyme; make enzyme avoid the opposing attack of compound; and can make when adding liquid enzymes enzyme be exposed to opposition compound in the washing composition matrix fully, so the laundry bars industry is unwilling to use liquid enzymes in laundry bars is produced because the remarkable stability of loss enzyme.Use the particulate shortcoming to be if they add in the process of mixing or the mold pressing/step of milling; part particle can be broken into pieces (torn out); thereby make enzyme be exposed to the opposition compound, also cause a large amount of losses of enzymic activity, thereby cause needs to add significantly excessive enzyme granulate.
For prevent particle mix and the step of milling in cracked, can after the aforesaid method step, add particle, as described in WO98/18897, but can cause the uneven distribution of enzyme in the laundry bars, and particle still can be cracked when the mold pressing step.
Yet we find surprisingly: compare with known product, by use the liquid enzymes product and its with stablize these liquid enzymes products with the Preblend form before soap mixes, we can significantly improve the enzyme stability of laundry bars.
If use the liquid preparation (formulation) that contains enzyme to replace particle, we obtain comparing the laundry bars with improved enzyme stability with the laundry bars that utilizes the conventional preparation of enzyme granulate surprisingly, and can also obtain enzyme more uniform distribution in laundry bars.It is liquid preparation that method of the present invention allows enzyme, can be before mixing or mixing process add, these are different with the method described among the WO98/54285.
Be contemplated that and when using enzyme granulate,, use liquid enzyme formulation most possibly to reduce the mechanical stress of enzyme product as comparing in containing in the enzyme laundry bars of routine.This may reduce the amount of the heat of friction that forms in the mixing process again.Liquid enzyme formulation also can distribute in soap blank more quickly, produces the more product of homogeneous at shorter time, reduces the preparation time of laundry bars thus.Liquid enzymes also is easy to make the enzyme stabilizers of adding approaching with it.For example proteolytic enzyme be easy to make enzyme stabilizers near and in avtive spot, form borax (Borax) complex compound, this causes the reversible inactivation.
Laundry bars is mainly sold in third world countries, so the cost of laundry bars is exactly an important factors.By our method, do not need in laundry bars, to add significantly excessive enzyme, this will reduce the final cost of laundry bars.
Preblend
Preblend of the present invention comprises enzyme, stablizer and polyvalent alcohol.This Preblend also can comprise pH control compound.
In a specific embodiments of the present invention, Preblend comprises: as the proteolytic enzyme of enzyme; As the boron-containing compound of stablizer for example borate and boric acid; Glycerine as polyvalent alcohol; And as the citric acid of pH control agent or free fatty acids C for example 12Acid.
Thoroughly mix Preblend, thereby before adding to soap, obtain uniform mixture.
Enzyme
Can be its effect of performance in the hand washing process by the stable enzyme of the inventive method, for example, any enzyme that in hand washing is used, has cleaning, fabric nursing, antiredeposition and clean effect, and described enzyme adds for such purpose.
Enzyme in the linguistic context of the present invention can be the combination of any enzyme or different enzymes.Therefore, when mentioning " enzyme ", be generally understood as the combination that comprises a kind of enzyme or enzyme.
Be appreciated that enzyme variants (for example enzyme that produces by recombinant technology) is also included within the implication of term " enzyme ".The example of these enzyme variants is disclosed in, for example, and EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV).
Can on the basis of 1992 enzyme nomenclature handbook enzyme be classified from NC-IUBMB, also referring to the ENZYME website on the Internet: Http:// www.expasy.ch/enzyme/ENZYME is the information storage relevant with enzyme nomenclature.It mainly is based on the suggestion of the NK of international biological chemistry and molecular biology federation (IUB-MB), Academic Press, Inc., 1992, it describes each type (Bairoch A.The ENZYME database of the enzyme that has characterized that provides its EC (Enzyme Commission (the enzyme council)) number, 2000, Nucleic Acids Res 28:304-305).This IUB-MB enzyme name sometimes also can be based on their molecule mechanism based on their substrate specificity.This classification does not reflect the constitutional features of these enzymes.
Proposed several years ago based on amino acid sequence similarity some glycoside hydrolase, be divided into the another kind of classification of family as endoglucanase, the poly-enzyme of wood sugar, Galactanase, mannase, dextranase and alpha-galactosidase.They fall into 90 different families at present: referring to internet site ((Coutinho, the P.M.﹠amp of CAZy (ModO); Henrissat, B. (1999) Carbohydrate-ActiveEnzymes server are in URL:http: //afmb.cnrs-mrs.fr/~cazv/CAZY/index.html (corresponding document: Coutinho, P.M.﹠amp; Henrissat, B. (1999) Carbohydrate-active enzymes:anintegrated database approach. is in " Recent Advances in CarbohydrateBioengineering ", H.J.Gilbert, G.Davies, B.Henrissat and B.Svensson compile, TheRoyal Society of Chemistry, Cambridge, pp.3-12; Coutinho, P.M.﹠amp; Hen-rissat, B. (1999) The modular structure of cellulases and other carbohydrate-activeenzymes:an integrated database approach. is in " Genetics; Biochemistry andEcology of Cellulose Degra-dation "., K.Ohmiya, K.Hayashi, K.Sakka, Y.Kobayashi, S.Karita and T.Kimura compile, Uni Publishers Co., Tokyo, pp.15-23).
The enzyme type that can incorporate in the laundry bars of the present invention comprises oxydo-reductase (EC 1.-.-.-), transferring enzyme (EC 2.-.-.-), lytic enzyme (EC 3.-.-.-), lyase (EC 4.-.-.-), isomerase (EC 5.-.-.-) and ligase enzyme (EC62.-.-.-).
Specially suitable enzyme comprises lyase or lytic enzyme (EC 3.-.-.-), particularly proteolytic enzyme, amylase, lipase, pectate lyase, carbohydrase and/or cellulase.
Preferred oxydo-reductase is peroxidase (EC 1.11.1), laccase (EC1.10.3.2) and notatin (EC 1.1.3.4) in the linguistic context of the present invention].The example of commercial available oxydo-reductase (EC 1.-.-.-) is Gluzyme TM(enzyme that can obtain from Novozyme A/S).More oxydo-reductase can obtain from other supplier.Preferred transferring enzyme is the transferring enzyme of any following subclass:
A shifts the transferring enzyme (EC 2.1) of a carbon-based group;
B shifts the transferring enzyme (EC 2.2) of aldehydes or ketones residue; Acyltransferase (EC 2.3);
C glycosyltransferase (EC 2.4);
D shifts aliphatic hydrocarbyl or aryl, does not comprise the transferring enzyme (EC 2.5) of methyl; With
E shifts the transferring enzyme (EC 2.6) of nitrogen-containing group.
Most preferred transferring enzyme type is a trans-glutaminases (protein-glutamine in the linguistic context of the present invention; EC 2.3.2.13).
Other example of suitable transglutaminase is described (Novo NordiskA/S) in WO96/06931.
Preferred lytic enzyme is in the linguistic context of the present invention: carboxylic ester hydrolase (EC3.1.1.-) is as lipase (EC3.1.1.3); Phytase (EC 3.1.3.-), for example 3-Phytase (EC 3.1.3.8) and 6-phytase (EC 3.1.3.26); Glycosylase (EC 3.2, and it falls into the group of the application with " carbohydrase " expression) is as α-Dian Fenmei (EC 3.2.1.1); Peptase (EC 3.4, also make proteolytic enzyme); And other carbonylic hydrolase.Commercial available phytase example comprises Bio-Feed TMPhytase (Novozymes), Ronozyme TMP (DSM Nutritional Products), Natuphos TM(BASF), Finase TM(AB Enzymes) and Phyzyme TMProduct line (Danisco).Other preferred phytase comprises those that describe among WO 98/28408, WO 00/43503 and the WO 03/066847.
In this linguistic context, term " carbohydrase " not only is used for representing to interrupt sugar chain (as starch or Mierocrystalline cellulose), particularly the enzyme of five yuan or six-membered ring structure (is a Glycosylase, EC 3.2), the enzyme that expression can isomerized sugar also for example turns to six-membered ring structure such as D-glucose isomerase the enzyme of five-membered ring structure such as D-fructose.
Relevant carbohydrase comprises following material (being EC number in the parenthesis): α-Dian Fenmei (EC 3.2.1.1), beta-amylase (EC 3.2.1.2), dextran 1,4-alpha-glycosidase (EC 3.2.1.3), interior-1,4-beta-glucanase (cellulase, EC 3.2.1.4), interior-1,3 (4)-beta-glucanases (EC 3.2.1.6), interior-1,4-beta-xylanase (EC3.2.1.8), dextranase (EC 3.2.1.11), chitinase (EC 3.2.1.14), polygalacturonase (EC 3.2.1.15), N,O-Diacetylmuramidase (EC 3.2.1.17), beta-glycosidase (EC 3.2.1.21), alpha-galactosidase (EC3.2.1.22), beta-galactosidase enzymes (EC 3.2.1.23), amylo-1:4,1:6-transglucosidase, 6-Glycosylase (EC 3.2.1.33), xylan 1,4-xylobiase (EC 3.2.1.37), dextran interior-1,3-β-D-Glycosylase (EC 3.2.1.39), Schardinger dextrin interior-1,6-alpha-glycosidase (EC3.2.1.41), sucrose alpha-glycosidase (EC 3.2.1.48), dextran interior-1,3-alpha-glycosidase (EC 3.2.1.59), dextran 1,4-beta-glycosidase (EC 3.2.1.74), dextran interior-1,6-beta-glycosidase (EC 3.2.1.75), Galactanase (EC 3.2.1.89), in the arabinan-1,5-α-L-arabinose glycosides enzyme (EC 3.2.1.99), Sumylact L (EC 3.2.1.108), chitosanase (chitosanases) (EC 3.2.1.132), in-mannase (EC 3.2.1.78) and xylose isomerase (EC 5.3.1.5).
In a specific embodiments of the present invention, enzyme is a proteolytic enzyme.In a specific embodiments, enzyme is a bacteria protease.
The example of commercial available proteolytic enzyme (peptase) comprises Kannase TM, Everlase TM, Esperase TM, Alcalase TM, Alcalase Ultra TM, Neutrase TM, Durazym TM, Savinase TM, Savinase Ultra TM, Ovozyme TM, Pyrase TM, Pancreatic Trypsin NOVO (PTN), Bio-Feed TMPro and Clear-Lens TMPro (all can be from Novozymes A/S, Bagsvaerd, Denmark obtains).Other preferred proteolytic enzyme comprises those that describe among WO 01/58275 and the WO 01/58276.
Other commercial available proteolytic enzyme comprises: Ronozyme TMPro, Maxatase TM, Maxacal TM, Maxapem TM, Opticlean TM, Propease TM, Purafect TMAnd PurafectOx TM(can obtain) from Genencor International Inc., Gist-Brocades, BASF or DSMNutriti onal Products.
Commercial available lipase example comprises Lipex TM, Lipoprime TM, Lipopan TM, Lipolase TM, Lipolase TMUltra, Lipozyme TM, Palatase TM, Resinase TM, Novozym TM435 and Lecitase TM(all can obtain) from NovozymesA/S.
Other commercial available lipase comprises: Lumafast TM(from pseudomonas mendocina (Pseudomonas mendocina) lipase of GenencorInternational Inc.); Lipomax TM(from pseudomonas pseudoalcaligenes (Ps.Pseudoalcaligenes) lipase of Gist-Brocades/Genencor Int.Inc.); And from bacillus bacterial classification (Bacillussp.) lipase of Solvay enzymes.More lipase can obtain from other supplier.
The example of commercial available carbohydrase comprises Alpha-Gal TM, Bio-Feed TMAlpha, Bio-Feed TMBeta, Bio-Feed TMPlus, Bio-Feed TMWheat, Bio-Feed TMZ, Novozyme TM188, Carezyme TM, Celluclean TM, Celluclast TM, Cellusoft TM, Celluzyme TM, Ceremyl TM, Citrozym TM, Denimax TM, Dezyme TM, Dextrozyme TM, Duramyl TM, Energex TM, Finizym TM, Fungamyl TM, Gamanase TM, Glucanex TM, Lactozym TM, Liquezyme TM, Maltogenase TM, Natalase TM, Pentopan TM, Pectinex TM, Promozyme TM, Pulpzyme TM, Novamyl TM, Termamyl TM, AMG TM(Amyloglucosidase Novo), Maltogenase TM, Sweetzyme TMAnd Aquazym TM(all can obtain) from NovozymesA/S.More carbohydrase can obtain from other supplier, as Roxazyme TMAnd Ronozyme TMProduct line (DSM Nutritional Products), Avizyme TM, Porzyme TMAnd Grindazyme TMProduct line (Danisco, Finnfeeds), and Natugrain TM(BASF), Purastar TMAnd Purastar TMOxAm (Genencor).
Other commercial available enzyme comprises Mannaway TM, Pectaway TM, Stainzyme TMAnd Renozyme TM
In a specific embodiments of the present invention, described enzyme is a proteolytic enzyme.
Proteolytic enzyme: can use any proteolytic enzyme that is applicable to laundry bars.Suitable proteolytic enzyme comprises animal, plant or microbe-derived enzyme.Microbe-derived is preferred.The mutant that comprises chemistry or genetic modification.Can be serine protease, preferred alkaline microbial protease or trypsinase-sample proteolytic enzyme.The example of Sumizyme MP is a subtilisin, particularly is derived from BacillusEnzyme, as subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168 (in WO 89/06279 describe).
In a specific embodiments of the present invention, the enzyme that adds laundry bars is that the mixture of proteolytic enzyme is selected from down the enzyme of group with one or more: cellulase, lipase, amylase, pectate lyase and carbohydrase.
Can incorporate into enzyme in the particle or incorporate liquid preparation into.In a specific embodiments of the present invention, enzyme is added method of the present invention as particle.In another specific embodiments of the present invention, enzyme is added this method as liquid preparation.
Stablizer
Stablizer of the present invention is for making the stable stablizer of enzyme in storage process.In a specific embodiments of the present invention, stablizer is a proteinase inhibitor.
Suitable stabilizers comprises the boric acid or derivatives thereof.In a specific embodiments, stablizer is boric acid or borate (borate).The many examples that have the borate compound that is applicable to the application.Preferably water dissolubility borate compound such as boric acid, although other compound such as borax, boron oxide, hydroborate and other alkali metal borate such as ortho-boric acid sodium, sodium metaborate and sodium pyroborate (sodium ortho-, metaand pyroborates) also are suitable.Boric acid that replaces such as phenyl-boron dihydroxide, butane boric acid and bromophenyl boric acid also be can be used for the application.The mixture of top borate compound also is applicable to the application.
Suitable enzyme stabilizers can be at the phenyl-boron dihydroxide derivative that carbonyl replaced of contraposition with contiguous phenyl-boron dihydroxide.
Phenyl-boron dihydroxide derivative enzyme stabilizers has following formula:
Figure A20091012992900101
Wherein R is selected from down group: hydrogen, hydroxyl, C 1-C 6The C of alkyl, replacement 1-C 6Alkyl, C 1-C 6The C of alkenyl and replacement 1-C 6Alkenyl.
In a specific embodiments of the present invention, Preblend comprises enzyme and the disclosed phenyl-boron dihydroxide derivative of following formula enzyme stabilizers, and wherein R is C 1-C 6Alkyl, special, R is CH 3, CH 3CH 2, CH 3CH 2CH 2, perhaps wherein R is a hydrogen.In a specific embodiments of the present invention, phenyl-boron dihydroxide derivative enzyme stabilizers is 4-FPBA.
In a specific embodiments of the present invention, laundry bars only contains the phenyl-boron dihydroxide derivative as enzyme stabilizers.In a more particular embodiment of the present invention, laundry bars only contains 4-FPBA as enzyme stabilizers.
Stablizer can exist with 0.01% to 30% amount by the weight of total bar composition.In a more particular embodiment, stablizer can exist with 0.05% to 20% amount by the weight of total bar composition.
Laundry bars can comprise 0.1% to 10%w/w stablizer of final bar composition.In a specific embodiment, laundry bars comprises 0.5% to 5%w/w stablizer.In a more particular embodiment, laundry bars comprises 0.5% to 4%w/w stablizer.In a specific embodiments, laundry bars comprises the stablizer of 0.001%w/w at least.In a specific embodiments, laundry bars comprises the stablizer of about 4%w/w of final bar composition.
Polyvalent alcohol
Can be used for polyvalent alcohol of the present invention is characterised in that: solubleness in the water, and the carbon backbone chain length of C2-C6 and a plurality of hydroxyl, preferred per molecule contains 2-6 hydroxyl.
The polyvalent alcohol that can be used for the application includes but not limited to: 1, and 2-butyleneglycol, 3-chloro-1,2-propylene glycol, ethylene glycol, 1,2-hexylene glycol, glycerine, seminose, propylene glycol, Sorbitol Powder, sucrose and their mixture.The polyvalent alcohol level is generally 0.5%-10% by the weight of final bar composition, is preferably 1%-5%, more preferably 1.5%-3%.
PH controls compound
Found to reduce the stability that pH improves enzyme.The pH control agent can be any suitable compound that can control pH.
In a specific embodiment, the pH control agent is acid.
In a specific embodiment, pH control compound can be selected from down group: lipid acid, acetate, equisetic acid, hexanodioic acid, eicosanoic acid, arachidonic acid, aspartic acid docosoic, butyric acid, capric acid, caproic acid, cerinic acid, citric acid, formic acid, fumaric acid, L-glutamic acid, pentanedioic acid, R-Glyceric acid, the glycerate-3-phosphate ester, Glyoxylic acid hydrate, isocitric acid, α-Yang Daiwuersuan, lactic acid, lauric acid, linolic acid, linolenic acid, toxilic acid, oxysuccinic acid, propanedioic acid, tetradecanoic acid, oleic acid, oxalic acid, oxaloacetic acid, palmitinic acid, Zoomeric acid, phosphatidic acid, phosphoenolpyruvic acid, pimelic acid, propionic acid, pyruvic acid, stearic acid, succsinic acid, tartrate (Tartraic acid) and valeric acid.
The pH control agent will be by the weight of final bar composition usually with 0.05% to about 8%, and is preferred 0.1% to 6%, and more preferably 0.2% to about 4% level exists.In a specific embodiment, the amount of pH control agent be soap bar 0.001% to 5%w/w.In a more particular embodiment, the amount of pH control agent be soap bar 0.01% to 2%w/w.In specific embodiment, the amount of pH control agent be soap bar 0.05% to 1%w/w.In a specific embodiment, the amount of pH control agent is the about 0.2%w/w of final bar composition.
Moisture (moisture) content
Moisture can strengthen the mixing of Preblend composition.Moisture is also supplied with the acceptable feel of laundry bars (feel) and other physical property.Moisture, for example water can be added into Preblend and/or be added into Preblend as free water by being included in the composition.
Laundry bars comprises about 5% to about 30% by the weight of final bar, preferred about 10% to about 25% moisture.
The laundry bars composition
Laundry bars of the present invention comprises Preblend and soap.Laundry bars also can comprise complexing agent such as EDTA and EDHP, spices and/or various weighting agent (filler).
Additional compound
The laundry soap bar can comprise additional compound.Described compound is not limited to for example negatively charged ion synthetic surfactant of tensio-active agent, increase agent/washing assistant (builder) clearly, polymerization dirt releasing agent (polymeric soilrelease agent), detergent chelant (chelant), glycerine, stablizer, weighting agent, dyestuff, tinting material, dye transfer inhibitor, oxyalkylated polycarbonate, suds suppressor, construction agent (structurant), tackiness agent, flocculating aids/leaching agent (leaching agent), bleach-activating agent, clay remover (clay soilremoval agent), anti redeposition agent, polymeric dispersant, brightener (brightener), fabric softening agent, spices and/or other compound known in the art.
Soap (soap)
The soap that is fit to use according to the present invention comprises the water-soluble salt of higher fatty acid.Soap can make by fat and the direct saponification of oil or the neutralization of free fatty acids.Suitable soap is to comprise about 8-24 carbon atom, as 12 sodium salt, sylvite, ammonium salt and alkane ammonium salts (alkyloammonium salts) to the higher fatty acid of about 18 carbon atoms.In a specific embodiments, soap is selected from the sodium salt and the sylvite of the fatty acid mixt that is derived from Oleum Cocois and Tallow, beef (tallow), as Tallow, beef and palmitic sodium salt or sylvite.In addition, macadamia nut oil (nut oil) can add by final bar weight 5-30% as Oleum Cocois or palm-kernel oil.
Glycerine
In known soap manufacturing processed, glycerine or remove or stay in the soap because of business reason.Therefore soap can be described as high glycerin soap or low glycerin soap.Low glycerin soap comprises 0 to 2% glycerine, if need more poly-glycerine, guarantees suitable picked-up or adds to soap base (soap noodle) thereby it can add in the soap manufacturing processed when soap is still liquid.In a specific embodiment, the laundry soap bar comprises 1 to 6% glycerine.In a kind of more particular embodiment of the present invention, comprise 2% to 5% glycerine by the weight of total soap bar laundry soap bar.In a kind of specific embodiment, the laundry soap bar comprises about 4% glycerine.
Tensio-active agent
Be applicable to that synthetic anion surface active agent of the present invention comprises water-soluble salt, the an alkali metal salt of preferred organic reaction of Salmon-Saxl product, ammonium salt and alkane ammonium salt, described organosulfur reaction product have about 10 alkyl and sulfonic group or sulfate groups to about 20 carbon atoms in its molecular structure.The example of this class synthetic surfactant is sodium alkyl sulfate and alkylsurfuric acid potassium, particularly passes through higher alcohols (C 8-18Carbon atom), as those higher alcoholss that the reduction of the glyceryl ester of Tallow, beef or Oleum Cocois is produced in addition sulfation obtained those; And sodium and potassium alkylbenzene sulfonate, wherein alkyl comprises about 9 to about 15 carbon atoms, is in the straight or branched configuration.Valuable especially is linear straight chain alkylbenzene sulfonate (LAS), and wherein the mean number of alkyl carbon atoms is about 11-13, is abbreviated as C 11-13LAS.The preferably an alkali metal salt of these tensio-active agents, particularly sodium salt.
Other example that is applicable to the application's anion synthetic detergent is that (sodium alkyl glyceryl ether sulfonates AES), particularly is derived from the ethers of the higher alcohols of Tallow, beef and Oleum Cocois to the alkyl glycerylether sodium sulfonate; Coco-nut oil fatty acid coconut monoglyceride and coco-nut oil fatty acid direactive glyceride sodium sulfate (sodium coconut oil fatty acid monoglyceride sulfonates and sulfates); And alkyl epoxy ethane ether sodium sulfate salt or sylvite (sodium or potassium salts of alkyl ethyleneoxide ether sulfates), its per molecule contains about 1 oxyethane to about 10 units, and wherein alkyl contains and has an appointment 10 to about 20 carbon atoms.
In addition, suitable anion synthetic detergent also comprises the water-soluble salt of α-sulfonated fatty acid ester, and it comprises about 6 to about 20 carbon atoms in fatty acid group, and comprises about 1 to about 10 carbon atoms in ester group; The water-soluble salt of 2-acyloxy alkane-1-sulfonic acid (2-acyloxyalkane-1-sulfonic acid), it comprises about 2 to about 9 carbon atoms in acyl group, contain about 9 to about 23 carbon atoms in alkane (alkane) part; Comprise about 12 to the alkene of about 20 carbon atoms and the water-soluble salt of paraffin sulfonate; And β-alkyl oxy alkyl sulfonate (beta-alkyloxy alkane sulfonate), it contains in alkyl (alkyl) has an appointment 1 to about 3 carbon atoms, and contains about 8 to about 20 carbon atoms in alkane (alkane) part.
The example of preferred anionic surfactants synthetic surfactant is C 10-18Alkyl-sulphate (AS), C 10-18Linear alkyl benzene sulfonate (LAS), C 10-14Alkyl glyceryl ether sulfonate (AES), and their mixture.
The example that is included in the component of conventional laundry bars (synthetic detergent bar) is: linear alkyl benzene sulfonate, coco fatty alcohol sulfate (coco fatty alcohol sulphate), SODA ASH LIGHT 99.2, sulfuric acid, tripoly phosphate sodium STPP, lime carbonate, coconut oil fat alcohol, TiO 2, cellulase, diethylenetriamine (methylene phosphonic acid), coconut monoethanol amide, fluorescent agent (fluorcent agents), the methylcellulose gum, spices, the moisture that replace.
The example that is included in the detergent component of conventional laundry bars (compound) is: LAS, soap, cellulase, proteolytic enzyme, boric acid, borax, sodium formiate, Trisodium Citrate, yellow soda ash, glycerine, propylene glycol, ethylene glycol, MgSO 4, SODA ASH LIGHT 99.2, STPP, talcum, moisture.
The preparation of laundry bars
Laundry bars of the present invention can be processed in the laundry bars producing apparatus of routine, and the laundry bars producing apparatus of described routine is such as, but not limited to mixing machine, moulding press (plodder) (for example two stage vacuum mold press), forcing machine, cutting machine, sign stamping press (logo-stamper), cooling duct (cooling tunnel) and wrapping machine.
Preparation Preblend earlier adds to it in soap again.
According to the present invention, described method is the method for incorporating enzyme into the laundry soap bar and also keeping enzymic activity.
The inventive method is used for preparation laundry soap bar, and it comprises the following steps:
A) prepare Preblend by enzyme, stablizer and the polyvalent alcohol that mixes as liquid preparation;
B) Preblend of step a) is mixed with soap;
C) with b) mixture be refined into refining soap; And
D) the refining soap of mold pressing step c).
Can Preblend of the present invention be added in the soap in the different steps of this process.In a specific embodiment of the present invention, before purification step, Preblend is added in the soap.
In a specific embodiment of the present invention, also be included in and add the pH control agent in the step a).
The mixing of Preblend, step a) can be carried out in mixing machine (for example at Double Sigma AmalgatorMSA-100 type mixing machine).Mixing step a) last preferably be no more than 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 45 minutes, be no more than 1 hour.
After preparation Preblend, its storage can be used to produce laundry bars until it, perhaps it can be used to produce laundry bars immediately.After preparation Preblend, it is added in the soap by metering.In a specific embodiment, Preblend is mixed with soap in purification step, thereby guaranteeing that Preblend suitably sneaks into soap.Purification step can be undertaken by online (in-line) refiner or the moulding press that screen cloth is installed at head (head), is perhaps undertaken by making with extra care in final moulding press.
In moulding press (for example duplex-mold press (Duplex plodder)), carry out the mold pressing step.Preferably, moulding press is operated under high vacuum, thereby removes inside (entrapped) air.
Extruded product will be extruded bar subsequently and deliver to cutting machine, and bar is cut into required bar length herein.Randomly, these sticks are embossed into net shape in stamping press (stamping press).The high speed stamping press is generally used for the high-volume production line.Preferred high speed press has cooling die.Laundry bars can be cooled off, as cooling off in cooling duct, its follow-up conventional steps is packing, cases and send to storage then.
Additional compound can be added in the mixture that comprises soap and Preblend.These compounds include but not limited to brightener, tinting material, construction agent, tackiness agent, photosensitive bleaching agent (photoactive bleach), dirt release polymer (soil release polymer) and anti-redeposition agent.
The application of laundry bars
Laundry bars of the present invention is used for hand-wash laundry or is used for washing bowl dish.
Further describe the present invention by following examples, described embodiment should not regard limitation of the scope of the invention as.
Embodiment
Embodiment 1
Present embodiment shows makes the ordinary method that contains the enzyme soap bar, wherein various compositions is added in the soap respectively.
Each stabilizing component is added in the soap respectively.
Tested three kinds of different proteolytic enzyme:
EVERLASE 16L by final laundry bars weight 0.2%;
SAVINASE 16L by final laundry bars weight 0.2%;
SAVINASE ULTRA 16L by final laundry bars weight 0.2%.
Add in the soap these proteolytic enzyme and mixing in room temperature (RT).Add to the citric acid of 2% glycerine and 0.2% in the soap respectively in addition and mix.
Sodium Tetraborate with 2% adds in the mixture that comprises Everlase 16L and Savinase 16L.
This mixture is transferred to refiner, is transferred to moulding press afterwards, at last it is impressed.
Stability result is shown as at 35 ℃ and stores the residual enzyme activity that 2,4,6 or 8 all backs are represented with percentage ratio.
Figure A20091012992900151
If loss of activity does not take place, so theoretical residual activity (100%) should be as shown in the table because of the water loss of soap in the storage process.
Figure A20091012992900161
Soap is stored in unlimited climatic chamber (climate chamber) and always causes water to evaporate from soap bar, causes weight loss.
Embodiment 2
In the present embodiment, stablizer is added in the Preblend, Preblend is mixed with soap, do not make with extra care.
The component of Preblend is:
EVERLASE?16L?0.2%,
Glycerine 2%,
Borax 2%,
Citric acid 0.2%.
Composition blend in mixing machine of Preblend is directly added in the soap then to make slurry.This mixture is directly delivered to moulding press, impress product thereafter.
Figure A20091012992900162
These results show that package stability is high surprisingly.
Embodiment 3
Stablizer is added in the Preblend, add to then and be refined into thin soap base (thin noodle) in the soap simultaneously, deliver to moulding press again and be used for final soap and extrude.Then it is impressed.
The component of Preblend is:
EVERLASE?16L?0.2%,
Glycerine 2%,
Borax 2%,
Citric acid 0.2%.
Because water loses from soap, once more result and obtainable theoretical maximum activity is compared.
Figure A20091012992900171
High-storage stability is maintained.
Embodiment 4
Prepared the Preblend that comprises stablizer.Component is:
EVERLASE?16L?0.2%,
Glycerine 2%,
Borax 2%,
EDHP 0.05% and EDTA 0.05%,
Citric acid 0.2%.
Preblend added to be refined into thin soap base in the soap simultaneously, add to then and be used for final soap in the moulding press and extrude.Add complexing agent EDHP and EDTA for the purpose of oxidation protection herein.
Because water loses from soap, once more result and obtainable theoretical maximum activity is compared.
Figure A20091012992900172
Complexing agent has original negative effect (titration activity) to package stability, yet package stability keeps constant in whole period.
Embodiment 5
Prepare Preblend by mixing following ingredients:
EVERLASE?16L?0.2%,
Glycerine 2%,
Borax 2%,
Citric acid 0.2%.
In two-step approach, Preblend is added to the part of cracked soap base.This mixture is added in the mixing machine, again mold pressing and impression.We are expected at the absorption that can take place in the production-scale processing the soap material.In order to improve described absorption, in one of mold pressing step, increase to make with extra care and extrude at last then, perhaps mix mold pressing then (depending on production line).
Because water loses from soap, once more result and obtainable theoretical maximum activity is compared.
Figure A20091012992900181
Ideally mate with theoretical 100% level of stability again.
Embodiment 6
Stablizer is added in the Preblend, add to then and be refined into thin soap base in the soap simultaneously, deliver to moulding press again and be used for final soap and extrude and impress.
Each component is:
EVERLASE?16L?0.2%,
Glycerine 2%,
Boric acid 2%.
Because water loses from soap, once more result and obtainable theoretical maximum activity is compared.
Figure A20091012992900182
Embodiment 7
The component of Preblend is
EVERLASE?16L?0.2%,
Glycerine 2%,
Boric acid 1.3%,
Borax 0.7%.
By being mixed with Preblend, it is added to be refined into thin soap base in the soap simultaneously then, again this mixture is added to final soap and extrude.
Because water loses from soap, once more result and obtainable theoretical maximum activity is compared.
Figure A20091012992900183
This combination also provides extraordinary stability.

Claims (16)

1. a method for preparing the soap bar of doing washing comprises the following steps:
A) prepare Preblend by enzyme, stablizer and the polyvalent alcohol that mixes as liquid preparation;
B) Preblend of step a) is mixed with soap;
C) with b) mixture be refined into refining soap; And
D) the refining soap of mold pressing step c).
2. the method for claim 1 also is included in and adds the pH control agent in the step a).
3. claim 1 or 2 method also are included in and add water in the step a).
4. each method among the claim 1-3, wherein said pH control agent are acid.
5. each method among the claim 1-4, the enzyme in the wherein said mixture is a proteolytic enzyme.
6. the method for claim 5, wherein said mixture also comprise the enzyme that is selected from down group: cellulase, lipase, amylase, pectate lyase and carbohydrase.
7. each method among the claim 1-6, wherein said stablizer is borate, boric acid or boric acid derivatives.
8. each method among the claim 1-7, wherein said stablizer is for phenyl-boron dihydroxide derivative, especially the 4-formyl radical-phenyl-boron dihydroxide of carbonyl at para-orientation.
9. each method among the claim 1-8, wherein said polyvalent alcohol is a glycerine.
10. can be by the laundry bars of each method acquisition among the claim 1-9.
11. be used for the Preblend in each the method for claim 1-9, it comprises enzyme, stablizer, pH control agent and polyvalent alcohol.
12. the Preblend of claim 11, wherein said stablizer are borate, boric acid or boric acid derivatives.
13. the Preblend of claim 11 or 12, wherein said enzyme are proteolytic enzyme.
14. the Preblend of claim 13, wherein this Preblend comprises that also one or more are selected from down the enzyme of group: cellulase, lipase, amylase, pectate lyase and carbohydrase.
15. the Preblend of claim 11 to 14, wherein said polyvalent alcohol are glycerine.
16. the laundry bars of claim 10 is used for the purposes of hand-wash laundry.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102549136A (en) * 2009-09-25 2012-07-04 诺维信公司 Detergent composition
CN103242989A (en) * 2013-05-02 2013-08-14 广州立白企业集团有限公司 High-stability system enzymatic laundry soap composition and production method thereof

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DE3918761C1 (en) * 1989-06-08 1990-06-28 Henkel Kgaa, 4000 Duesseldorf, De
JPH0775620B2 (en) * 1991-04-08 1995-08-16 トーメー産業株式会社 Liquid formulation for hydrous contact lens and method for washing hydrous contact lens
DE69621131T2 (en) * 1995-06-13 2002-11-28 Novozymes A/S, Bagsvaerd 4-SUBSTITUTED-PHENYLBORONIC ACIDS AS ENZYME STABILIZERS

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102549136A (en) * 2009-09-25 2012-07-04 诺维信公司 Detergent composition
CN103242989A (en) * 2013-05-02 2013-08-14 广州立白企业集团有限公司 High-stability system enzymatic laundry soap composition and production method thereof
CN103242989B (en) * 2013-05-02 2016-03-30 广州立白企业集团有限公司 A kind of High-stability system enzymatic laundry soap composition and production method thereof

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