CN1330707A - Detergent composition - Google Patents
Detergent composition Download PDFInfo
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- CN1330707A CN1330707A CN99814555.6A CN99814555A CN1330707A CN 1330707 A CN1330707 A CN 1330707A CN 99814555 A CN99814555 A CN 99814555A CN 1330707 A CN1330707 A CN 1330707A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Abstract
A transparent liquid detergent comprising an encapsulated enzyme, enclosed within a translucent/transparent container.
Description
Invention field
The present invention relates to the liquid washing agent field, particularly Bao Zhuan transparent liquid detergent composition.
Background of invention
Transparent liquid detergent composition is known in the art.GB-A1,303,810 disclose a kind of clarifying liquid detergent composition, and said composition has transparent moisture or non-water base material, and this base-material comprises with eyesight and seems very clearly particulate, and this diameter of expecting slightly is at least 0.5mm.US-A-3,812,042 have described a kind of clarifying liquid detergent composition in transparent plastic containers.US-A-5,427,708 have described a kind of transparent liquid soap in transparent vessel.W0 97/26315 (Colgate) has described a kind of transparent vessel with the specific colourity that limits by x and y value.Particular dye is used for liquid to mate with container.These reference capsular enzyme of all unexposed bag or with respect to not wrapping capsular enzyme, its validity in transparent vessel and liquid.
When transparent liquid washing agent was packaged in the transparent vessel, the susceptibility composition in detergent composition may be influenced by the UV radiating.For example, the UV radiation may cause the variable color of liquid detergent composition in transparent vessel.DE-A-2034562 and DE-A2034563 have described and have used the nitro alkanol to overcome the bleaching problem of colored liquid detergent composition.
Because of improving clean-up performance, the preferred liquid detergent composition that comprises enzyme that uses.Have found that when transparent liquid was packaged in the transparent vessel, the activity of enzyme also can be subjected to the effect of UV radiating and variation.
Therefore, the purpose of this invention is to provide a kind of detergent composition through packing that comprises transparent vessel and transparent enzyme aqueous liquid detergent compositions, wherein, enzyme is protected avoids UV radiating harmful effect.Be surprisingly found out that, when enzyme when transparent container is in the transparent liquid washing agent, can reduce the harmful effect of UV radiation by this kind of enzyme being made capsule to enzyme.
Summary of the invention
The invention provides a kind of detergent composition and a kind of transparent enzyme-containing detergent compositions that comprises in the transparent container, it is characterized in that described enzyme incapsulates.
The preferred embodiments of the invention provide a kind of liquid detergent composition of packing, it comprises transparent container and transparent enzyme-containing detergent compositions, wherein, enzyme is loaded into glue skirt, wherein, in transparent container (as polyethylene), the liquid washing agent that comprises the capsular 20g of 1.5wt% enzyme quickened storage after 7 days, wherein, sample is exposed to UV light (as UV-B light) simultaneously 37 ℃ of storages down, thereby liquid sample be positioned at from the bottom of the bottle to the position of the about 20cm distance of UV light source, enzymic activity is enhanced (as surpassing 40% than former increased activity, preferably surpass 50%, more preferably surpass 60%).
Another embodiment of the invention provides a kind of packed liq detergent composition, and it comprises transparent/translucent container and transparent/translucent enzyme-containing detergent compositions, wherein, enzyme is loaded in the capsule, wherein, liquid washing agent is the washing composition that structure is arranged, preferred external structure washing composition.Detailed Description Of The Invention
The invention provides a kind of detergent composition that comprises transparent or semitransparent container and transparent or semitransparent enzyme aqueous detergent compositions, it is characterized in that described enzyme is loaded into capsule and protective enzyme is avoided UV radiating harmful effect through packing.Preferably, after 4 weeks of storage under 37 ℃, the enzyme in described packed detergent composition has the protoenzyme activity above 40%, more preferably surpasses 50%, and is first-selected above 60%.Container
In the spectrographic visible-range (approximately 410-800 nanometer), transparent vessel of the present invention preferably its transmittance surpasses 25%, more preferably surpasses 30%, and is also preferred above 40%, preferably surpasses 50%.
When low-down uv b radiation passed through the transparence of wall of container, the enzyme deactivation that causes owing to the UV-damage may take place.
Perhaps, transparency may be defined as absorbancy and is lower than 0.6, or transmittance is greater than 25%, and wherein, the % transmittance equals:
(1/10
Absorbancy) * 100%
For the purposes of this invention, if its wavelength in visible-range have surpass 25% transmission this, then it can regard transparent/translucent as.
Transparent vessel of the present invention comprises (high-density) polyethylene (PE), polypropylene (PP), polycarbonate (PC) and/or Polyethylene Terephthalates (PETE), but also is not limited to this.
Polythene container is used for UV stability experiment of the present invention, and its transparence under 310nm is 8%, is 17.5% under 400nm, is 25% under 500nm and is 31% under 600nm.
Container of the present invention can be and is applicable to that storage and packed liq are with any form or the size of family expenses.For example, container can be any size, but the maximum capacity of container is 0.05-15L usually, preferred 0.1-5L, more preferably 0.2-2.5L.Preferably, container suits from being easy to handle.For example, container can have a handle or part, and its size should make and be easy to one portable or carry.
Container preferably has and is applicable to the parts that liquid detergent composition is poured into, and again with the parts of container closure.Pour parts into and can have virtually any size or form, but preferably it is enough wide with the convenient liquid detergent composition that quantitatively adds.Packaged unit can have any form or size, but it is spiral or is stuck on the container with closed container usually.Packaged unit can have a lid, and it can unload from container.Perhaps, but described lid angle link to each other with container, no matter container is opened or is sealed.Packaged unit also can with being integral of container.
Container can have the suitable form that is used to recharge.For example, container can comprise the perforate of a Reclosable, and its size and position are applicable to easily it and recharge.Therefore, container of the present invention also comprises and recharges packing: these vessel forms are applicable to that the packing of liquid detergent composition recharges.These recharge packing can have any form and size, but generally will be flexible materials, does not have the parts that are used for sealing again, as pouch or Tetrapak
TMThe class container.Liquid washing agent
Liquid washing agent of the present invention can be moisture or water-free liquid washing agent.Liquid, aqueous inner structure or the outer structureization of can be.Preferred liquid washing agent of the present invention is an outer structureization.
Outer structure liquid can comprise polymkeric substance, as colloidal state colloid (gellan), xanthan gum, polyacrylic ester, phycocolloid, guar gum, rhamsan, carrageenin, carbopol
TMWith carbopol base polymer and its mixture.Preferably, the liquid of outer structureization can comprise the polymkeric substance that is selected from colloidal state colloid, kappa carrageen glue, xanthan gum or its mixture.Outer structure liquid also can comprise clay, silicate or its mixture as structurizing reagent.
Composition of the present invention under the preferred 570-690nm, adopts its optical transmittance of cuvette of 1 centimetre to be at least 50% at wavelength 410-800nm, and wherein, composition is substantially free of dyestuff.
Perhaps, the transparency of composition can be lower than 0.3 tolerance at visible wavelength (about 410-800nm) internal absorbance, and it is equivalent to the transmittance that adopts above-mentioned cuvette and wavelength at least 50%.Therefore, in the present invention, as long as in the visible wavelength range internal transmittance greater than 50%, think that then it is a transparent/translucent.
Transparent liquid detergent of the present invention is meant, under 410-800nm, the absorbancy of liquid washing agent is less than 0.3, or its transmittance is greater than 50%, and wherein, transmittance equals:
(1/10
Absorbancy) * 100%
Under the very low transmission of uv b radiation, the enzyme deactivation that the UV-infringement causes can take place.Detergent active material
Composition of the present invention contains one or more tensio-active agents, and it is selected from anion surfactant, nonionogenic tenside, cats product, amphoterics and zwitterionics or its mixture.The surfactant detergent that is preferred among the present invention is the mixture of anion surfactant and nonionogenic tenside, certainly, be appreciated that any tensio-active agent all can use separately or be used in combination with any other one or more tensio-active agents.The anion surfactant washing composition
The anion surfactant that can be used among the present invention is that those comprise the long chain hydrocarbon hydrophobic grouping in its molecular structure and hydrophilic radical is the surface active cpd of water soluble group such as carboxylate salt, sulfonate or vitriol or its corresponding sour form.Anion surfactant comprises the water-soluble senior alkyl arylsulphonate of basic metal (for example sodium and potassium), alkylsulfonate, alkyl-sulphate and alkyl, polyether vitriol.They also can comprise lipid acid or fatty acid soaps.One group of basic metal, ammonium or alkanol amine salt and senior alkyl vitriolic basic metal, ammonium or alkanol amine salt that the preferred anionic surfactants tensio-active agent is the senior alkyl aryl sulfonic acid.Preferred higher alkyl sulfates comprises 8-26 carbon atom for alkyl wherein, preferably 10-22 carbon atom, more preferably those of 12-18 carbon atom.Alkyl in alkylaryl sulphonate preferably comprises 8-16 carbon atom, more preferably 10-15 carbon atom.Particularly preferred alkylaryl sulphonate is C
10-C
16The sodium of Phenylsulfonic acid, potassium or ethanolamine salt, for example, linear alkyl benzene sulphonate.The primary and secondary alkyl-sulphate can make as the sodium bisulfite reaction response by making long-chain alpha-olefin and sulphite or hydrosulphite.As US patent 2,503,280,2,507,088,3,372,188 and 3,260,741 is described, and alkyl-sulphate also can be made by the conventional paraffinic hydrocarbons of long-chain and sulfurous gas and oxygen reaction, obtains to be applicable to uncle or secondary higher alkyl sulfates as surfactant detergent.
Alkyl substituent is preferably the straight chain substituting group, i.e. straight chained alkyl, and, also can adopt branched-chain alkyl sulfonate, although they are not good aspect biological degradation.Alkane is that alkyl substituent can be sulfonated endways or can for example be connected on the 2-carbon atom of chain, promptly can be secondary sulfonate.This area is appreciated that substituting group can be connected on any carbon atom of alkyl chain.Senior alkyl sulfonate can be used as an alkali metal salt, for example sodium and sylvite.Preferred salt is sodium salt.Preferred alkylsulfonate is C
10-C
18Uncle's straight chained alkyl sodium sulfonate and potassium, more preferably C
10-C
15Uncle's linear alkyl benzene sulphonic acid.
Can use the mixture of senior alkyl benzene sulfonate and higher alkyl sulfates and the mixture of senior alkyl benzene sulfonate and senior alkyl polyether thiourea hydrochlorate.
The consumption of alkyl aryl sulphonic acid basic metal or ethanolamine salt can be 0-70wt%, preferred 2-50wt%, more preferably 5-20wt%.An alkali metal salt of alkylsurfuric acid or ethanolamine salt can mix use with alkylbenzene sulfonate, and consumption is 0-70wt%, preferred 5-50wt%, more preferably 5-20wt%.
Equally, straight chained alkyl and branched-chain alkyl vitriol (as primary alkyl sulphates) can be used as anionic group.
The senior alkyl polyethoxye vitriol that is used for the present invention can be the straight or branched alkyl and comprises the lower alkoxy that can contain 2 or 3 carbon atoms.Straight chain senior alkyl polyether thiourea hydrochlorate is preferred, and because of it has higher biodegradability than branched-chain alkyl, rudimentary poly-alkoxy base is preferably oxyethyl group.
The many ethoxy sulfates of preferred senior alkyl that are used for the present invention are expressed from the next:
R
1-O(CH
2CH
2O)
p-SO
3M，
Wherein, R
1Be C
8-C
20Alkyl, preferred C
10-C
18, more preferably C
12-C
15P is 2-8, preferred 2-6, more preferably 2-4.M is a basic metal, as sodium and potassium, or ammonium cation.Preferred sodium and sylvite.
The many ethoxylated sulfates of a kind of preferred senior alkyl are the triethoxy C with following formula
12-C
15The alcohol sodium sulfate salt:
C
12-15-O-(CH
2CH
2O)
3-SO
3Na
The example that can be used for the suitable alkyl ethoxy sulfate among the present invention is C
12-
15Straight chain or primary alkyl triethoxy sodium sulfate; Positive decyl diethoxy sodium sulfate; C
12Primary alkyl diethoxy ammonium sulfate; C
12Primary alkyl triethoxy sodium sulfate; C
15Primary alkyl tetraethoxy sodium sulfate; Blended C
14-15Mixing three of linear primary alkyl and tetraethoxy sodium sulfate; Stearyl five oxyethyl group sodium sulfate; With blended C
10-C18Linear primary alkyl triethoxy vitriolate of tartar.
The straight chained alkyl ethoxy sulfate is easy to carry out biology to be reduced, thereby is preferred.Many lower alkoxies of alkyl vitriol can be mutual mixture and/or use with the mixture of above-mentioned senior alkyl benzene sulfonate or alkyl-sulphate.
The many ethoxy sulfates of basic metal senior alkyl can use with alkylbenzene sulfonate and/or alkyl-sulphate, and its consumption is 0-70wt%, preferred 5-50wt%, and more preferably 5-20wt% is with whole composition weight meter.Nonionogenic tenside
According to the present invention, the part of surfactant composition can be a nonionogenic tenside.Usually, no matter whether nonionogenic tenside is sugar surfactant, its content should be about 10-100wt%, and preferred 20-50wt% is in the total surfactant composition.
Be applicable to that sugar of the present invention or polyglycoside surfactant promoting agent are included in those described in the following patent: US 5,573,707 (Cole etc.), US 5,562,848 (Wofford etc.), US5,542,950 (Cole etc.), WO 96/15305 (Cole etc.), US 5,529,122 (Thach), WO 95/33036 (Urfer etc.) and DE 4,234,241 (Schmidt).These reference all are incorporated herein by reference.
Adoptable ionic surfactant pack is drawn together polyhydroxy amides, as US 5,312, and the described and two alditol acid amides of 954 (Letton etc.), as US 5,389,279 (Au etc.) are described, and these two pieces of reference all are incorporated herein by reference.
The another kind of tensio-active agent based on sugar that can adopt comprises N-alkoxyl group or N-aryloxy polyhydroxy fatty acid amide, and as WO 95/07256 (Schiebel etc.), WO 92/06071 (Connor etc.) and WO 92/06160 (Collins etc.) are described.These reference all are incorporated herein by reference.
Also having a class is sugar ester based on the tensio-active agent of sugar, as described in following document: GB2,061,313, GB 2,048,670, EP 20122 and US 4,259,202 (Tanaka etc.), these reference all are incorporated herein by reference.
Except that sugar surfactant, other nonionogenic tenside is as described below:
Just as known in the art, nonionogenic tenside is characterised in that and has hydrophobic group and organic hydrophilicity group, and it is normally undertaken by organic aliphatic series or alkyl aromatic hydrophobic compound and oxyethane (being hydrophilic in nature), and condensation produces.Typical suitable nonionic surfactants be following document described those: US 4,316,812 and 3,630,929.
Usually, nonionogenic tenside is the lipophile of poly-alkoxylation, and wherein, required hydrophilic-lipophilic balance partly obtains by the many lower alkoxies of wetting ability are added to lipotropy.Preferred nonionic is oxyalkylated alkanol, and wherein, alkanol has 9-18 carbon atom, and wherein, the mole number of (2 or 3 carbon atoms) alkylidene oxide is 3-12.In this material, what preferably adopt is following alkanol, and it is the Fatty Alcohol(C12-C14 and C12-C18) of 9-11 or 12-15 carbon atom, and every mole comprises 5-8 or 5-9 alkoxyl group.
This examples for compounds is following those: wherein, alkanol has 10-15 carbon atom, and every mole comprises about 5-9 oxidation ethylidene, for example Neodol 25-9 and Neodol 23-6.5, and they are Shell Chemical Company, Inc.The product of producing.The former is the mixture of high fatty alcohol of average about 12-15 carbon atom and the condensation product of about 9 moles oxyethane, and the latter is a corresponding mixture, wherein, the carbonatoms of high fatty alcohol is 12-13, and the average quantity of oxidation ethylidene group is about 6.5.Higher alcohols is a primary alkanol.
Another kind of adoptable oxyalkylated tensio-active agent subclass comprises accurate alkyl chain length, but not the alkyl chain of aforesaid alkoxy-based surface-active agent distributes.Typically, this is meant the alcoxylates of close limit.The example of these tensio-active agents comprises Neodol-1
(R)Series of surfactants is produced by Shell Chemical Company.
Other useful nonionogenic tenside is the commercially available known nonionogenic tenside from BASF trade name Plurafac.Plurafacs is the reaction product between senior straight chain alcohol and oxyethane and propylene oxide mixture, and it comprises the combination chain of oxidation ethylidene and oxypropylene, and end envelope group is a hydroxyl.Its specific examples comprises the C of fused 6 moles of ethylene oxide and 3 moles of propylene oxide
13-C
15Fatty Alcohol(C12-C14 and C12-C18) condenses the C of 4 moles of ethylene oxide and 7 moles of propylene oxide
13-C
15Fatty Alcohol(C12-C14 and C12-C18) condenses the C of 10 moles of ethylene oxide and 5 moles of propylene oxide
13-C
15Fatty Alcohol(C12-C14 and C12-C18), or above-mentioned any mixture.
Another kind of liquid nonionic surfactants is for being purchased the ChemicalCompany from Shell, the trade name Dobanol of Inc. or Neodol series: Dobanol 91-5 is on average having the C of the ethoxylation of 5 moles of ethylene oxide
9-C
11Fatty Alcohol(C12-C14 and C12-C18), Dobanol25-7 are the C that every mole of Fatty Alcohol(C12-C14 and C12-C18) on average has the ethoxylation of 7 moles of ethylene oxide
12-C
15Fatty Alcohol(C12-C14 and C12-C18).
In composition of the present invention, preferred nonionic comprises the C that has at the narrow relatively oxidation ethylidene content of about 6-9 mole
12-C
15Uncle's Fatty Alcohol(C12-C14 and C12-C18) and with the C of the oxyethane ethoxylation of about 5-6 mole
9-C
11Fatty Alcohol(C12-C14 and C12-C18).Cats product
Many cats products are known in the art, and almost any cats product that has at least about the long chain alkyl group of 10-24 carbon atom all is applicable to the present invention.This compound is stated in following document: " cats product ", Jungermann, 1970, the document is incorporated herein by reference.It is described specifically to can be used among the present invention cats product such as the US 4,497,718 as tensio-active agent, and the document is incorporated herein by reference.
With regard to nonionic and anion surfactant, composition of the present invention can adopt separately cats product or with other tensio-active agent commonly known in the art in any is used in combination.Certainly, composition of the present invention can not contain cats product fully.
If adopt, the content of cats product is 0-20%, and preferred 1-10% is in composition total weight.Amphoterics
The both sexes synthetic surfactant broadly is described as the aliphatic derivatives of the heterocycle second month in a season and tertiary amine, wherein, aliphatic group is a straight or branched, wherein, one of aliphatic series substituting group comprises about 8-18 carbon atom, and one of them comprises the anionic water-soluble group at least, as carboxylate radical, sulfonate radical, sulfate radical.The examples for compounds that meets this definition is 3-(lauryl amino) Sodium Propionate, 3-(lauryl amino) propane-1-sodium sulfonate, 2-(lauryl amino) sodium ethyl sulfate, 2-(dimethylamino) octadecanoic acid sodium, 3-(N-carboxymethyl lauryl amino) propane 1-disodium sulfonate, octadecyl-imino-(immino) oxalic acid disodium, 1-carboxymethyl-2-undecyl imidazole sodium and N, N-two (2-hydroxyethyl)-2-sulfato-3-dodecyloxy propyl group amine sodium.Preferred 3-(lauryl amino) propane-1-sodium sulfonate.
Zwitterionics broadly is described as the derivative of secondary and tertiary amine, the derivative of the heterocycle second month in a season and tertiary amine, the perhaps derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Positively charged ion in quaternary compound can be a heterocyclic part.In all these compounds, should there be an aliphatic group at least, it is a straight or branched, comprise about 3-18 carbon atom, also comprise an aliphatic substituting group at least, it comprises the anionic water-soluble group, as carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical.
The specific examples of spendable zwitterionics is at US 4,062, provides in 647, and the document is incorporated herein by reference.
The amount of the active substance that is adopted can be 10-85wt%, preferred 15-75wt%, more preferably 20-70wt%.
Preferred surfactants system of the present invention comprises straight-chain alkyl sulfate, LES, nonionogenic tenside and soap class (monoethanolamine-soap, Na-soap) optionally.Washing assistant/ionogen
The washing assistant that can be used among the present invention comprises conventional inorganic or organic alkaline washing washing assistant, and its consumption should be roughly the 0-20.0wt% of composition weight, the preferred about 10.0wt% of 1.0-, more preferably 2-5wt%.
Ionogen can adopt makes any water-soluble salt.Ionogen also can be washing auxiliary detergent, and as the inorganic builders tripoly phosphate sodium STPP, perhaps it also can be the non-functional ionogen, as sodium sulfate or sodium-chlor.Preferred inorganic builders comprises all or part of ionogen.Be that the term ionogen has comprised washing assistant and salt.
The example of adoptable suitable inorganic alkaline washing auxiliary detergent is water-soluble alkali phosphoric acid salt, polyphosphate, borate, silicate and carbonate.The specific examples of these salt is triphosphoric acid, tetra-sodium, ortho-phosphoric acid, pregnancy sodium and the sylvite for phosphoric acid, tetraboric acid, silicic acid and carbonic acid.
The example of suitable organic basic washing auxiliary detergent salt is: (1) water soluble amino multi-carboxylate, as sodium ethylene diamine tetracetate and potassium, sodium nitrilo triacetate and potassium and N-(2-hydroxyethyl)-nitrilo sodium diacelate and potassium; (2) water-soluble salt of phytinic acid is as sodium phytate and potassium (referring to US 2,379,942); (3) water-soluble polyphosphonic acid salt specifically comprises ethane-1-hydroxyl-1, the sodium of 1-di 2 ethylhexyl phosphonic acid, potassium and lithium salts; The sodium of methylenediphosphonate (MDP), potassium and lithium salts; The sodium of ethylidene diphosphonic acid, potassium and lithium salts; And ethane-1,1, the sodium of 2-tri methylene phosphonic acid, potassium and lithium salts.Other example comprises: ethane-2-carboxyl-1,1-di 2 ethylhexyl phosphonic acid hydroxyl methanebisphosphonic acid, hydroxyl methanebisphosphonic acid, carboxyl di 2 ethylhexyl phosphonic acid, ethane-1-hydroxyl-1,1,2-tri methylene phosphonic acid, ethane-2-hydroxyl-1,1,2-tri methylene phosphonic acid, propane-1,1,3,3-tetra methylene phosphonic acid, propane-1,1,2,3-tetra methylene phosphonic acid and propane-1,2,2, an alkali metal salt of 3-tetra methylene phosphonic acid; (4) water-soluble salt of many carboxylate polymers and multipolymer, as US 3,308,067 is described.
In addition, the multi-carboxy acid salt washing agent can use satisfactorily, comprises the water-soluble salt of mellic acid, citric acid and carboxymethyl oxygen base succsinic acid, the salt of the polymkeric substance of methylene-succinic acid and toxilic acid, tartrate monosuccinic acid salt, tartrate disuccinate and its mixture (TMS/TDS).
Can adopt some zeolite or silico-aluminate.A kind of this type of silico-aluminate is at GB1, detailed description arranged in 470,250.
It is crystalline that another kind is used for water-insoluble synthetic aluminosilicate ion exchange material of the present invention, at GB 1,429, detailed description is arranged in 143.Particularly preferred washing assistant comprises Trisodium Citrate and sodium tetraborate pentahydrate.Enzyme
Below describe one or more enzymes that can be used in the composition of the present invention in detail.
If use lipase, this lipolytic enzyme can be the fungi lipase that can be produced by Humicola lanuginosa and Thermomyces lanuginosus, or the antibody of the lipase that the mutation lipolyticum NRRL B-3673 by microorganism thickness look bacillus is produced shows the bacterium lipase of positive immunology cross reaction.This microorganism is recorded in the dutch patent specification 154 of Toyo Jozo KabushikiKaisha, in 269, and be deposited in (the FermentationResearch Institute of fermentation research institute of Tokyo Ministry of International Trade and Industry industrial science and technology administration, Agency of Industrial Science andTechnology, Ministry of International Trade and Industry, Tokyo, Japan), permanent preserving number is KO Hatsu Ken Kin Ki 137, the public can be from the USDA of Illinoi State, The United States Peoria, farming research department, the northern application and development place (United States Department of Agriculture, Agricultural Research Service, Northern Utilization andDevelopment Division at Peoria, Illinois USA) obtains, and preserving number is NRRL B-3673.Lipase by this microorganisms can buy hereinafter referred to as " TJ lipase " from Toyo JozoCo. (Tagata, Japan).Adopt the described standard of Ouchterlony with known immunodiffusion method (Acta.Med.Scan., 133,76-79 page or leaf (1950), these bacillary lipase reply TJ lipase antibody show the cross reactions of male immunology.
Above-mentioned TJ lipase antibody is shown that the bacillary lipase of positive immunology cross reaction all is the lipase that is applicable to embodiment of the present invention.Its typical example is can be from (the Nagoya of Amano drugmaker, Japan) the lipase that obtains with the trade name of Amano-P lipase from Pseudomonas fluorescens IAM 1057, from the lipase of Pseudomonas fragi FERM P 1339 (can trade name Amano-B obtain), lipase from Pseudomonas nitroreducens lipolyticum mutation FERMP1338, the lipase that can trade name Amano CES obtains from the Rhodopseudomonas kind, lipase from the onion Burkholderia, lipase from thickness look bacillus, the mutation lipolyticum NRRL B-3673 of thickness look bacillus for example, can buy from Toyo Jozo Co. (Tagata, Japan); And from other thickness look bacillus lipase of U.S. Biochemics Inc. (U.S.) and Diosynth Co (Holland), and from the gladiolus pseudomonas.
The example of fungoid lipase defined above is from the lipase of Humicola lanuginosa (can obtain with trade name Amano CE from Amano); Above-mentioned european patent application 0,258, lipase described in 068 (NOVO) from Humicola lanuginosa, and the gene by clone Humicola lanuginosa and this gene is expressed resulting lipase in aspergillus oryzae, can obtain with trade name " Lipolase " from NOVO industri A/S.This Lipolase is used for preferred lipase of the present invention.
Though more than described various concrete lipase, be appreciated that can give composition all can use with any lipase of required lipolytic activity, the present invention is not subjected to the concrete any qualification selected of lipase.
The content of the lipase of the embodiment of the present invention in liquid detergent composition is, when with preparation with about 1-10, when more preferably the level that rises of 5-7, first-selected 1-2g/ is used, the lipolytic activity of final composition in cycles of washing is 100 to 0.005LU/ml, and preferred 25 to 0.05LU/ml.
Lipase unit (LU) be can be under the pH value described in the following condition per minute produce the amount of the lipase of the titratable lipid acid of 1/Fmol: 30 ℃ of temperature; PH=9.0; Substrate is the emulsion of 3.3wt% sweet oil and 3.3% gum arabic, at 13mmol/1 Ca
2+With under the existence of 20mmol/1 NaCl in 5mmol/1 Tris-damping fluid.
Certainly, can use the mixture of above-mentioned lipase.Lipase can use with unpurified form or with the form of purifying, for example by the known absorption method lipase of phenyl sepharose adsorption technology purifying for example.
Proteolytic ferment can be from plant, animal or microorganism.Preferably, comprise yeast, fungi, mould and bacterium from the white lytic enzyme of microorganism.The proteolytic enzyme of special preferred bacterium subtilisin type, it can obtain from the specific bacterial strain of for example bacillus subtilis and lichens bacillus.The suitable examples of proteases that buys is Alcalase, Savinase, Esperase (being the product of NOVO Industri A/S); Purafect and Properase (from Genencor); Maxatase and Maxacal (from Gist-Brocades); Kazusase (from Showa Denko); BPN and BPN ' proteolytic enzyme; Optimase (from Solvay) etc.The content of proteolytic ferment in composition is 0.05-50,000GU/mg, and preferred 0.1 to 50GU/mg, in final composition.Certainly, also can use the mixture of different proteolytic ferments.
When as above having described various concrete enzymes, be appreciated that and adopt any proteolytic enzyme that to give composition desirable proteins hydrolytic activity that this embodiment of the present invention also is subjected to the restriction of the concrete selection of protease never in any form.
Except lipase or proteolytic enzyme, also can adopt other enzyme commonly known in the art in the composition of the present invention, as cellulase (Carezyme
TM, Clazinase
TM, Celluzyme
TM), oxydase, amylase, peroxidase etc.Enzyme can promote the required cofactor of enzymic activity to use with need, and if necessary promptly, they can be used in the enzyme system.Should be appreciated that the enzyme (for example, being designed for performance and/or stable enhanced enzyme) that has sudden change on all places also belongs within the design scope of the present invention.A kind of example of commercially available enzyme of design is the Durazym from Novo
TMThe selectivity composition
Except aforesaid enzyme, also can use many other selectivity compositions.
The ealkaline buffer that can add in composition of the present invention comprises monoethanolamine, trolamine, borax etc.
Other material such as clay, particularly the water-insoluble clay can be used as the auxiliary agent of the present composition.Useful especially is wilkinite.Be applicable to that the wilkinite (promptly not containing any gravel, sand etc.) as the more purified form of washing composition comprises at least 50% montmorillonite, thereby its cation exchange capacity (CEC) is at least about 50-75meq/100g wilkinite.
Particularly preferred wilkinite is Wyoming or Western US wilkinite, and it is to be sold by Georgia Kaolin Co with Thixo-jels 1,2,3 and 4.The known textiles that softens of these wilkinites is as described in following document: GB 401,413 (Marriott) and GB461,221 (Marriott and Guam).
In addition, in Betengent product, also can comprise other various washing composition compounds or auxiliary agent increasing required performance, or the character on the function, or apparent performance.
Improving the physical stability and the resistance to settling of composition can realize as aluminum stearate by the sorbyl alcohol of a small amount of significant quantity of adding or the aluminium salt of higher fatty acid in composition.The add-on of aluminum stearate stablizer is 0-3%, preferred 0.1-2.0%, more preferably 0.5-1.5%.
In preparation, also can comprise a spot of soil-suspending agent or anti redeposition agent, as polyvinyl alcohol, fatty amide, Xylo-Mucine, Vltra tears.Preferred anti redeposition agent comprises Alcosperse 725
TMAnd Xylo-Mucine, the ratio of its CM/MC is 2: 1, sells with trade(brand)name Relatin DM 4050.
Also can use the white dyes that is used for cotton, polymeric amide and polyester textile.Suitable white dyes comprises: Iinopal LMS-X, Tinopal UNPA-GX, toluylene, triazole and benzidine sulfone composition, particularly the triazinyl toluylene that replaces of sulfonated, sulfonated aphthotriazoles toluylene, benzidine sulfone etc., first-selected toluylene and triazole combination.Preferred whitening agent is toluylene whitening agent N4, and it is a dimorpholine diphenylamino toluylene sulfonate.
The defoamer that also can add a small amount of significant quantity, as silicon compound, Silicane L7604 for example.
Also can use sterilant, as tetrachloro-salicylanilide and Perchlorobenzene, mycocide, dyestuff, pigment (water dispersible), sanitas is as formalin, UV light absorber, anti-yellow agent such as Xylo-Mucine, pH regulator agent and pH buffer reagent, color-safe SYNTHETIC OPTICAL WHITNER, spices and dye well blueing such as Iragon Blue L2D, Detergent Blue 472/572 and ultramarine.
Equally, also can use and pollute release polymers and cationic softening agent.Anionic polymer
Anionic polymer of the present invention has polymkeric substance with the covalently bound electronegative group of chain for those.The example of synthetic anionic polymer is the polyacrylic acid unit of part and whole ionized form, the polyvinyl sulfonic acid of part and whole ionized form, poly-(methacrylic acid) of part and whole ionized form, poly-(phosphoric acid) and its salt, poly-(vinyl sulfuric acid) and poly-(vinyl alcohol-be total to-vinyl sulfuric acid) and its salt.Other synthetic anionic polymer is stated in following document: " water-soluble synthetic polymer: character and behavior ", P.Molyneux, Vol.II, CRC Press, 1985, this reference is incorporated herein by reference.The example of commercially available synthetic anionic polymer is the Sokalan series and the ACusol series of polyacrylic acid and vinylformic acid and maleic acid, is purchased respectively from BASF and Rohm ﹠amp; Haas.
The example of the natural anionic polymer of unmodified and modification is alginic acid and its salt and treated starch such as carboxymethyl cellulose.Unmodified and natural anionic polymer modification is stated in following document: " polymkeric substance and thickening material complete works ", R.Y.Lochhead and W.R.Fron inCosmetics and Toiletries, Vol, 108, May 1993, and this reference is incorporated herein by reference.
The consumption of anionic polymer is 0.1-10wt%, and preferred 0.25-5wt% is with composition weight meter.
Other adoptable optimum composition is a hydrotropic solvent.Usually, add hydrotropic solvent and help high-load tensio-active agent to mix in isotropic liquid washing agent, otherwise tensio-active agent might be separated with water.Hydrotropic solvent also can change the ratio of dissimilar tensio-active agents, and promptly the ratio of anion surfactant, nonionogenic tenside, cats product and zwitterionics is not separated and can not cause.Therefore, they can increase the adaptability of preparation.Hydrotropic solvent is had an effect by one of following mechanism: i) by changing the solvent ability of water, hydrotropic solvent can increase the solubleness of tensio-active agent at aqueous phase; Example in this case is a short chain alcohol, as ethanol, Virahol and glycerine and propylene glycol; Ii) prevent that by the packing division that makes the hydrocarbon chain of tensio-active agent in micelle tensio-active agent from forming mesomorphic phase; Example in this case is an alkali metal salt of alkyl aryl sulphonic acid, as an alkali metal salt of xylenesulfonate, cumene sulfonate and alkylaryl disulfonic acid, as is purchased DOWFAX from Dow Chemicals
(R)Family's hydrotropic solvent.
Preferably water soluble additive in the present composition is a polyvalent alcohol, and it also plays the enzyme stabilizers effect, as propylene glycol, ethylene glycol, glycerine, sorbyl alcohol, sweet dew alcohol and glucose.Enzyme encapsulate capsule
Enzyme encapsulate capsule of the present invention protective enzyme is effectively avoided UV radiating harmful effect.Thereby enzyme must suitably be contained in the encapsulate capsule preventing and enter in the liquid detergent composition a large amount of leakage of storage period glucose-6-phosphate dehydrogenase.
Enzyme encapsulate capsule can comprise macromolecular material, but this is not a restricted condition.If there is polymkeric substance in capsule, then at least a portion of macromolecular material would not be dissolved in the liquid washing agent, and they can disperse or dissolve when dilution.The example of synthesized polymer material is:
The polyvinyl alcohol of-different molecular weight and degree of hydrolysis (PVA), it is defined as a kind of homopolymer or multipolymer, wherein, vinyl acetate is the starting monomer unit, and wherein, most of or whole acetate parts can (for example be hydrolyzed into alcohol moiety subsequently, from the Airvol series of Air Products, from the Mowiol series of Hoechst)
-polymeric amide (diamines and di-carboxylic acid reaction obtain)
-polyester (dibasic alcohol and di-carboxylic acid reaction obtain)
-polyureas
-urethane
-Resins, epoxy
The example of other natural polymer comprises:
-methylcellulose gum (as, Methocal A15LV is available from Dow Chemical)
-hydroxy propyl cellulose (as, Klucel L or K1ucel G are available from Aqualon)
-HYDROXY PROPYL METHYLCELLULOSE
-carrageenin (κ or ι form) (all kinds are available from FMC)
-alginate (as, Manucol DM or DH are available from Kelco)
-gelling colloid (as, Kelcogel is available from Kelco)
-gelatin
Other reference: be used for the polymkeric substance and the thickening material complete works of makeup, vol.108, May 1993,95-135.
If there is polymkeric substance in capsule, then they exist with little solid particulate, perhaps are scattered in the whole particle, perhaps are preferably placed at capsular part, for example capsular skin.Polymkeric substance also can exist by the hydration particle, perhaps is scattered in the whole particle, perhaps is arranged in a capsular part.Polymkeric substance also may reside in the capsular core, with the onion ring form in the capsule, perhaps as the shell around core.
The enzyme capsule also can comprise hydrophobicity or fat material.
The example is:
-paraffinic hydrocarbons (preferred mineral jelly)
-tri-glyceride
-lipid acid
-Fatty Alcohol(C12-C14 and C12-C18)
The mixture of-lipid acid and fatty acid soaps
-ester (as, spermaceti acyl stearyl-stearate)
If capsule comprises hydrophobic material, they should be able to protective enzyme avoid the effect of moisture.Hydrophobic material should be sealed the enzyme solid particulate or the droplet that are present in the capsule.
Capsule also comprises other composition:
-density activator is as sucrose
-structurizing reagent, as, silicon-dioxide or zeolite
-filling agent, as, talcum, wilkinite
-scavenging agent, as, ammonium sulfate
-softening agent
-anti-coalescing agent or anti-layering agent
-releasing agent
Therefore, in a preferred embodiment, enzyme encapsulate capsule of the present invention can comprise macromolecular material.Preferred enzyme encapsulate capsule comprises and is selected from following macromolecular material: polyvinyl alcohol, polymeric amide, polyester, polyureas, urethane, Resins, epoxy, methylcellulose gum, hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, carrageenin, alginate, colloidal state colloid, gelatin and its mixture.
The capsular example of enzyme bag is stated in following document: WO-93/07263, EP-A585295, EP-A-356239, US-A-5,281,356, US-A-5,281,355 and GB2,186,884.
Enzyme encapsulate capsule of the present invention is 30-5000 μ m, preferred 300-3000 μ m, first-selected 500-2500 μ m.Particle shape can change to spherical from irregular; In a preferred form, they answer subglobular, but this should not be a kind of restriction.
The capsular enzyme encapsulate of the enzyme bag of the present invention capsule density of measuring according to detergent solution is 700-2500kg/m
3, more preferably 800-2000kg/m
3, first-selected 900-1500kg/m
3
Enzyme can be uniformly distributed in the particle (matrix capsule), is arranged in the core of capsule (core-shell capsule), perhaps is present in capsular any other limited zone, as in the annular zone of onion.
Enzyme can be present in the capsule by short grained solid form, and it can comprise true protein or optional be protein and other mixtures of material (optionally with the matrix of other component in).Enzyme also can enzyme solution the small droplets form be present in the capsule, perhaps as solid and mixtures of liquids (slurries).
Enzyme encapsulate capsule of the present invention can comprise any detergent enzyme, comprises proteolytic enzyme, lipase, amylase, peroxidase, cellulase or its mixture.
The example of proteolytic enzyme is for being purchased type, as the Alcalase from Novo Nordisk
TM, Durazym
TM, Relase
TM, Sayinase
TMWith Optimase from GenencorInternational
TM, Purafect
TM, Properase
TM
The example of lipase is the Lipolase from Novo Nordisk
TM, from the Lipomax of GenencorInternational
TM
The example of cellulase is the Celluzyme from Novo Nordisk
TMAnd Carezyme
TM, from the Clazinase of Genencor International
TM
Diastatic example is the Termamyl from Novo Nordisk
TMWith Maxamyl from Genencor International
TM
The preferred enzyme of the present invention is a proteolytic enzyme.
When enzyme of the present invention was proteolytic enzyme, Protein content was preferably 0.1-20%, more preferably 0.5-10%, first-selected 1-5%.
When enzyme of the present invention was proteolytic enzyme, enzymic activity was 100GU/mg-20000GU/mg, more preferably 500-10000GU/mg, first-selected 1000-5000GU/mg.
Embodiment
As state embodiment the present invention is described in further detail, and they are not limitation of the present invention.
Except as otherwise noted, all percentage number averages refer to weight percentage.
All numerical value in specification sheets, claims and embodiment and scope are modified by speech " pact ".
Equally, when being used for claims or specification sheets, comprising and be meant and comprise all key elements, feature etc.
Embodiment 1
Be prepared as follows the enzyme capsule:
Prepare a kind of polymers soln: 3.3 parts polyvinyl alcohol (available from the Airvol 540 of Air ProductsInc) are dissolved in 60.7 parts the water.The polyacrylic acid acryl ester that adds 6.0 parts then is (available from Rohm ﹠amp; The Acrysol ASE-60 of Haas), the 2%NaOH aqueous solution that adds 30 parts again.
The enzyme dispersion liquid of preparation in lyophobic dust: under 60 ℃, (Solvay, the present branch of Genencor International Inc.) is scattered in 59.5 parts Snow white petrolatum (being purchased from Penreco) with 15 parts Optimase powder.The Trogrees Spray S (being purchased) that in dispersion liquid, adds 25.5 parts subsequently from Penreco, remix 30 minutes.
Prepare the emulsion of 1 part of enzyme dispersion liquid in 6 parts of polymers solns: " I.D.12 parts static mixer, productivity are 12ml/min in employing 3/8.This emulsion adopts SprayingSystems 35100 double-liquid nozzles to atomize under the 7100cc/min air speed.
The drop that forms is collected in the hardening solution, and described hardening solution comprises 83.5 parts water, 15 parts sodium sulfate (being purchased the N.A. from Elf Atochem), 1.5 parts sodium tetraborate decahydrate (being purchased the Chemicals from Textile), 0.001 part sodium lauryl sulphate (being purchased from Aldrich) and 0.001 part froth breaking Silicon AF-544 (being purchased from DowCorning).By screening the enzyme capsule is separated from hardening solution subsequently.These capsular enzymic activitys are 5.10
4GU/g.
Embodiment 2
Adopt the enzyme capsule preparation of embodiment 1 preparation to contain enzyme liquid detergent composition (size is 500-1000 μ m).The level of enzyme capsule with 1.5wt% is scattered in the transparent liquid detergent of 20g, and its composition is as shown in table 1, and the enzymic activity that makes liquid detergent composition is 7.610
2GU/g.
The preparation another kind contains the enzyme liquid detergent composition: the aqueous solution of Optimase powder (Solvay, the present branch of Genencor International Inc.) is added in the composition transparent liquid detergent as shown in table 1.Be chosen in the enzyme concn in the aqueous solution so that the enzymic activity in liquid detergent composition is 7.610
2GU/g.
Handled is so that have the enzymic activity that the enzymic activity of the capsular liquid detergent composition of enzyme equals enzyme is added to the detergent composition that obtains in the aqueous solution.
To comprise the sample of the 20g washing composition with dissolving Optimase and comprise the sample with the capsular 20g washing composition of Optimase and preserve in transparent polythene container, the diameter of container is 47mm, and height is 95mm.
The UV-B light source (Philips TL20W12) that these samples are stored in two 20W is in from the bottle bottom to UV-B light source 20cm distance sample in 37 ℃ of following radiating accelerated tests.Comparative sample is preserved in accelerated tests in 37 ℃ under unglazed photograph.
After storage 2 days and 7 days, take out sample, and analyze the residual enzyme activity with respect to the active original bulk of storage preferment.
Residual enzyme activity and the funtcional relationship of time when following table 2 has been listed storage.
Carry out following significant observation:
1) for the enzyme that adds by the aqueous solution, under UV light exposure than unglazed inactivation down carry out faster.
2) if clear vial is exposed with UV light, the storage stability of the enzyme that adds with capsule form will strengthen than the storage stability that adds to the enzyme in the liquid washing agent with the solution form.
3) there be not difference with the UV rayed with under between the capsular inactivation of enzyme without the UV rayed.This shows that the enzyme in the capsule is protected, and avoids the harmful effect of UV light.
Table 1: detergent formulation
| 100% active composition | ????wt％ |
| Nonionogenic tenside | ????15.6 |
| The alcohol ethoxy sulfuric ester | ????9.0 |
| Linear alkylbenzene sulphonic acid | ????5.9 |
| Fatty acid distribution of coconut oil | ????0.8 |
| Propylene glycol | ????6.0 |
| Monoethanolamine | ????0.2 |
| Trisodium citrate dihydrate | ????2.5 |
| The sodium tetraborate pentahydrate | ????1.5 |
| Kappa carrageenan | ????0.2 |
| A small amount of additive and water | To 100% |
Table 2
Enzyme and the capsular storage stability of enzyme in transparent or semitransparent bottle in the liquid washing agent, irradiation and under UV light without rayed.The residual enzyme activity is (with respect to the activity before the storage, %) as the function of storage time
| The active % of residual enzyme | ||||
| Storage time (my god) | The 0ptimase that solution adds is without rayed | The 0ptimase that solution adds uses the UV rayed | The 0ptimase that capsule adds uses the UV-rayed | The Optimase that capsule adds is without rayed |
| ????0 | ????100％ | ????100％ | ????100％ | ????100％ |
| ????7 | ????50％ | ????37％ | ????63％ | ????59％ |
Can clearly be seen that inactivation will be faster than adopting capsular the time when not adopting capsule, thus explanation, and capsule can prevent the UV rayed.
Embodiment 3 experiment conditions
It is 1.5 that the liquid washing agent sample (5g) (table 1) that will comprise proteolytic enzyme and lipase adds to diameter " glass disc in, remove lid, with the irradiation 4 days under about 254nm of UV-C light, at 110 mwatt/cm
2(measure down apart from light source 28 ").Every 24 hours,, and remove lid at the water that replaces evaporation to samples weighing.For from capsule, discharging enzyme, with capsule 10, under the 000rpm in 2% Neodol 25-9 solution homogeneous.Enzymic activity in homogeneous solution adopts casein to measure as substrate.The initial activity that does not carry out the UV pre-irradiation with sample is a basic calculation residual activity percentage ratio.
Adopt the UV-A/B chamber similarly to test (UVA=1.01mW/cm
2, UVB=6.17mW/cm
2(lamp)).To comprise the capsular HDL ' of enzyme s and use UV rayed 4 days.
Table 3
Detergent formulation (shows with scope, wishes free ﹠amp; Clarification (Wisk Free ﹠amp; Clear))
| 100% active composition | ????wt％ |
| ????Neodol?25-9 * | ????6-8 |
| The alcohol ethoxy sulfuric ester | ????12-15 |
| Linear alkylbenzene sulphonic acid | ????6-9 |
| Trisodium citrate dihydrate | ????3-6 |
| Propylene glycol | ????4-8 |
| Sorbyl alcohol | ????3-6 |
| The sodium tetraborate pentahydrate | ????2-4 |
| A small amount of additive and water | To 100% |
*C12-C15 ethoxylated alkyl chain with 9 oxidation ethylidene unit ethoxylations
| Under UV-A/B | At the postradiation residual activity % of UV | |
| The 1st day | The 4th day | |
| Enzyme (Purafect 4000L) with the liquid adding | ????7 | ????0 |
| Capsule (Optimase) according to embodiment 1 preparation | ????81 | ????69 |
| Under UV-C | ||
| Enzyme (Savinase) with the liquid adding | ????61 | ????51 |
| Capsule (Optimase) according to embodiment 1 preparation | ????100 | ????97 |
Demonstrating stability when equally, adopting capsule improves.
Claims (13)
1. the liquid detergent composition of a packing, it comprises transparent container and transparent enzyme-containing detergent compositions, it is characterized in that, and described enzyme is by the encapsulate capsule;
Wherein, to be defined as at wavelength be that transmittance is 25% or bigger under the 410-800nm to described transparent vessel;
Wherein, it is under the 410-800nm that described transparent liquid is defined as at wavelength, and the transmittance in the cuvette time of employing 1cm is greater than 50%.
2. according to the detergent composition of the packing of claim 1, wherein, enzyme encapsulate capsule comprises macromolecular material.
3. according to the detergent composition of the packing of claim 2, wherein, enzyme encapsulate capsule macromolecular material is selected from: polyvinyl alcohol, polymeric amide, polyester, polyureas, urethane, Resins, epoxy, methylcellulose gum, hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, carrageenin, alginate, colloidal state colloid, gelatin and its mixture.
4. according to the detergent composition of the packing of claim 1, wherein, the capsular 30-5000 μ m that is of a size of of enzyme bag.
5. according to the detergent composition of the packing of claim 1, wherein, the capsular density of enzyme bag that records in detergent solution is 700-2500kg/m
3
6. according to the detergent composition of the packing of claim 1, wherein, enzyme is a proteolytic enzyme.
7. according to the detergent composition of the packing of claim 6, wherein, the content of proteolytic enzyme is 0.1-20%.
8. according to the detergent composition of the packing of claim 6, wherein, the enzymic activity of proteolytic enzyme is 100GU/mg-20000GU/mg.
9. according to the detergent composition of the packing of claim 1, wherein, described enzyme encapsulate capsule comprises a kind of detergent enzyme, and it is selected from proteolytic enzyme, lipase, amylase, peroxidase, cellulase and its mixture.
10. according to the detergent composition of the packing of claim 1, wherein, liquid washing agent is an aqueous detergent.
11. according to the detergent composition of the packing of claim 1, wherein, liquid washing agent is an external structureization.
12. detergent composition according to the packing of claim 11, wherein, liquid washing agent is with being selected from following polymkeric substance external structureization: colloidal state colloid, xanthan gum, polyacrylic ester, phycocolloid, guar gum, rhamsan, carrageenin, carbopol base polymer and its mixture.
13. according to the detergent composition of the described packing of aforementioned each claim, wherein, transparent container comprises a kind of following material that is selected from: (high-density) polyethylene, polypropylene, polycarbonate, PET and its mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21304698A | 1998-12-16 | 1998-12-16 | |
| US09/213,046 | 1998-12-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1330707A true CN1330707A (en) | 2002-01-09 |
Family
ID=22793525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99814555.6A Pending CN1330707A (en) | 1998-12-16 | 1999-11-09 | Detergent composition |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP1141206B1 (en) |
| CN (1) | CN1330707A (en) |
| AR (1) | AR026104A1 (en) |
| AT (1) | ATE249510T1 (en) |
| AU (1) | AU746412B2 (en) |
| BR (1) | BR9916230A (en) |
| CA (1) | CA2355132A1 (en) |
| DE (1) | DE69911254T2 (en) |
| ES (1) | ES2207318T3 (en) |
| HU (1) | HUP0104643A3 (en) |
| TR (1) | TR200101712T2 (en) |
| TW (1) | TW460580B (en) |
| WO (1) | WO2000036067A1 (en) |
| ZA (1) | ZA200104082B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942998A (en) * | 2012-10-30 | 2013-02-27 | 湖南日用化学科学研究所有限公司 | Washing auxiliary agent for removing protein stains |
| CN105164244A (en) * | 2013-05-03 | 2015-12-16 | 诺维信公司 | Microencapsulation of detergent enzymes |
| CN112980607A (en) * | 2021-02-26 | 2021-06-18 | 中山百科清洁用品制造有限公司 | Long-acting mosquito-repelling laundry detergent and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10111536A1 (en) * | 2001-03-10 | 2002-09-12 | Beiersdorf Ag | Aqueous cosmetic and dermatological preparations containing suspended solid particles, gas bubbles and / or liquid droplets, furthermore containing a combination of xanthan gum and gellan gum |
| US6420333B1 (en) * | 2001-08-28 | 2002-07-16 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Manufacture of capsules for incorporation into detergent and personal care compositions |
| GB0129983D0 (en) * | 2001-12-14 | 2002-02-06 | Unilever Plc | Unit dose products |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2136913B1 (en) * | 1971-05-07 | 1973-05-11 | Colgate Palmolive Co | |
| EG18543A (en) * | 1986-02-20 | 1993-07-30 | Albright & Wilson | Protected enzyme systems |
| GB9110408D0 (en) * | 1989-08-24 | 1991-07-03 | Allied Colloids Ltd | Polymeric compositions |
| US5281355A (en) * | 1992-04-29 | 1994-01-25 | Lever Brothers Company, Division Of Conopco, Inc. | Heavy duty liquid detergent compositions containing a capsule which comprises a component subject to degradation and a composite polymer |
| ES2147217T3 (en) * | 1993-11-12 | 2000-09-01 | Unilever Nv | DETERGENT COMPOSITION. |
| DK0876205T3 (en) * | 1995-12-29 | 2002-08-12 | Ciba Spec Chem Water Treat Ltd | Polymer sheath particles and their preparation |
| AU1535897A (en) * | 1996-01-18 | 1997-08-11 | Colgate-Palmolive Company, The | Filled package of light duty liquid cleaning composition |
| WO1998053035A1 (en) * | 1997-05-19 | 1998-11-26 | The Procter & Gamble Company | Clear or translucent fabric softener compositions using mixture of solvents |
| EP0913462A1 (en) * | 1997-10-31 | 1999-05-06 | The Procter & Gamble Company | Liquid aqueous bleaching compositions packaged in a UV-resistant container |
-
1999
- 1999-11-09 WO PCT/EP1999/008893 patent/WO2000036067A1/en not_active Application Discontinuation
- 1999-11-09 DE DE69911254T patent/DE69911254T2/en not_active Revoked
- 1999-11-09 TR TR2001/01712T patent/TR200101712T2/en unknown
- 1999-11-09 AT AT99963312T patent/ATE249510T1/en not_active IP Right Cessation
- 1999-11-09 CN CN99814555.6A patent/CN1330707A/en active Pending
- 1999-11-09 AU AU19667/00A patent/AU746412B2/en not_active Ceased
- 1999-11-09 BR BR9916230-0A patent/BR9916230A/en not_active Application Discontinuation
- 1999-11-09 EP EP99963312A patent/EP1141206B1/en not_active Revoked
- 1999-11-09 HU HU0104643A patent/HUP0104643A3/en unknown
- 1999-11-09 ES ES99963312T patent/ES2207318T3/en not_active Expired - Lifetime
- 1999-11-09 CA CA002355132A patent/CA2355132A1/en not_active Abandoned
- 1999-12-15 AR ARP990106396A patent/AR026104A1/en unknown
- 1999-12-27 TW TW088123039A patent/TW460580B/en not_active IP Right Cessation
-
2001
- 2001-05-18 ZA ZA200104082A patent/ZA200104082B/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942998A (en) * | 2012-10-30 | 2013-02-27 | 湖南日用化学科学研究所有限公司 | Washing auxiliary agent for removing protein stains |
| CN102942998B (en) * | 2012-10-30 | 2013-12-18 | 湖南日用化学科学研究所有限公司 | Washing auxiliary agent for removing protein stains |
| CN105164244A (en) * | 2013-05-03 | 2015-12-16 | 诺维信公司 | Microencapsulation of detergent enzymes |
| CN112980607A (en) * | 2021-02-26 | 2021-06-18 | 中山百科清洁用品制造有限公司 | Long-acting mosquito-repelling laundry detergent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2207318T3 (en) | 2004-05-16 |
| AU1966700A (en) | 2000-07-03 |
| BR9916230A (en) | 2001-09-04 |
| AU746412B2 (en) | 2002-05-02 |
| ZA200104082B (en) | 2002-06-18 |
| HUP0104643A3 (en) | 2002-12-28 |
| DE69911254D1 (en) | 2003-10-16 |
| DE69911254T2 (en) | 2004-04-01 |
| TR200101712T2 (en) | 2001-12-21 |
| WO2000036067A1 (en) | 2000-06-22 |
| TW460580B (en) | 2001-10-21 |
| EP1141206A1 (en) | 2001-10-10 |
| HUP0104643A2 (en) | 2002-04-29 |
| AR026104A1 (en) | 2003-01-29 |
| ATE249510T1 (en) | 2003-09-15 |
| CA2355132A1 (en) | 2000-06-22 |
| EP1141206B1 (en) | 2003-09-10 |
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