CN1181104A - Detergent compositions comprising nonionic polysaccharide ethers and lipase enzymes - Google Patents
Detergent compositions comprising nonionic polysaccharide ethers and lipase enzymes Download PDFInfo
- Publication number
- CN1181104A CN1181104A CN 96193171 CN96193171A CN1181104A CN 1181104 A CN1181104 A CN 1181104A CN 96193171 CN96193171 CN 96193171 CN 96193171 A CN96193171 A CN 96193171A CN 1181104 A CN1181104 A CN 1181104A
- Authority
- CN
- China
- Prior art keywords
- detergent composition
- somebody
- turn
- lipase
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
Abstract
The present invention relates to a detergent composition comprising a lipase enzyme in combination with a nonionic polysaccharide ether for improved stain removal performance.
Description
Invention field
The present invention relates to contain the detergent composition of lipase and nonionic polysaccharide ether, it provides improved detergency ability.
Background of invention
The purposes that lipase is mixed in the detergent composition to assist in removing based on the spot of triglyceride level or fatty acid ester is well-known.For example WO92/05249 discloses some lipase mutation with improved properties and their preparation method.WO94/25577 discloses the detergent composition that new lipase mutation and every gram washing composition contain 0.02～200 milligram of this lipase additive.
Usually, the lipase detergency ability is directly relevant with their concentration in detergent composition, so the increase of lipase usage quantity will strengthen its detergency ability.But it is found that under intensified condition, under the situation such as short wash(ing)cycle, low temperature or the very dirty substrate of existence, can reach the best effect of lipase at a certain content.Increase lipase content at this again more than the amount and can not improve clean effect.And, another shortcoming that strengthens lipase content in the detergent composition be cause in the known stench problem that is washed on the fabric more serious.
It is found that now when lipase was used in combination with nonionic polysaccharide ether, its detergency ability can unexpectedly improve under intensified condition.
A further advantage of the invention is and only removing the spot benefit as can be seen after a wash(ing)cycle.This forms contrast with decontamination and/or the antiredeposition benefit relevant with nonionic polysaccharide ether and lipase, and the latter needs the multicycle use just can see these benefits.
Another advantage of the present invention is not have relevant stench problem.
The existing in the art narration of purposes as stain remover of nonionic polysaccharide ether.For example, US4740326 discloses the laundry product that contains with the matrix material of decontamination polymer-coated, and this product has improved the scourability to the hydrophobic dirt on synthetic and synthetic and the natural BLENDED FABRIC.Soil release polymer comprises having molar substitution (ds) is 2000100000 for 15-2.7 and molecular-weight average, alkyl or the hydroxyalkyl cellulose ether of preferred 10000-30000.Wherein mention enzyme, but do not mentioned lipase particularly.
US 4174305 disclose contain LAS and have ds up to 3 and dp be the detergent composition of the etherified cellulose stain remover of 100-10000.Wherein mentioned enzyme, particularly proteolyzing enzyme and lipolytic enzyme be not although mention their content.Lipase is not included among the embodiment.
US 4136038 discloses that to comprise molecular weight be that 3000-10000 and ds are the fabric-conditioning compositions of the detergency enzymes that is selected from proteolytic enzyme, lipase, amylase and their mixture of the ether of cellulose of 1.8-2.7 and 0.05%-2%.Wherein do not illustrate the composition that contains lipase and ether of cellulose.
EP 0495257 discloses the closely knit detergent composition that contains high active cellulase.Anti redeposition agent such as derivatived cellulose are disclosed, methylcellulose gum especially, carboxymethyl cellulose (CMC) and Natvosol, but do not have to disclose their dp and ds value.Wherein also disclose other enzymes and comprised lipase, but not mentioned content.
Therefore, the purpose of this invention is to provide a kind of detergent composition that contains lipase, it provides the improved removal performance to triglyceride level and lipid acid ester group dirt, and especially effect is better under intensified condition.All unexposed lipase combines the feature performance benefit that brings in above-mentioned all prior art files with nonionic polysaccharide ether, and this present invention just had.
Summary of the invention
The present invention relates to contain the detergent composition of at least 1% tensio-active agent, it is characterized in that this detergent composition surpasses 10000 nonionic polysaccharide ether in conjunction with comprising lipase and molecular weight, lipase has activity, thereby makes this detergent composition have the activity of 0.001LU/ milligram at least.
Except as otherwise noted, all quantity, content and percentage number average provide with the weight percentage of detergent composition.Detailed Description Of The Invention
Detergent composition of the present invention contains and the lipase of nonionic polysaccharide ether bonded as basal component.Lipase
The lipase that is applicable to washing composition comprises by the microorganism in the Rhodopseudomonas family, as those lipase of Situ Ci Shi (stutzeri) aeruginosa atcc 19154 generations, as those disclosed in English Patent 1372034.Also referring to the lipase of speciallyying permit on February 24th, 1978 among the disclosed Japanese patent application 53-20487.This lipase can be by Amano PharmacuticalCo.Ltd.Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other commercial lipase comprises Amano-CES, lipase ex pigment bacillus (Chromobacter) viscosum, for example, pigment bacillus viscosum varlipolyticum NRRLB 3673, they commercial can be from Toyo Jozo Co., Tagata, Japan has bought; With other pigment bacillus viscosum lipase, they can be from U.S.Biochemical Corp., and U.S.A. and Disoynth Co. (Holland) have bought and lipase ex gladiolus pseudomonas (Pseudomonas gladioli).Plant that Pseudomonas fetal hair bacterium (Humicolalanuginosa) obtains and be the preferred herein lipase that uses by corruption at the commercial LIPOLASE enzyme that can buy by Novo (equally referring to EP341947).
Another lipase that preferably uses of this paper is to plant the derive D96L lipolytic enzyme mutation of the native lipase that obtains of Pseudomonas fetal hair bacterium by corruption.What most preferably use is that Pseudomonas fetal hair bacteria strain DSM4106 is planted in corruption.
The mutation of D96L lipolytic enzyme is meant as the lipase mutation of describing in WO 92/05249, and wherein native lipase ex corruption is planted Pseudomonas fetal hair bacterium aspartic acid (D) residue and 96 is transformed into leucine (L) in the position.According to this term, 96 pairs in the position leucic replacements of the aspartic acid that is somebody's turn to do are designated as: D96L.The LU assay method of use standard is measured the activity (analytical procedure, mternal Novo Nordisk number AF 95/6-GB 1991.02.07) of enzyme D96L.Use Sudan Gum-arabic as the Substrate of emulsifying agent by emulsification tributyrin (Merck) preparation D96L.Use pH stat. method to measure lipase activity at pH7.
Lipase is with every milligram of detergent composition 0.001LU to 100LU, and the content of preferred 0.005LU to 10LU is incorporated into according in the composition of the present invention.More preferably the content with every milligram of detergent composition 0.01LU to 5LU adds.Nonionic polysaccharide ether
According to the present invention, another basal component of detergent composition is a molecular weight greater than 10000 nonionic polysaccharide ether.From chemically, polysaccharide is made up of pentose class and hexasaccharide.Be applicable to that polysaccharide herein is selected from ether of cellulose, starch ethers, dextran ether and their mixture.This nonionic polysaccharide ether preferred cellulose ether.Ether of cellulose derives from plant tissue and fiber usually, comprises cotton and wood pulp.
The hydroxyl of cellulosic anhydroglucose unit can react with all ingredients, uses the hydrogen of other chemical group substituted hydroxies thus.Various alkylations and hydroxyalkylation reagent can react with ether of cellulose, with preparation alkyl, hydroxyalkyl or alkyl-hydroxyalkylcelluloswith ether or their mixture.That the present invention most preferably uses is C
1-C
4Alkyl cellulose ether or C
1-C
4Hydroxyalkyl cellulose ether or C
1-C
4Alkyl hydroxy alkyl cellulose ether or their mixture.The preferred substitution value of polysaccharide of the present invention is 0.5-2.8, and more preferably 1-2.5 most preferably is 1.5-2 (comprising 1.5 and 2).
Suitable nonionic cellulose ether comprises methyl cellulose ether, hydroxypropyl methyl cellulose ether, hydroxyethylmethyl-cellulose ether, hydroxypropylcelluloether ether, hydroxy butyl methyl cellulose ether, second hydroxyethyl cellulose ethers, cellulose ether and hydroxyethyl cellulose ethers.This polysaccharide is methyl cellulose ether most preferably.These reagent can have been bought on market, as METHOCEL (DowChemicals).
According to the present invention, the polysaccharide molecular weight that is somebody's turn to do is 10000 to 200000, most preferably is 30000 to 150000.Its weight-average molecular weight is obtained by the standard method of analysis described in " polymer handbook ".Preferable methods is the polymers soln light scattering method that is defined by Debye as at first.
The amount that composition of the present invention contains this nonionic polysaccharide ether is 0.01%-10%, preferred 0.01%-3%, most preferably 0.1%-2%.
It is 10000: 1 to 1: 10 that detergent composition according to the present invention comprises ratio, preferred 1000: 1 to 1: 1 this lipase and polysaccharide.The amount of lipase represents that with LU the amount of nonionic polysaccharide ether is represented detersive surfactants with milligram
Detergent composition according to the present invention comprises at least 1% surfactant system.The tensio-active agent that is used for this paper comprises common C
11-18Alkylbenzene sulfonate (" LAS ") and primary alkyl, side chain and random C
10-20Alkyl-sulphate (" AS "), chemical formula is CH
3(CH
2)
x(CHOSO
3M
+) CH
3And CH
3(CH
2)
v(CHOSO
3M
-) CH
2CH
3C
10-18Secondary (2,3) alkyl-sulphate, wherein x and (y+1) be to be at least approximately 7 preferably is at least about 9 integer, and M is a water-soluble cationic, sodium ion especially, unsaturated vitriol such as oleyl sulfate, C
10-18Alkyl alkoxy sulfate (" AE
xS "; Especially C E01-7 ethoxy sulfate),
10-18Alkyl alkoxy carboxylate salt (especially E01-5 ethoxy carboxylate), C
10-18Glyceryl ether, C
10-18Alkylpolyglycosides and the poly-glycosides of corresponding sulphating thereof, and C
12-18α-sulfonated fatty acid ester.
If necessary, common nonionic and amphoterics are as comprising the C of so-called narrow peak alkylethoxylate
12-18Alkylethoxylate (" AE ") and C
6-12Alkylphenol alcoxylates (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C
12-C
18Trimethyl-glycine and sultaine (" sultaines "), C
10-C
18Amine oxide or the like also can be included in above-mentioned all compositions.The present invention also can use C
10-18N-alkyl polyhydroxy fatty acid amide.Typical example comprises C
12-18The N-methyl glucose amide.Referring to WO92/06154.Other sugar surfactants comprise N-alkoxyl group polyhydroxy fatty acid amide, as C
10-18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C
12-18Glucamide can be used for low the foaming.Also can use C
10-20Common soap.Highly bubble if desired, can use side chain C
10-16Soap.The mixture of negatively charged ion and nonionogenic tenside is particularly useful.In the textbook that useful tensio-active agent that other are common such as cats product are listed in standard.
The amount that composition according to the present invention contains tensio-active agent is 1%-80%, is preferably 5%-50%, most preferably is 10%-40%.Preferred surfactants used herein is a linear alkylbenzene sulfonate, alkyl-sulphate and alkyl alkoxylated nonionogenic tenside or their mixture.Optional components
Can contain many optional conventional detergent additives according to detergent composition of the present invention, as washing assistant, sequestrant, polymkeric substance, anti redeposition agent or the like.Washing assistant
Washing auxiliary detergent optionally is included in the composition of the present invention to help the control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant typically is used for the removal of fabric cleaning composition to help microgranular dirt.
The content of washing assistant can change in wide region according to end-use and its required physical form of composition.When using washing assistant, typically contain at least 1% washing assistant in the composition.The weight that liquid preparation typically comprises washing auxiliary detergent is 5% to 50%, more typically is about 5% to 30%.The weight that granular preparation typically comprises washing auxiliary detergent is 10% to 80%, more typically is 15% to 50%.But this does not also mean that the washing assistant content that eliminating is lower or higher.
Inorganic or phosphorous washing auxiliary detergent includes but not limited to: basic metal, ammonium, the polyphosphate of alkanol (triphosphate for example, pyrophosphate salt, orthophosphoric acid salt and glassy polymeric metaphosphate), phosphonate, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate (referring to, for example, U.S. Pat 3159581; 3213030; 3422021; 3400148 and 3422137).
But, need nonphosphate builders in some occasion.Importantly, even so-called " weak " washing assistant (with phosphate ratio) as Citrate trianion in the presence of, or the what is called when using zeolite or stratification silicate-like builder " owes to help and washes " under the situation, and composition of the present invention still shows surprising premium properties.
The example of silicate-like builder is an alkalimetal silicate, particularly those SiO
2: Na
2The stratification silicate of the ratio of O in 1.6: 1 to 32: 1 scopes is as the stratification water glass of describing in the U.S. Pat 4664839 that licenses to H.P.Rieck on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " usually) by the stratification crystalline silicate of Hoechst sale.Do not resemble zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na
2SO
5The stratification silicate of form.The method preparation of being somebody's turn to do among its available DE-A-3417649 and the DE-A-3742043.SKS-6 is the layered silicate that this height is preferably used for this paper, also can use other layered silicate, has general formula NaMSi as those
xO
2x+1YH
2The layered silicate of O, wherein M is sodium or hydrogen, and x is 1.9 to 4, is preferably 2, and y is 0 to 20, is preferably 0.Various other layered silicates of buying from Hoechst comprise NaSKS-5, and NaSKS-7, and NaSKS-11 are α, β and γ form.Just as mentioned above, δ-Na
2SO
5(NaSKS-6 form) most preferably used herein.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as the setting agent in the granular preparation, as the stablizer of oxidation bleaching and the component of control foam system.
The example of carbonate builders is alkaline earth and alkaline carbonate, as be published in the German patent application 2321001 on November 15th, 1973 disclosed.
In the heavy loading granular detergent composition that major part is sold at present, the silico-aluminate washing assistant is considerable component, and it also can be that effectively helping in the liquid detergent compositions washed component.The silico-aluminate washing assistant comprises the material with following empirical formula:
M
z[(SiO
2)
w(zAlO
2)
y] xH
2O is w wherein, and z and y are at least 6 integer, and the mol ratio of z and y is 1.0～about 0.5, x is about 15 to about 264 integer.
Useful aluminosilicate ion exchange material has commercial offers.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.The method for preparing aluminosilicate ion exchange material is disclosed in and licensed in people's such as Krummel the U.S. Pat 3985669 on October 12nd, 1976.The preferred synthetic crystallization aluminosilicate ion exchange material that is used for this paper can be that ZeoliteA, ZeoliteP (B), Zeolite MAP and Zeoliet X buy by registered trademark.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has following formula:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein x is about 20 to about 30, is about 27 especially.This material is called Zeolite A.Dehydration zeolite (x=0-10) also can use in this article.Preferably, aluminosilicate particle is of a size of the about 0.1-10 micron of diameter.
The organic washing-assisting detergent that is fit to purposes of the present invention includes but not limited to various multi-carboxy compounds." multi-carboxy compound " used herein refers to have the compound of a plurality of carboxyls, preferably contains 3 carboxyls at least.The multi-carboxy compound washing assistant can add in the composition with sour form usually, but also can add with the form of the salt that is neutralized.When using with the form of salt, basic metal, as sodium, potassium and lithium or alkanol ammonium salts are preferred.
Be included in the multi-carboxy compound washing assistant is various useful materials.A kind of multi-acid salt washing assistant of important kind comprises the ether multi-carboxylate, comprise the oxidation disuccinate, as being issued to the U.S. Pat 3128287 of Berg on April 7th, 1964 and being issued to those disclosed in people's such as Lamberti the U.S. Pat 3635830 on January 8th, 1972.Also referring to " TMS/TDS " washing assistant in the U.S. Pat 4663071 that was issued to people such as Bush on May 5th, 1987.The ether multi-carboxylate who is fit to also comprises ring compound, particularly alicyclic compound, as described at U.S. Pat 3923679, US3835163, US41 58635, US4120874 and US4102903 those.
Other useful detergent builder compounds comprise ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and the various basic metal of carboxymethyl oxidation Succinic Acid, ammonium and get the poly-acetate of ammonium are as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and multi-carboxy compound such as mellitic acid, succsinic acid, oxygen disuccinic acid, polymaleic acid, 1,3,5-benzene tricarboxylic acid, carboxymethyl succinate oxidation and their water-soluble salt.
The Citrate trianion washing assistant, for example, citric acid and its water-soluble salt (particularly sodium salt) are the multi-carboxy acid salt washing agents of particularly important in the heavy duty liquid detergent formulations, reason is that they can be obtained and their biodegradability by renewable resource.Citrate trianion also can be used for particulate composition, especially is used in combination with zeolite and/or stratification silicate-like builder.The oxygen disuccinate also is useful especially in these compositions and mixture.
It is disclosed 3 that also having of being adapted at using in the detergent composition of the present invention was issued in the U.S. Pat 4566984 of Bush on January 28th, 1986,3-dicarboxyl-4-oxa--1,6-adipate and related compound thereof.Useful succsinic acid washing assistant comprises C
5-C
20Alkyl and alkenyl succinic and their salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The specific examples of succinate washing assistant comprises: lauryl succinate, nutmeg base succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in this group, is described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.
Other multi-carboxylates that are fit to are disclosed in and are issued in the U.S. Pat 3308067 of Diehl in the U.S. Pat 4144226 and on the March 7th, 1967 that were issued to people such as Crutchfield on March 13rd, 1979.Also referring to U.S. Pat 3723322.
Lipid acid, for example C
12-C
18Monocarboxylic acid also can mix in the composition individually, or combines with above-mentioned washing assistant especially Citrate trianion and/or succinate washing assistant and to mix in the composition, washes activity so that extra helping to be provided.Use lipid acid typically can cause whipability to reduce like this, this prescription teacher should consider.Sequestrant
Cleaning composition of the present invention can also randomly contain the sequestrant of one or more iron and/or magnesium.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelating agent of multifunctional replacement and composition thereof, all sequestrants are as hereinafter definition.Though should not accept the restriction of opinion, it is believed that the advantage of these materials partly is to have the excellent properties of removing magnesium and iron ion by formation soluble chelating thing from washing soln.
The aminocarboxylate of useful as selective sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.
When allowing at least to have low total phosphorous in detergent composition of the present invention, amino phosphonates do also is suitable as the sequestrant in the present composition, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt) is as DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl above six carbon atom.
In the present composition, can also use the aromatic chelating agent of multifunctional replacement.Be issued to people's such as Connor U.S. Pat 3812044 referring on May 21st, 1974.The preferred compound of this class acid form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.
The preferred in the present invention biodegradable cheating agent of using is ethylenediamine disuccinate (" EDDS "), especially its [S, the S] isomer as describing in the U.S. Pat 4704233 that is issued to Hartman and Perkins on November 3rd, 1987.
If the use sequestrant, then its consumption is generally 0.1% to 10% of detergent composition weight of the present invention, more preferably is 0.1% to 3.0%.The polymerization stain remover
Well known to a person skilled in the art that any polymerization stain remover all can randomly be used for the compositions and methods of the invention.The polymerization stain remover is characterised in that it contains hydrophilic segment and hydrophobic part simultaneously, and wherein hydrophilic segment makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; Hydrophobic part attached to the surface of hydrophobic fiber and in whole washing and rinse cycle all the time attached to fiber surface on, therefore hydrophilic segment is played fixed action.This makes through easier being cleaned in washing process thereafter of the spot after the detergent-treatment.
The polymerization stain remover that the present invention uses especially comprises the polymerization stain remover with following composition: (a) one or more nonionic hydrophilic components, it is at least 2 polyoxyethylene part by form (i) polymerization degree as the lower section basically, (ii) the propylene oxide or the polymerization degree are the polyoxypropylene part of 2-10, wherein this hydrophilic segment does not comprise any oxypropylene unit, except this unit terminal with proximate portion combines by ehter bond at each, (iii) contain aerobic ethene and the unitary mixture of the unitary oxygen alkene of about 1-30 oxypropylene, the mixture that wherein is somebody's turn to do contains abundant oxygen ethylene unit, thereby the wetting ability that makes hydrophilic component is big to the wetting ability that can increase normal polyester synthon surface, stain remover is promptly attached on this surface, this hydrophilic segment preferably contains the oxygen ethylene unit at least about 25%, contains 20-30 the oxypropylene unit and be particularly preferred at least about the component of 50% oxygen ethylene unit of having an appointment; Or (b) one or more hydrophobic components, comprise (i) C
3Oxygen alkene terephthalic acid ester moiety, if wherein this hydrophobic components also comprises the oxygen ethylene terephthalate, then oxygen ethylene terephthalate and C
3The unitary ratio of oxygen alkene terephthaldehyde base acid esters is about 2: 1 or is lower, (ii) C
4-C
6Alkene or oxidation C
4-C
6Alkene part, or their mixture, (iii) poly-(vinyl ester) part, preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester).
Typically, be about 200 in the polymerization degree of (a) polyoxyethylene part in (i), although also can use the higher polymerization degree, preferred 3 to about 150; 6 to about 100 the polymerization degree more preferably.Suitable oxidation C
4-6The alkene hydrophobic part comprise (but being not limited to this) as be issued to 26 days January in 1988 at Gosselink in the U.S. Pat 4721580 disclosed those as MO
3S (CH
2) nOCH
2CH
2The polymerization stain remover end-blocking part of O-, M is a sodium in the formula, n is the integer of 4-6.
The polymerization stain remover that uses among the present invention also comprises the copolymerization block and the analogue thereof of glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalate or polyoxypropylene terephthalate.
Poly-to contain (vinyl ester) hydrophobic part is that the stain remover of feature comprises the graft copolymer such as the C of poly-(vinyl ester)
1-6Vinyl ester preferably grafts on poly-(vinyl-acetic ester) on polyoxygenated alkene main chain such as the polyoxyethylene main chain.European patent application 0219048 referring to people such as disclosed Kud on the 22nd April in 1987.This commercially available class stain remover comprises SOKALAN type material, and for example SOKALAN HP-22 is produced by BASF (West Germany).
A preferred class stain remover is the multipolymer with glycol terephthalate and polyoxyethylene (PEO) terephthalate random block.The molecular weight of this polymerization stain remover is about 25000 to about 55000.Referring to the U.S. Pat 3959230 that was issued to Hays on May 25th, 1976 be issued to the U.S. Pat 3893929 of Basadur on July 8th, 1975.
Another kind of preferred polymerization stain remover is the polyester that has the glycol terephthalate repeating unit, wherein contain the glycol terephthalate unit of 10%-15% (weight) and the polyoxyethylene terephthalate unit of 90%-80% (weight), it is that the polyoxyethylene glycol of 300-5000 obtains by weight-average molecular weight.The example of this polymkeric substance comprises commercially available ZELCON5126 (Dupont production) and MILEASE T (ICI production).Be issued to the U.S. Pat 4702857 of Gosselink referring on October 27th, 1987.
Also having a kind of preferred polymerization stain remover is the sulfonated products that is essentially the linear ester oligopolymer, contains terephthaloyl and oxygen ethyleneoxy group repeating unit oligomer ester main chain, and the terminal portions that links to each other with this main chain covalency.The U.S. Pat 4968451 that be issued to J.J.Scheibel and E.P.Gosselink November 6 nineteen ninety has complete description to these stain removers.Other polymerization stain removers that are suitable for comprise the terephthalate polyester in the U.S. Pat 4711730 that was issued to people such as Gosselink on December 8th, 1987, be issued to the negatively charged ion end-blocking oligomer ester in the U.S. Pat 4721580 of Gosselink on January 26th, 1988 and be issued to block polyester oligopolymer in the U.S. Pat 4702857 of Gosselink on October 27th, 1987.
Preferred polymerization stain remover also comprises the stain remover in the U.S. Pat 4877896 that was issued to people such as Maldonado on October 31st, 1989, this patent disclosure the negatively charged ion end capped terephthalate of sulfo group aroyl particularly.
If the use stain remover, then its consumption be generally detergent composition weight of the present invention about 0.01% to about 10.0%, typically be about 0.1% to about 5%, preferred about 0.2% to about 3.0%.
Another kind of preferred stain remover is the oligopolymer that has terephthaloyl unit, the different terephthaloyl of sulfo group unit, oxygen ethyleneoxy group and oxygen-propylene repeating unit.Repeating unit forms oligopolymer main chain and preferred isethionate end-blocking termination with improvement.Particularly preferred such stain remover contains 1 the different terephthaloyl of the sulfo group unit of having an appointment; 5 terephthaloyl unit; ratio is about 1.7 to about 1.8 oxygen inferior ethoxyl and oxygen-1, the inferior propoxy-unit of 2-and two 2-(2-hydroxyl-oxethyl)-ethylsulfonic acid sodium end-blocking unit.The stain remover that is somebody's turn to do also contains about 0.5% to about 20% minimizing crystallization-stable agent of oligopolymer weight, and this stablizer is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and their mixture.Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach activator
Detergent composition of the present invention can randomly contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach activators.When containing SYNTHETIC OPTICAL WHITNER, SYNTHETIC OPTICAL WHITNER typically is detergent composition, in particular for 1% to 40% of the detergent composition of laundering of textile fabrics, more typically is 5% to 30%.If contain bleach activator, its content typically is 0.1% to 60% of the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach activator, more typically is 0.5% to 40%.
SYNTHETIC OPTICAL WHITNER used herein can be to detergent composition at cleaning fabric, clean crust, or other is known now or with any SYNTHETIC OPTICAL WHITNER useful in the known cleaning use.They comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.
The present invention also can use peroxygen bleach.Suitable peroxy bleaching agent compound comprises yellow soda ash peroxyhydrate and its equivalent " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is by the DuPont commercial production).
It is about 500 to about 1000 microns dried particles that preferred percarbonate bleach comprises median size, and this particle is less than about 200 microns about 10% (weight) that is no more than, greater than about 1250 microns about 10% (weight) that is no more than.Percarbonate can optionally use silicate, borate or water soluble surfactant active to apply.Preferred coating agent is based on the mixture of carbonate/sulfate.Percarbonate can be from various commercial source such as FMC, and Solvay and Tokai Denka obtain.
The another kind of SYNTHETIC OPTICAL WHITNER that can use without restriction comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-nonyl amino-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the U.S. Pat 4483781 that on November 20th, 1984 was issued to Hartman, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740446, February in 1985 people's such as disclosed Banks on the 20th european patent application 0133354 and November 1 nineteen eighty-three are issued in people's such as Chung the U.S. Pat 4412934.Highly preferred SYNTHETIC OPTICAL WHITNER also comprises as 6-nonyl amino-6-oxo of describing in the U.S. Pat 4634551 that licenses to people such as Burns on January 6th, 1987 crosses oxy hexanoic acid.
The present invention also can use the mixture of SYNTHETIC OPTICAL WHITNER.Peroxygen bleach, perborate, Sodium peroxoborate (for example its monohydrate or tetrahydrate) for example, percarbonate etc. preferably are used in combination with bleach activator, and this causes producing on the spot the peroxy acid corresponding to bleach activator in the aqueous solution (promptly at washing process).The various non-limiting examples of activator are disclosed in and license in people's such as Mao the U.S. Pat 4915854 and U.S. Pat 4412934 April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are typical activators, also can use their mixture.Typical SYNTHETIC OPTICAL WHITNER of useful herein other and activator are in addition referring to U.S. Pat 4634551.
Highly preferred acyl derivative bleach activator is the bleach activator with following formula:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L is R wherein
1Be to contain 6 the alkyl of having an appointment, R to about 12 carbon atoms
2Be to contain 1 the alkylidene group of having an appointment, R to about 6 carbon atoms
5Be H or contain have an appointment 1 alkyl, aryl or alkylaryl that L is the leavings group of any appropriate to about 10 carbon atoms.Leavings group is owing to perhydroxyl radical negatively charged ion nucleophilic attack on bleach activator, the substituted any group of result.Preferred leavings group is a phenolsulfonate.
The preferred embodiment of following formula bleach activator comprises (6-capryloyl-hexanoyl) oxygen base benzene sulfonate, (6-nonanoyl hexanoyl) oxygen base benzene sulfonate, (6-decanoyl-hexanoyl) oxygen base benzene sulfonate; with their mixture; as in the United States Patent (USP) 4634551 should, incorporate into herein, draw and be reference.
Another kind of bleach activator comprises in the U.S. Pat 4966723 that is issued to people such as Hodge October 30 nineteen ninety (incorporate into herein, draw be with reference to) disclosed benzo oxazinyl promoting agent.The preferred promoting agent of the height of benzo oxazinyl is:
Another kind of preferred bleach activator comprises the acyl lactam promoting agent, especially acyl caprolactam and acyl group Valerolactim, and chemical formula is:
R wherein
6Be H or have 1 alkyl, aryl, alkoxy aryl or alkylaryl to about 12 carbon atoms.Highly preferred lactan promoting agent comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5, the 5-trimethylammonium is acyl group Valerolactim and their mixture.Also (incorporate into herein, draw and be reference referring to the U.S. Pat 4545784 that was issued to Sanderson on October 8th, 1985.), wherein disclose acyl caprolactam and be adsorbed in the Sodium peroxoborate.Another kind of preferred bleach activator comprises the cationic bleach promoting agent.
Those SYNTHETIC OPTICAL WHITNER except the oxygen bleaching agent also are well known in the art, and can be used for the present invention.Make us an interested class non-oxygen bleaching agent especially and comprise photosensitization SYNTHETIC OPTICAL WHITNER such as sulfonated Phthalocyanine Zinc and/or aluminium.Also license to people's such as Holcombe U.S. Pat 4033718 referring on July 5th, 1977.If use, detergent composition typically contains such SYNTHETIC OPTICAL WHITNER of 0.025% to 1.25% (weight), especially Phthalocyanine Zinc sulfonate.
If necessary, bleaching compounds can be used manganic compound catalysis.This compounds is a compound well known in the art, it comprises, for example disclosed manganese-based catalyst in U.S. Pat 5246621, US5244594, US 5194416, US 5114606 and European patent EP 549271A1, EP549272A1, EP 544440A2 and EP 544490A1.The preferred embodiment of such catalyzer comprises Mn
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
2, Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
3, Mn
IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH
3)
3(PF
6) and their mixture.Other metal matrix bleaching catalysts are included in those disclosed among U.S. Pat 4430243 and the US 5114611.The purposes that has the manganese of various complex ligands also has report: US4728455 in following United States Patent (USP), US 5284944, and US 5246612, and US 5256779, and US 5280117, and US 5274147, and US 5153161, and US 5227084.Polymeric dispersant
It is more favourable that polymeric dispersant can be used for the present composition with the content of 0.1% to 7% (weight), especially when zeolite and/or layered silicate washing assistant exist.Suitable polymeric dispersant comprises polymeric multi-carboxylate and polyoxyethylene glycol, and other known polymeric dispersants of this area also can use.Though should not stick to theory, but it is believed that when polymeric dispersant to discharge peptization and anti-redeposition and other washing assistant (comprising low-molecular-weight multi-carboxy compound) when being used in combination by means of crystal growth restraining effect, particulate soil, it has improved the performance of total detergent builder compound.
By suitable unsaturated monomer, the polymerization of the unsaturated monomer of preferred acid form or copolymerization can prepare the polymeric polycarboxylic acid salt material.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the unsaturated monomer acid that polymerization prepares suitable multi-carboxylate polymer.Herein among the multi-carboxylate polymer, contain the monomer segment that does not have carboxylate groups such as vinyl methyl ether, vinylbenzene, ethene etc. and be fit to, as long as it is no more than about 40% (weight).
Specially suitable multi-carboxylate polymer can obtain from vinylformic acid.Can be used for herein such is the water-soluble salt of polymeric acrylic acid based on the polymerizing acrylic acid thing.The molecular-weight average of this base polymer that exists with sour form is preferably about 2000-10000, and more preferably about 4000-7000 most preferably is about 4000-5000.The water-soluble salt of such acrylate copolymer can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.Such soluble polymer is a materials known.Be issued on March 7th, 1967 in the U.S. Pat 3308067 of Diehl and disclose such application of polypropylene hydrochlorate in detergent composition.
Multipolymer based on vinylformic acid/toxilic acid also can be as the preferred ingredient of dispersion/anti redeposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer that exists with sour form is preferably about 2000-100000, and more preferably about 5000-90000 most preferably is about 7000-80000.The ratio of acrylate moiety and toxilic acid part is generally about 30: 1 to about 1: 1, more preferably about 70: 30 to 30: 70 in this analog copolymer.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.The water-soluble salt of this class vinylformic acid/maleic acid is the known substance of describing in the disclosed european patent application 66915 in December 15 nineteen eighty-two, and the known substance of describing in the disclosed European patent EP 193360 on September 3rd, 1986, the latter has also described this base polymer that contains hydroxypropyl acrylate.Another kind of useful dispersion agent comprises the terpolymer of toxilic acid/vinylformic acid/vinyl alcohol or vinylacetate.This material also is disclosed in EP193160, comprises, for example, vinylformic acid/toxilic acid of 45/45/10/vinyl alcohol terpolymer.
The another kind of polymeric material that can be comprised is polyoxyethylene glycol (PEG).PEG also has the performance of dispersion agent except can be used as dirt removal-anti redeposition agent.The molecular-weight average that is used for the polyoxyethylene glycol of this purpose typically is about 500-100000, is preferably about 1000-50000, more preferably about 1500-10000.
The present invention also can use the polyamino acid dispersion agent, such as polyaspartic acid salts and polyglutamic acid dipersant, especially is used in combination with zeolite builders.Dispersion agent such as polyaspartic acid salts preferably have about 10000 molecular-weight average.Dirt removal/anti redeposition agent
Composition of the present invention can also optionally contain the water-soluble ethoxylated amine with dirt removal and antiredeposition performance.The granular detergent composition that contains these compounds typically contains the 0.01% water-soluble ethoxylated amine to about 10.0% (weight) of having an appointment; Liquid detergent composition typically contains has an appointment 0.01% to about 5%.
Most preferred decontamination and anti redeposition agent are the ethoxyquin tetrens.The example of ethoxylated amine further is described in being issued to the U.S. Pat 4597898 of VanderMeer on July 1st, 1986.Another kind of preferred dirt removal-anti redeposition agent is a disclosed cation compound in the European patent application EP 111965 of on June 27th, 1984 disclosed Oh and Gosselink.Other dirt removal/anti redeposition agents that can use in the present invention are included in disclosed ethoxylated amine polymer in the European patent application EP 111984 of disclosed Gosselink on the 27th June in 1984; Disclosed amphiphilic polymers in the European patent EP 112592 of disclosed Gosselink on the 4th July in 1984; With disclosed amine oxide in the U.S. Pat 4548744 that is issued to Connor on October 22nd, 1985.Other dirts as known in the art remove and/or anti redeposition agent also can be used in the composition of the present invention.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.Dye transfer inhibitor
The present composition can comprise that also one or more effectively suppress dyestuff from the material of a kind of fabric to another kind of fabric migration in cleaning process.Usually, this dye transfer inhibitor comprises polyvinylpyrrolidonepolymers polymers, polyamines N-oxide polymer, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, manganese phthalocyanine, peroxidase and their mixture.If use, the content of these reagent typically is 0.01% to 10% of composition weight, and is preferred 0.01% to 5%, more preferably 0.05% to 2%.
Particularly, be preferred for polyamines N-oxide polymer of the present invention and contain the unit with following structural: R-A
xThe unit of-P; Wherein P is a polymerizable unit, and the N-O base can be connected with this unit or the N-O base can form polymerizable unit a part or N-O base can be connected with two these unit; A be down one of array structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is a fatty group, the ethoxyquin fatty group, and aromatic base, heterocyclic radical or alicyclic radical or they are combination arbitrarily, and wherein the nitrogen-atoms of N-O base can be connected with this group or the N-O group is the part of these groups.Preferred polyamines N-oxide compound be those wherein R be heterocyclic radical such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and their derivative.
The N-O group can be represented with following formula:
R wherein
1, R
2, R
3Be fat, aromatics, heterocycle or alicyclic group or their combination; X, v and z are 0 or 1; The nitrogen of N-O group can or form any part of aforementioned group by attack.Amine oxide unit pK＜10 of polyamines N-oxide compound, preferred pK＜7, more preferably pK＜6.
The present invention can use any main polymer chain, as long as the amine oxide polymkeric substance that forms is water miscible and has the dye migration rejection.The example of suitable polymer main chain is polyethylene polyolefine, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is that amine n-oxide and another kind of monomer type are the N-oxide compounds.The amine n-oxide polymkeric substance typically has 10: 1 to 1: 1000000 the amine and the ratio of amine n-oxide.But the quantity that is present in the azyloxy in the polyamine oxidase thing polymkeric substance can change by suitable copolymerization or suitable N-oxidisability.The polyamine oxidase thing can obtain with any polymerization degree almost.Typically, its average molecular weight range is 500-1000000; More preferably 1000-500000; 5000-100000 most preferably.Such preferable material can be called " PVNO ".
The most preferred polyamines N-oxide compound that can be used in the detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50000, and the ratio of amine and amine n-oxide is about 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being called " PVPVI ") also is preferred for herein.Preferred PVPVI has 5000-1000000, more preferably 5000-200000 and the most preferably molecular-weight average of 10000-20000.(average molecular weight range by as at " chemical analysis " of Barth etc., the 113rd volume, light scattering method of describing in " modernism of polymer property " determines that its disclosure is incorporated into herein, draws to be reference.)。The PVPVI multipolymer typically has 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1 the N-vinyl imidazole and the molar ratio of N-vinyl pyrrolidone.These multipolymers can be line style or branched.
The present composition also can use has molecular-weight average for about 5000 to about 400000, preferred about 5000 to about 200000 and more preferably from about 5000 to about 50000 Polyvinylpyrolidone (PVP) (" PVP ").PVP is known to the skilled in the detergent applications; For example, referring to EP-A-262897 and EP-A-256696, they are incorporated into herein, draw to be reference.It is about 500 to about 100000 that the composition that contains PVP also can contain molecular-weight average, preferred about 1000 to about 10000 polyoxyethylene glycol (" PEG ").Preferably, what discharge generation in washing soln is about 2: 1 to about 50: 1 by the PEG of ppm and the ratio of PVP, more preferably from about 3: 1 to about 10: 1.
Also can optionally contain the hydrophilic white dyes of general type of 0.005% to 5% (weight) in the detergent composition of the present invention, it also provides the dye migration restraining effect.If use, preferably contain this white dyes of 0.01% to 1% (weight) in the present composition.
Can be used for hydrophilic white dyes of the present invention and have structural formula:
R wherein
1Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; M is salt-forming cation such as sodium or potassium ion.
In following formula, work as R
1Be anilino, R
2Be N-2-two-when hydroxyethyl and M were positively charged ion such as sodium, whitening agent was 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid and disodium salt thereof.Such special whitening agent can be bought from Ciba-Geigy company is commercial according to trade(brand)name Tinopal-UNPA-GX.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that can be used in the detergent composition of the present invention.
In following formula, work as R
1Be anilino, R
2Be N-2-hydroxyethyl-N-2-methylamino-and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid disodium salt.Such special whitening agent can be bought from Ciba-Geigy company is commercial according to trade(brand)name Tinopal 5BM-GX.
In following formula, work as R
1Be anilino, R
2Be morpholino and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid, sodium salt.Such special whitening agent can be bought from Ciba-Geigy company is commercial according to trade(brand)name TinopalAMS-GX.
Other special white dyess that selection is used for the present invention provide especially effectively dye migration rejection when being used in combination with selected above-described polymeric dye migration inhibitor.This selected polymeric material (for example, PVNO and/or PVPVI) provide obviously better dye migration restraining effect with being used in combination in wash water solution of this selected white dyes (for example, Tmopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) than the situation of using one of their two kinds of detergent composition components separately.Though do not answer bound by theory, it is believed that it is because they have high-affinity to the fabric in the washing soln that such whitening agent works by this way, therefore can be at a good pace attached on these fabrics.This whitening agent can be by being called the parameter-definition of " consumption coefficient " attached to the degree on the fabric in washing soln.Consumption coefficient is typically expressed as: a) attached to whitening agent material and b on the fabric) ratio of initial whitening agent concentration in the washing liq.On this point of the present invention, the whitening agent with high relatively consumption coefficient is suitable for suppressing dye migration most.
Certainly, be understandable that the compound of the white dyes type that other are conventional can optionally be used for the present composition, so that the conventional fabric effect of " brightening " to be provided, rather than real dye migration restraining effect.This purposes is common with known in detergent formulations.
Can contain normally used any other component in conventional detergent composition according to detergent composition of the present invention, as soap, suds suppressor, softening agent, whitening agent, auxiliary enzymes and enzyme stabilizers.The application of nonionic polysaccharide ether and lipase binding substances
The present composition can be used for laundry detergent composition, fabric treatment composition and fabric sofetening composition and hard surface cleaner.Composition can be mixed with conventional particulate state, strip, pasty state, Powdered or liquid agent.This detergent composition is made in a usual manner, for example, for powder detergent composition, can use spraying drying or spray mixing method.
Polysaccharide of the present invention and the lipase mixt concentration in washing soln water is with 1ppm to 500ppm, preferred 5ppm's to 300ppm, the pH value of preferred washing soln is 7-11, more preferably 9-10.5.
The invention still further relates to the method for laundering of textile fabrics, it comprises that the fabric with this contacts with the scrubbed component that contains the routine of describing herein and the laundry aqueous solution of lipase of the present invention and nonionic polysaccharide ether.In a preferred method, use polyester and polyester-cotton BLENDED FABRIC.
The abbreviation of using in the EXAMPLE Example
In detergent composition of the present invention, the definition of abbreviation component has following meanings: XYAS C
1X-C
1YSodium alkyl sulfate 25EY and the oxyethane of average Y mole comprehensive with C
12-15Be main straight chain primary alcohol XYEZ with the oxyethane of average Z mole comprehensive with C
1X-C
1YIt is main straight chain
Every mole of primary alconol XYEZS and the oxyethane of average Z mole comprehensive with C
1X-C
1YAlkyl
Sodium sulfate TFAA C
16-18Alkyl N-methyl glucose amide silicate amorphous sodium silicate (SiO
2: Na
2O ratio=2.0) the NaSKS-6 chemical formula is δ-Na
2Si
2O
530: 70 the toxilic acid/main particle size range of acrylic acid multipolymer zeolite A of crystallization stratification silicate carbonate anhydrous sodium carbonate MA/AA molecular-weight average about 70000 be Na at the chemical formula of 1-10 micron
12(AlO
2SiO
2)
1227H
2The hydrated sodium aluminosilicate Citrate trianion two hydration trisodium citrate percarbonate of O water glass (SiO
2: Na
2O ratio=2: 0) applies the nothing that agent applies
Water SPC-D SYNTHETIC OPTICAL WHITNER, wherein the weight ratio of percarbonate and water glass is
39: 1CMC Xylo-Mucine DETPMP with trade(brand)name Dequest 2060 by Monsanto Company (Monsanto) sell two
Ethylidene triamine five (methylene phosphonic acid) PVNO molecular-weight average is the poly-of 10000 vinyl imidazole and vinyl pyrrolidone
(4-vinylpridine)-N-oxide block copolymer terre verte mud calcium montmorillonite for example, Colin Stewart Minchem Lid granular suds suppressing agent 12% siloxanes/silicon-dioxide, 18% Stearyl alcohol, 70% starch, with
There is the LAS straight chain C in particle form
12The sad secondary soap surfactant phosphoric acid salt tripoly phosphate sodium STPP TAED tetra acetyl ethylene diamine PVP polyvinylpyrrolidonepolymers polymers HMWPEO high molecular weight peo MC1 molecular weight of sodium alkyl benzene sulfonate TAS tallow alkyl sodium sulfate SS formula 2-butyl is 110000 to 130000 methyl cellulose ether, can be with trade(brand)name
Metolose has bought MC2 tylose MH50 from Shin Etsu Chemicals, has the molecular weight greater than 10000, can from
Hoechst has bought MC3 Methocel F50, has the molecular weight greater than 10000, can be from Dow
Chemicals has bought the lipase that lipase 2 is sold with trade(brand)name lipolase by Novo Nordisk A/S, its tool
There is the active lipase 1 of 100KLU/ gram to plant lipase TAE25 tallow alcohol ethoxylate (25) embodiment 1 that Pseudomonas fetal hair bacteria strain DSM4106 derives and obtains by corruption
Prepare following laundry detergent composition A, B, C, D, E, F and G.
A B C D E F G45AS/25AS 9.1 9.1 9.1 9.1 9.1 9.1 9.1 ( 3∶1 ) 35AE3S 2.3 2.3 2.3 2.3 2.3 2.3 2.324E5 4.5 4.5 4.5 4.5 4.5 4.5 4.5TFAA 2.0 2.0 2.0 2.0 2.0 2.0 2.0A 10.2 10.2 10.2 10.2 10.2 10.2 10.21-----0.4 0.42-0.5 0.5 0.5 0.5--MC1--1 0.2 0.5 0.2 0.5Na SKS-6/ 10.6 10.6 10.6 10.6 10.6 10.6 10.6 ( 79∶21 ) 7.6 7.6 7.6 7.6 7.6 7.6 7.6TAED 5 6.67 6.67 6.67 6.67 6.67 6.67 22.5 22.5 22.5 22.5 22.5 22.5 22.5DETPMP 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.55 0.55 0.55 0.55 0.55 0.55 0.55 3.1 3.1 3.1 3.1 3.1 3.1 3.1CMC 0.4 0.4 0.4 0.4 0.4 0.4 0.4PVNO 0.03 0.03 0.03 0.03 0.03 0.03 0.03 1.5 1.5 1.5 1.5 1.5 1.5 1.5/ 100％
Use the Miele washing machine, short circulation, 40 ℃, hardness is the Newcastle town water of 12dH, single dose carries out detergency test.Even will pollute mixture with brush and be coated on the fabric and be allowed to condition at dried overnight on the experiment table.
With the different degreasing performance of the unit of scoring of group (psu) record, positive number represents to have better properties than reference product.Use following grading system (psu grade):
0=is identical
I think that this is better 1=
I know that this is good slightly 2=
3=this get well a lot
This is best for 4=
Scoring is to be finished by expert's scorer under light control bar spare.The repeat samples number of Shi Yonging is 6 in test.
S represents that observed difference is significant, confidence level 95%.Common 0+1.0s+2.1s starch spot Ragu on the scoring detergent composition A of unit of the group detergent composition B detergent composition C cotton
*The common spot Ragu of 0+1.8s+3.5sChicken** 0+0.6+1.65Tuna*** 0+0.7+1.2polycotton last 0+0.25+1.25
*0+0.1+0.9Chicken
*0+0.4s+1.6sRagu
*: Ragu Traditional Recipe
TM, Pasta sauce, Brooke Bond FoodsLtd.Chicken
**：Chicken?Provencal，Schwartz
TM，Mc?Cormick?Foods。Tuna
***：Tuna?Provencal，Colman’s?sauce?for?tuna
TM，Colmans。Embodiment 2
Be prepared as follows according to particulate state fabric cleaning composition of the present invention:
I II III IV lipase 1 0.5 0.5 0.5 0.5MC1 0.75--0.75MC2-0.5--MC3--0.5-LAS 22.0 22.0 22.0 22.0 phosphate 23.0 23.0 23.0 23.0 carbonate 23.0 23.0 23.0 23.0 silicate 14.0 14.0 14.0 14.0 Wessalith CSs 8.2 8.2 8.2 8.2DETPMP 0.4 0.4 0.4 0.4 sodium sulphate 5.5 5.5 5.5 5.5 lipase 2---0.5 water/submember adds to 100% embodiment 3
Be prepared as follows according to particulate state fabric cleaning composition of the present invention:
I II III IVLAS 12.0 12.0 12.0 12.0 Wessalith CSs 26.0 26.0 26.0 26.0SS 4.0 4.0 4.0 4.024AS 5.0 5.0 5.0 5.0 citrates 5.0 5.0 5.0 5.0 sodium sulphate 17.0 17.0 17.0 17.0 perborate 16.0 16.0 16.0 16.0TAED 5.0 5.0 5.0 5.0MC2-0.5--0.6 water/submember adds to 100% embodiment 4 to MC1 0.5--0.5MC3--0.5-lipase 11111 lipase 2---
Be prepared as follows according to the granular fabric cleaning composition that is particularly useful for washing yarn dyed fabric of the present invention:
I II III IV V VILAS 11.4 10.7 11.4 10.7--TAS 1.8 2.4 1.8 2.4--TFAA----4.0 4.045AS 3.0 3.1 3.0 3.1 10.0 10.045E7 4.0 4.0 4.0 4.0--25E3S----3.0 3.086E11 1.8 1.8 1.8 1.8--25E5----8.0 8.0 14.0 15.0 14.0 15.0 7.0 7.0----10 10 3.0 2.5 3.0 2.5 3.0 3.0A 32.5 32.1 32.5 32.1 25.0 25.0Na-SKS-6----9.0 9.0MA/AA 5.0 5.0 5.0 5.0 5.0 5.0DETPMP 1.0 0.2 1.0 0.2 0.8 0.8MC2--0.75 0.75 0.75-MC1 0.75 0.75---0.752 0.5 0.5 0.5 0.5 0.5 0.5 2.0 2.5 2.0 2.5-- 3.5 5.2 3.5 5.2 3.0 3.0PVP 0.3 0.5 0.3 0.5-- ( 4-----0.2 0.2 )-N-/- 0.5 1.0 0.5 1.0-- 0.1 0.2 0.1 0.2--/ 100％5
Be prepared as follows according to particulate state fabric cleaning composition of the present invention:
I II IIILAS 6.5 8.0 8.0 sulfate 15.0 18.0 18.0 Wessalith CSs 26.0 22.0 22.0 sodium nitrilo triacetates 5.0 5.0 5.0PVP 0.5 0.7 0.7TAED 3.0 3.0 3.0 boric acid 4.0--perborate 0.5 1.0 1.0 phenolsulfonates 0.1--MC3 0.5--MC1-0.75 0.75 lipase 1--0.5 lipase 2 0.5 0.5-silicate 5.0 5.0 5.0 carbonate 15.0 15.0 15.0 water/submember adds to 100% embodiment 6
Be prepared as follows according to the granular fabric cleaning composition that softness is provided by washing of the present invention:
I II III IV V VI45AS--10.0 10.0-10.0LAS 7.6 7.6--7.6-68AS 1.3 1.3--1.3-45E7 4.0 4.0--4.0-25E3--5.0 5.0-5.0-- 1.4 1.4 1.0 1.0 1.4 1.0- 5.0 5.0 3.0 3.0 5.0 3.0Na-SKS-6--11.0 11.0-11.0A 15.0 15.0 15.0 15.0 15.0 15.0MA/AA 4.0 4.0 4.0 4.0 4.0 4.0DETPMMP 0.4 0.4 0.4 0.4 0.4 0.4 15.0 15.0--15.0---15.0 15.0-15.0TAED 5.0 5.0 5.0 5.0 5.0 5.0 10.0 10.0 1.00 10.0 10.0 10.0HMWPEO--0.1 0.1-0.1MC3-0.75-0.75--MC1 0.75-0.75-0.75 0.751----0.6 0.62 0.75 0.75 0.75 0.75-- 3.0 3.0 5.0 5.0 3.0 5.0 10.0 10.0 10.0 10.0 10.0 10.0 1.0 1.0 4.0 4.0 1.0 4.0CMC 0.2 0.2 0.1 0.1 0.2 0.1/ 100％7
Be prepared as follows according to liquid fabric cleaning composition of the present invention:
I II25AS 16.5-25AE3S 3.00 18.00TFAA 5.50 4.5024E5 5.63 2.00 aliphatic acid/oleic acid 7.50 2.00 citric acids 1.00 3.00 ethanol 1.37 3.49 propane diols 11.75 7.50MEA 8.00 1.00NaCS-2.50Na/Ca formic acid-0.09NaOH 1.00 3.11 lipase 1 0.13 0.12 proteinase-10 .48 0.88 cellulose ether 0.03 0.05 amylase 0.13 0.120 boric acid (Borax)/calcium formate 3.25 3.50 brightening agents, 0.15 0.05MA/AA 0.22 1.18MC1,0.5 0.5DETPMP 0.94-water and submember add to 100%
Claims (13)
1. detergent composition, it contains at least 1% tensio-active agent, the detergent composition that it is characterized in that this is in conjunction with containing lipase and the molecular weight nonionic polysaccharide ether greater than 10000, and the activity that the lipase that is somebody's turn to do has makes every milligram of composition that is somebody's turn to do have the activity of 0.001LU at least.
2. according to the detergent composition of claim 1, the lipase that wherein is somebody's turn to do plants Pseudomonas fetal hair bacterium by corruption or its mixture obtains.
3. according to the detergent composition of one of claim 1 or 2, the lipase that wherein is somebody's turn to do is planted Pseudomonas fetal hair bacterium mutation D96L by corruption and is obtained.
4. according to each detergent composition in the aforementioned claim, the lipase that wherein is somebody's turn to do is that Pseudomonas fetal hair bacteria strain DSM 4106 is planted in corruption.
5. according to the detergent composition of one of claim 1 or 2, the nonionic polysaccharide ether that wherein is somebody's turn to do has 0.5 to 2.8 substitution value.
6. according to each detergent composition in the aforementioned claim, the nonionic polysaccharide ether that wherein is somebody's turn to do is ether of cellulose, starch ethers, dextran ether or their mixture.
7. according to the detergent composition of one of claim 1 or 2, the nonionic polysaccharide ether that wherein is somebody's turn to do is selected from non-ionic C
1-4Alkyl, C
1-4Hydroxyalkyl-, C
1-4Alkyl hydroxyalkyl polysaccharide and their mixture.
8. according to each detergent composition in the aforementioned claim, the nonionic polysaccharide ether that wherein is somebody's turn to do is methyl cellulose ether, ethyl hydroxyethyl cellulose ethers or their mixture.
9. according to each detergent composition in the aforementioned claim, the active lipase that wherein is somebody's turn to do (LU) is 10000: 1 to 1: 10 with the ratio of the nonionic polysaccharide ether (mg) that is somebody's turn to do.
10. according to each detergent composition in the aforementioned claim, the lipase that wherein is somebody's turn to do has makes every milligram of detergent composition have the activity of 0.005LU to 10LU.
11. according to each detergent composition in the aforementioned claim, the detergent composition that wherein is somebody's turn to do contains 0.01% to 10% the nonionic polysaccharide ether that is somebody's turn to do.
12. according to each detergent composition in the aforementioned claim, it contains 5% to 50% the surfactant system that is somebody's turn to do, the tensio-active agent that wherein is somebody's turn to do is selected from negatively charged ion, nonionic, zwitter-ion, amphoterics and their mixture.
13. a method of handling fabric, it comprises that the fabric with this contacts with the liquid, aqueous of binding substances of lipase that is somebody's turn to do that contains 1ppm to 500ppm and nonionic polysaccharide ether.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9502917A GB2297979A (en) | 1995-02-15 | 1995-02-15 | Detergent compositions containing a lipase enzyme |
| GB9502917.9 | 1995-02-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1181104A true CN1181104A (en) | 1998-05-06 |
Family
ID=10769613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96193171 Pending CN1181104A (en) | 1995-02-15 | 1996-02-06 | Detergent compositions comprising nonionic polysaccharide ethers and lipase enzymes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0820502A4 (en) |
| JP (1) | JPH11501958A (en) |
| CN (1) | CN1181104A (en) |
| BR (1) | BR9607507A (en) |
| GB (1) | GB2297979A (en) |
| WO (1) | WO1996025477A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501173B (en) * | 2006-01-23 | 2011-12-14 | 宝洁公司 | Enzyme and photobleach containing compositions |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2315767A (en) * | 1996-08-01 | 1998-02-11 | Procter & Gamble | Detergent compositions for laundering clothes with metal sulphate and a chelant |
| US5658870A (en) * | 1996-09-26 | 1997-08-19 | Leu; Shiow Jiuan Freida | Composition of super molecule active solid cleaning agent |
| DE19850012A1 (en) * | 1998-10-30 | 2000-05-04 | Aladin Ges Fuer Innovative Mik | New Paenibacillus pabuli strain DSM 10049 and 2-component cleaner, e.g. pipe degreaser, for biological disposal system containing triglyceride or fatty acid and nutrients in emulsion and supported microorganism spores |
| US7319112B2 (en) | 2000-07-14 | 2008-01-15 | The Procter & Gamble Co. | Non-halogenated antibacterial agents and processes for making same |
| EP1976966B1 (en) * | 2006-01-23 | 2013-12-18 | The Procter and Gamble Company | Enzyme and photobleach containing compositions |
| JP5378140B2 (en) * | 2009-10-07 | 2013-12-25 | 花王株式会社 | Method for producing liquid detergent composition |
| EP2581438A1 (en) * | 2011-10-12 | 2013-04-17 | The Procter and Gamble Company | Detergent composition |
| JP2019099821A (en) * | 2017-12-06 | 2019-06-24 | 花王株式会社 | Liquid washing agent composition for textile product |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174305A (en) * | 1975-04-02 | 1979-11-13 | The Procter & Gamble Company | Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents |
| US4136038A (en) * | 1976-02-02 | 1979-01-23 | The Procter & Gamble Company | Fabric conditioning compositions containing methyl cellulose ether |
| US4532067A (en) * | 1984-01-11 | 1985-07-30 | Lever Brothers Company | Liquid detergent compositions containing hydroxypropyl methylcellulose |
| US4740326A (en) * | 1987-02-19 | 1988-04-26 | The Procter & Gamble Company | Soil release polymer coated substrate containing a laundry detergent for improved cleaning performance |
| KR930702514A (en) * | 1990-09-13 | 1993-09-09 | 안네 제케르 | Lipase variant |
| DK46693D0 (en) * | 1993-04-23 | 1993-04-23 | Novo Nordisk As |
-
1995
- 1995-02-15 GB GB9502917A patent/GB2297979A/en not_active Withdrawn
-
1996
- 1996-02-06 WO PCT/US1996/001644 patent/WO1996025477A1/en not_active Application Discontinuation
- 1996-02-06 EP EP96904584A patent/EP0820502A4/en not_active Withdrawn
- 1996-02-06 CN CN 96193171 patent/CN1181104A/en active Pending
- 1996-02-06 BR BR9607507A patent/BR9607507A/en not_active Application Discontinuation
- 1996-02-06 JP JP8525003A patent/JPH11501958A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501173B (en) * | 2006-01-23 | 2011-12-14 | 宝洁公司 | Enzyme and photobleach containing compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9502917D0 (en) | 1995-04-05 |
| JPH11501958A (en) | 1999-02-16 |
| BR9607507A (en) | 1997-12-23 |
| WO1996025477A1 (en) | 1996-08-22 |
| GB2297979A (en) | 1996-08-21 |
| MX9706228A (en) | 1997-10-31 |
| EP0820502A4 (en) | 1998-12-23 |
| EP0820502A1 (en) | 1998-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1086732C (en) | Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents | |
| CN1117765C (en) | Laundry detergent compositions with cellulosic based polymers to provide appearance and integrity benefits to fabrics laundered therewich | |
| CN1151753A (en) | Handwash laundry detergent composition having improved mildness and cleaning performance | |
| CN1247558A (en) | Laundry detergent compsns. with cellulosic polymers available for appearance and integrity of washing fabric | |
| CN1302325A (en) | Laundry detergent compositions with cellulosic based polymers to provide appearance and integrity benefits to fabrics laundered therewith | |
| CN1170916C (en) | Laundry detergent compositions comprising dye fixatives | |
| CN102159693A (en) | Dual character biopolymer useful in cleaning products | |
| CN1159824A (en) | Handwash laundry detergent compositions | |
| CN1025870C (en) | Detergent compositions | |
| CN1387563A (en) | Bleaching detergent compositions | |
| CN1145093A (en) | Laundry detergent bars with improved whitening and dye transfer inhibition | |
| CN1181104A (en) | Detergent compositions comprising nonionic polysaccharide ethers and lipase enzymes | |
| CN1233274A (en) | Hand wash laundry detergent compositions containing a combination of surfactants | |
| JP2735663B2 (en) | Detergent composition containing cellulase granules | |
| CN1142850A (en) | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions | |
| CN1086733C (en) | Detergent composition comprising amylase enzyme and nonionic polysaccharide ether | |
| CN1184500A (en) | Detergent composition comprising nonionic polysaccharide ether and non-soap anionic surfactant | |
| CN1174569A (en) | Detergent composition containing combination of nonionic polysaccharide ether with synthetic oxyalkylene-containing soil release agent | |
| CN1104488C (en) | Detergent compositions having suds suppressing properties | |
| CN1175278A (en) | Perfumed bleaching compositions | |
| CN1083004C (en) | Bleach compositions comprising protease enzyme | |
| AU616545B2 (en) | Detergent composition with fabric softening properties | |
| CN1142849A (en) | Percarbonate detergent compositions | |
| CN1193992A (en) | Peroxide bleaching compositions containing fabric protecting agent | |
| CN1131968A (en) | Granular detergent composition containing secondary (2,3) alkyl sulfate surfactant and bleach/bleach activator system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |