CN1138874A - Detergent compsn. containing polyamine N-oxide pllymers - Google Patents

Abstract

Use of polyamine N-oxide polymers which contain units having structural formula (I) as a chelating agent in detergent formulations, wherein P is a polymerisable unit, whereto the N-O group can be attached to or wherein the N-O group forms part of the polymerisable unit. A is (a), (b), (c), -O-, -S-, (d); x is O or 1; R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.

Description

The detergent composition that comprises polyamine N-oxide pllymers

Invention field

The present invention relates to comprise the detergent composition of polyamine N-oxide pllymers.More particularly, the present invention relates to the usage that polyamine N-oxide pllymers is removed the pigment stain.

Background of invention

For many years, detergent composition comprises the sequestrant and/or the SYNTHETIC OPTICAL WHITNER of pigment stain such as the tea, coffee, wine and the fruit stain that are used to remove relevant family expenses washing.

Therefore sequestrant and the heavy metal reaction that is present in this stain provide the stain removal effect by extracting metals ion from stain.

P contained compound has been proved to be and has been very suitable for as sequestrant.Yet because this compound causes the eutrophication in lake and river, the use in detergent composition has caused people's growing interest to P contained compound.This forces the detergent formulation teacher to limit the phosphorus content of detergent composition, needs preparation to comprise the cloth-washing detergent that efficient is lower than the sequestrant of conventional phosphoric acid salt that uses or polyphosphate.These requirements make total according to cleaning efficiency and to prepare effective detergent composition according to soil-removing action particularly complicated.Therefore, very hope can be prepared and be comprised the phosphorus component that contains that has reduced amount, but still has the good cleaning and the composition of clean effect.

Have now found that some polyamine N-oxide pllymers is very effective aspect removal pigment stain.This discovery makes it possible to be made into the good cleaning of demonstration and the detergent composition of clean effect.

Summary of the invention

The present invention relates to comprise the detergent composition that contains the unitary polyamine N-oxide pllymers of following structural formula:

Wherein, P is a polymerizable unit, the N-O group can be connected thereto face or wherein the N-O group constitute the part of polymerizable unit or the combination of the two.A is

-O-,-S-,

X is 0 or 1;

R is the group of aliphatic, ethoxylated fat family, aromatic, heterocyclic or alicyclic ring, or its arbitrary combination, and the nitrogen of N-O group can be connected thereto face, or wherein the nitrogen of N-O group constitutes the part of these groups.

The detailed description of invention

Composition of the present invention comprises the polyamine N-oxide pllymers as a kind of neccessary composition, and it comprises the unit of following structural formula:

P is a polymerizable unit, the N-O group can be connected thereto face or wherein the N-O group constitute the part of polymerizable unit or the combination of the two.A is

-O-,-S-, X is 0 or 1

R is aliphatic, ethoxylated fat family, aromatic, heterocyclic or the group of alicyclic ring or their arbitrary combination, and the nitrogen of N-O group can be connected thereto face, or wherein the nitrogen of N-O group is the part of these groups.

The N-O group can be represented with following general formula:

R wherein ₁, R ₂, R ₃Be aliphatic group, group or its combination fragrance, heterocyclic or alicyclic ring, x or/and y or/and z is 0 or 1, wherein the nitrogen of N-O group can be connected, or wherein the nitrogen of N-O group constitutes the part of these groups.

The N-O group can be that the part of polymerizable unit (P) maybe can be connected on the polymer backbone, or the combination of the two.

Wherein the N-O group constitutes the suitable polyamine N-oxide of a polymerizable unit part, comprises that wherein R is selected from polyamine N-oxide aliphatic, aromatic, alicyclic ring or the heterocyclic group.

The said polyamine N-oxide of one class comprises that the nitrogen of N-O group wherein constitutes the polyamine N-oxide group of the part of this R-group.Preferred polyamine N-oxide compound be those wherein R be a class such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.

Another kind of said polyamine N-oxide comprises that the N of N-O group wherein links the polyamine N-oxide group on the R-group.

Other suitable polyamine N-oxide is that the N-O group is linked the polyamine oxide compound on the polymerizable unit.A preferred class of these polyamine N-oxide is the polyamine N-oxide with general formula (I), and wherein R is the group of fragrant, heterocyclic or alicyclic ring, and wherein the nitrogen of N-O functional group is the part of said R group.The example of these classifications is that wherein R is a kind of polyamine oxide compound such as heterogeneous ring compounds such as pyridine, pyrroles, imidazoles and derivatives thereof.

Another kind of preferred polyamine N-oxide compound is the polyamine oxide compound with general formula (I), and wherein R is the group of fragrant, heterocycle or alicyclic ring, and wherein the nitrogen of N-O functional group is linked on the said R group.

The example of these classifications is that wherein the R base is aromatic polyamine oxide compound such as phenyl.

As long as the amine oxide polymkeric substance that forms is water miscible, then any polymer backbone can use.The example of suitable polymer backbone is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and composition thereof.

Amine n-oxide polymkeric substance of the present invention typically has amine to amine n-oxide ratio 10: 1 to 1: 1000000.Yet being present in the amine oxide in the polyamine oxide polymer or the quantity of group can change with suitable copolymerization or suitable N-oxidisability.Preferably, amine is 2: 3 to 1: 1000000 to the ratio of amine n-oxide.More preferably 1: 4 to 1: 1000000, most preferably 1: 7 to 1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and wherein a kind of monomer is an amine n-oxide, and another kind of monomer is amine n-oxide or is not.The amine oxide unit PK of polyamine N-oxide _a＜10, preferred PK _a＜7, more preferably PK _a＜6.

The polyamine oxide compound can be with almost any polymerization degree acquisition.If this material has required water-soluble and dirt suspending power, the polymerization degree is not crucial so.

Typically, molecular-weight average in 5,000 to 1000,000 scopes, preferably 5,000-100,000, more preferably 10,000-100,000, most preferably 30,000-50,000.

Typically, polyamine N-oxide amount of the present invention is 0.01%-10%, more preferably 0.05%-5%, most preferably 0,1%-3% (based on the weight of detergent composition).Make the method for polyamine N-oxide:

The production of polyamine N-oxide can be by making amine monomers polymerization and finishing with a kind of suitable resulting polymkeric substance of oxygenant oxidation, and perhaps amine oxide monomer self can be aggregated and obtains polyamine N-oxide.

Polyamine N-oxide synthetic can be by polyvinyl-pyridine N-oxides synthesize to come example.

Derive from Polysciences poly 4 vinyl pyridine (mw.50000,5.0g 0.0475mole) are pre-dissolved in the 50ml acetate, and through dropper with peracetic acid solution (25g Glacial acetic acid, 6.4g 30%Vol.H ₂O ₂Solution and several H ₂SO ₄Obtain the 0.0523mols peracetic acid) handle.Mixture stirred 30 minutes down in envrionment temperature (32 ℃).Use then the oil bath heated mixt to 80-85 ℃ 3 hours, placement is spent the night.The polymers soln that obtains mixes with 11 acetone under stirring then.The pale brown look thick slurry that forms at the bottom of bottle is used 11 washing with acetones once more, obtains the light coloured crystalline solid.Solid is used washing with acetone by gravity filtration, uses P then ₂O ₅Dry.

The amine of this polymkeric substance: the amine n-oxide ratio is 1: 4.Detergent additives

Various tensio-active agents can be used in the detergent composition.The negatively charged ion of one quasi-representative, nonionic, amphoteric and zwitterionic enumerate and the kind of these tensio-active agents is disclosed in and authorized in the United States Patent (USP) 3,664,961 of Norris on May 23rd, 1972.

The mixture of anion surfactant is specially adapted to herein, and especially weight ratio is 5: 1 to 1: 2, and preferred 3: 1 to 2: 3, the more preferably mixture of 3: 1 to 1: 1 sulfonate and sulfate surfactant.Preferred sulfonate is included in the alkylbenzene sulfonate that has 9-15, a particularly 11-13 carbon atom in the alkyl, and α-sulfonated fatty acid methyl ester, and wherein lipid acid is from C ₁₂-C ₁₈The fat source material is preferably from C ₁₆-C ₁₈The fat source material.In each case, positively charged ion all is a basic metal, preferred sodium.Preferred sulfate surfactant is the alkyl-sulphate that 12-18 carbon atom arranged in the alkyl, in its optional and alkyl 10-20 is arranged, and preferably the average degree of ethoxylation of 10-16 carbon atom is the vitriol mixing of the ethoxylation of 1-6.Here the example of preferred alkyl-sulphate is tallow alkyl vitriol, coconut alkyl-sulphate and C _14-15Alkyl-sulphate.Positively charged ion in every kind of situation also all is an alkali metal cation, preferred sodium.

The nonionogenic tenside that one class is suitable in the present invention is the condenses of oxyethane and a kind of hydrophobic part, obtains a kind of average hydrophile-lyophile balance (ALB) value and is 8-17, preferably 9.5-13.5, the more preferably tensio-active agent of 10-12.5.Hydrophobic (oleophylic) part can be aliphatic or aromatic in nature; Can easily be regulated with the length of the polyoxyethylene thiazolinyl of any concrete hydrophobic group condensation, obtained having between a kind of wetting ability and hydrophobic parts the water-soluble cpds of required quality of balance.

Particularly preferred this class nonionogenic tenside is the C that every mole alcohol contains 3-8moles oxyethane ₉-C ₁₅Primary alcohol ethoxylate, especially every mole alcohol contains the C of 6-8moles oxyethane ₁₄-C ₁₅Primary alconol and every mole alcohol contain the C of 3-5moles oxyethane ₁₂-C ₁₄Primary alconol.

Another kind of ionic surfactant pack is drawn together the following alkyl polyglycoside compound of general formula:

RO (C _nH _2nO) _tZ _xWherein Z is a kind of part from glucose; R is a saturated hydrophobic alkyl that contains 12-18 carbon atom; T is 0-10, and n is 2 or 3; X is 1.3-4, and this compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the many glycosides of short-chain alkyl that are less than 50%.This compounds and be disclosed in EP-B 0070077,0075996 and 0094118 in detergent application.

What also be suitable as nonionogenic tenside is the following polyhydroxy fatty acid amide surfactant of molecular formula: R wherein ¹Be H, or R ¹Be C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R ²Be C _5-31Alkyl, and Z be a kind of have have at least 3 polyhydroxy alkyls of directly linking the straight-chain alkyl chain of the hydroxyl on the chain, or its oxyalkylated derivative.Preferably, R ¹Be methyl, R ²It is a straight chain C _11-15The alkyl or alkenyl chain, as the coconut alkyl, or its mixture and Z are from a kind of reducing sugar, such as glucose, fructose, maltose, lactose in a kind of reductive amination reaction.

Composition of the present invention also can comprise builder system.The builder system of any routine is applicable to herein, comprise silico-aluminate material, silicate, multi-carboxylate and lipid acid, such as edetate, such as metal ion chelation agents such as amino polyphosphate, particularly ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acids.

Suitable washing assistant can be a kind of inorganic ion exchange material, normally inorganic hydrated aluminosilicate material, and the synthetic zeolite of a kind of hydration of more specifically saying so is such as hydrated zeolite A, X, B or HS.

Another kind of suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is a kind of by water glass (Na ₂Si ₂O ₅) crystalline layered silicate formed.

The suitable multi-carboxylate who comprises a carboxyl is included in disclosed lactic acid, glycol acid and ether derivant thereof in Belgian patent 831,368,821,369 and 821,370.The multi-carboxylate who comprises two carboxyls is included in German Offenlegenschrift 2,446,686 and 2,446,687 and United States Patent (USP) 3,935, the water-soluble salt of the succsinic acid described in 257, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, connection oxyacetic acid, tartrate, tartronic acid and fumaric acid, and ether carboxylate and at the sulfinyl carboxylate salt described in the Belgian patent 840,623.The multi-carboxylate who contains three carboxyls comprises, especially, in English Patent 1,379, water-soluble citric acid, aconitate and citraconate described in 241 and succinic acid derivative such as carboxy methoxy-succinic acid salt, the newborn oxygen base succinate of in Holland application 7205873, describing and in English Patent 1,387, oxygen Quito carboxylate salt described in 447, as 2-oxa--1,1,3-tricarballylic acid salt.

In English Patent 1,261, the disclosed multi-carboxylate who contains four carboxyls comprises the oxidation disuccinate in 829: 1,1,2, and 2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and comprise, be disclosed in British Patent No. 1,398, in 421 and 1,398,422 and U.S. Patent number 3,936, sulfosuccinic acid derivative in 448 is in British Patent No. 1,082, the sulfonated pyrolysis citric acid of describing in 179, and phosphorous substituent multi-carboxylate is disclosed in British Patent No. 1,439, in 000.

Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2, the 5-tetrahydrofuran (THF)-along a dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the methyl-derivatives of 6-cyclohexane-six hydrochlorate and polyvalent alcohol is as winestone alcohol, mannitol and Xylitol.In British Patent No. 1,425, disclosed aromatic multi-carboxy acid's salt comprises pyromellitic acid, 1,2,4,5-pyromellitic acid and phthalic acid derivative in 343.

More than preferred multi-carboxylate be that each molecule contains nearly hydroxycarboxylate, the especially citric acid of three carboxyls.

Be used in the mixture that preferred builder system in the composition of the present invention comprises a kind of water-insoluble property silico-aluminate washing assistant, as zeolite A or a kind of lamellated silicate (SKS/6) and a kind of water-soluble carboxylate sequestrant such as citric acid.

A kind of suitable sequestrant that is used for detergent composition of the present invention is quadrol-N, N-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, alkaline-earth metal, ammonium or substituted ammonium salt, perhaps their mixture.Form and its sodium or magnesium salts that preferred EDDS compound is a free acid.The example of the sodium salt of these preferred EDDS comprises Na ₂EDDS and Na ₄EDDS.The example of the magnesium salts of this preferred EDDS comprises MgEDDS and Mg ₂EDDS.Magnesium salts most preferably is contained in the composition of the present invention.

For liquid, using the suitable fatty acids washing assistant here is saturated or undersaturated C especially _10-18Lipid acid, and corresponding soap.Preferred saturated fatty acid or corresponding soap are that 12 to 16 carbon atoms are arranged on the alkyl chain.Preferred unsaturated fatty acids is an oleic acid.

Be used in the mixture that preferred builder system in the granular composition comprises a kind of water-insoluble silico-aluminate washing assistant such as zeolite A and a kind of water-soluble carboxylate sequestrant such as citric acid.

Other washing assistant material that can constitute a builder system part that is used in the granular composition of the present invention comprises inorganic material, as alkaline carbonate, di-carbonate, silicate, and organic materials, as organic phosphoric acid salt, amido polyalkylene phosphoric acid salt and amido multi-carboxylate.

Other suitable water-soluble organic salt is homopolymerization or co-polymeric acids or their salt, and wherein poly carboxylic acid comprises at least two quilts and is no more than the carboxyl that two carbon atoms separate.This polymkeric substance is disclosed in GB-A-1, in 596,756.The example of such salt is that MW is the polyacrylic ester and they multipolymers with maleic anhydride of 2000-5000, and such molecular weight of copolymer is 20,000 to 70,000, particularly about 40,000.

The detergency builder salt generally accounts for 10% to 80% of composition weight, preferably accounts for 20% to 70%, accounts for 30% to 60% the most usually.

The detergent ingredients that can be used in the detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER.

These bleaching components can comprise one or more oxygen bleaching agents, and, according to selected SYNTHETIC OPTICAL WHITNER, one or more bleach-activating agents can be arranged.When using, the bleaching compounds that is added in this detergent composition accounts for about 1% to about 10% of composition.In general, bleaching compounds is the component of choosing wantonly in on-liquid Formulation Example such as granulated detergent.If add, the amount of bleach-activating agent typically account for bleaching composition about 0.1% to about 60%, more typically account for about 0.5% to about 40%.

The bleaching components that is used for here can be any SYNTHETIC OPTICAL WHITNER useful to detergent composition, comprises oxidative bleaching agent and other SYNTHETIC OPTICAL WHITNER known in the art.

The present invention also provides a kind of and particularly has been lower than under about 40 ℃ temperature being lower than about 50 ℃ on the other hand, the method for coming cleaning fabric, fiber, textiles with a kind of detergent composition that contains polyamine N-oxide pllymers, optional auxiliary detergency tensio-active agent, optional detergency additive component and a SYNTHETIC OPTICAL WHITNER.

Being suitable for SYNTHETIC OPTICAL WHITNER of the present invention can be an activatory or inactive SYNTHETIC OPTICAL WHITNER.

A spendable class oxidative bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The example that this class SYNTHETIC OPTICAL WHITNER is suitable comprises hexahydrate, the magnesium salts of metachloroperbenzoic acid, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and the diperoxy dodecandioic acid of monoperphthalic acid magnesium.Such SYNTHETIC OPTICAL WHITNER is disclosed in United States Patent (USP) 4,483, and 781, in U.S. Patent application 740,446, european patent application 0,133,354 and the United States Patent (USP) 4,412,934.At United States Patent (USP) 4,634, the SYNTHETIC OPTICAL WHITNER of describing in 551 very preferably comprises that also 6-nonyl amine base-6-oxo crosses oxy hexanoic acid.

The another kind of SYNTHETIC OPTICAL WHITNER that can be used comprises the halogen SYNTHETIC OPTICAL WHITNER.For example, the example of inferior halogenide SYNTHETIC OPTICAL WHITNER comprises TCCA (Trichloroisocyanuric acid) and dichloroisocyanuric acid sodium and potassium, N-chlorine and N-bromo sulphonamide.Usually to account for the heavy 0.5-10% of finished product, the amount that preferably accounts for the heavy 1-5% of finished product adds this material.

Preferably, be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention comprises peroxygen bleach.The example of suitable water-soluble solid peroxygen bleach comprises hydrogen peroxide releasing agent such as hydrogen peroxide, perborate, as perborate monohydrate, perborate tetrahydrate, persulphate, percarbonate, peracetic dithionite, superphosphate and peroxyhydrate.Preferred SYNTHETIC OPTICAL WHITNER is percarbonate and perborate.

The hydrogen peroxide releasing agent can be united use with bleach-activating agent, as tetraacetyl ethylene diamine (TAED), nonanoly acyloxy benzene sulfonate (NOBS, US 4,412, describe in 934), 3,5-trimethyl hexanol oxygen base benzene sulfonate (ISONOBS describes among the EP 120,591) or five acetyl are for glucose (PAG), these materials form the peracid as active bleaching agent after being crossed hydrolysis, can improve bleaching effect like this.Suitable activator also has acylated citrate esters (ATC), is disclosed in common unsettled European Patent Application No. 91870207.7.

By adding a kind of enzyme catalysis system (being a kind of enzyme and its Substrate) that can in beginning or washing process neutralization or water washing process, produce hydrogen peroxide, also can obtain hydrogen peroxide.Such enzyme catalysis system is disclosed in the european patent application of submitting on October 9th, 1,991 91202655.6.

Other is suitable for peroxygen bleach of the present invention and comprises organic peroxide acid such as percarboxylic acids.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent is also known in the art, and can be used to herein.One class has the non-oxide SYNTHETIC OPTICAL WHITNER of specific benefits to comprise the photoactivation SYNTHETIC OPTICAL WHITNER, as sulfonated zinc and/or aluminium phthalocyanine.These materials can be deposited on the Substrate in the washing process.Use rayed in the presence of oxygen, as clothing is hung up drying daytime, sulfonation zinc phthalocyanine phthalocyanine is activated, and Substrate is bleached as a result.Preferred zinc phthalocyanine and a kind of photoactivation bleaching process be at United States Patent (USP) 4,033, is described in 718.Typically, detergent composition comprises the sulfonation zinc phthalocyanine phthalocyanine of weight ratio about 0.025% to about 1.25%.

Other detergent ingredients in can being included in is the detergency enzyme, and it can be included in the detergent formulation, is used for various different purposes, as the removal of the stain of protein-based, saccharide-based or triglyceride level base, and the transfer that stops dyestuff.The enzyme that is impregnated in comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, and their mixture.The enzyme that also can contain other type.They may come from any proper raw material, as plant, animal, bacterium, mould and yeast.

Enzyme reaches the about 5mg of every gram composition to be enough to provide usually, and the amount of more typically about 0.05 to about 3mg heavy organized enzyme is impregnated in.

Suitable examples of proteases is the subtilysin from the Bacillus subtillis of special system and the acquisition of lichenoid form bacillus.The proteolytic ferment that is suitable for removing the protein stain available on the market comprises: Alcalase, the Sarinase and the Esperase that are sold by Novolndustries A/S (Denmark); By InternationalBio-Synthetics, the Maxatase that Inc. (The Netherlands) sells; FNbase by the Genencor sale; Optimase and opticlean by the MKC sale.

Useful proteolytic ferment particularly for liquid detergent composition, is the enzyme that is referred to as protease A and proteolytic enzyme B here.In the european patent application 130,756 protease A has been described.Proteolytic enzyme B has been described in the european patent application series number 87303761.8.For example, amylase comprises the amylase that the lichenoid form bacillus by a kind of special system obtains, and has a detailed description in British Patent Spcification No.1296839 (Novo).Starch decomposing protein matter comprises, for instance, and Rapidase, Maxanyl (InternationalBio-Sythetics, Inc.) and Termamyl, (Novo mdustries).

The available cellulase comprises bacterium and fungal cellulase among the present invention.Preferably, they have a best PH scope: between the 5-9.5.Suitable cellulase is disclosed in the U.S.Patent4 of Barbesgoard etc., and in 435,307, it discloses the fungal cellulase that originates from Humicola insolens.Suitable cellulase is also at GB-A-2.075.028; Be disclosed among GB-A-2.095.275 and the DE-OS-2.247.832.

The example of this cellulase has: by Humicala insolens system (Humicola grisea var.thermoidea), especially Humicola is the cellulase that DSM1800 produces, by cellulase or 212-producing cellulase that belongs to the genus Aeromonas of the mould production of a Bacillus N, the cellulase that from the liver pancreas of extra large mollush, extracts (Dolabella Auricula Solander).

Other suitable cellulase is the cellulase that is derived from Humicola insulens, and its molecular weight is about 50KD _a, iso-electric point is 5.5, contains 415 amino acid.This cellulase has description in the common unsettled European Patent Application No. of submitting on March 19th, 1,993 93200811.3.

Specially suitable cellulase is the cellulase that helps the color protection.The example of this cellulase has description in the European Patent Application No. 91202879.2 of Carezyme on November 6 (Novo) in 1991 submission.

The suitable lipase that is used for washing composition comprises those enzymes by the microorganisms of false unit cell group, as Pseudomonas stutzeri ATCC 19.154, is disclosed in English Patent 1,372, in 034.Suitable lipase comprises that the antibody with lipase shows those lipase of positive immunological cross-reaction, and this is produced by microbe Pseudomonas fluorescent IAM 1057.This lipase can be from Amano Pharmaceutical Co.Ltd., Nagoya, and Japan has bought, and brand is lipase P " Amano ", hereinafter referred to as " Amano-P ".Specially suitable lipase is Ml Lipase (Ibis) and Lipolase (Novo).

Peroxidase is and oxygen source, and for example: percarboxylic acids salt, perborate, persulphate, hydrogen peroxide or the like are united use.They are used as " solvent SYNTHETIC OPTICAL WHITNER ", promptly stop dyestuff or the pigment disposed from Substrate in the washing process to be transferred on other Substrate washing lotion.Peroxidase as known in the art comprises, for example horseradish peroxidase, ligninase, haloperoxidase are as chlorine and bromine peroxide enzyme.The detergent composition that contains peroxidase is disclosed among the PCT Internation ApplicationWO89/0998 13 and European Patent application EP No.91202882.6 that submitted on November 6th, 1991.

In liquid formulations, preferably use a kind of enzyme stabilization system.The enzyme stabilization technique that is used for aqueous detergent compositions is well known in the art.For example, a kind of enzyme stabilization technique in the aqueous solution relates to the use of free calcium ions, and calcium ion is obtained by lime acetate, calcium formiate, calcium propionate.Calcium ion can with short chain carboxy acid's salt, preferably formate is united use.Referring to United States Patent (USP) 4,318,818.Also mixture (for example, diethanolamine, three ethanol fat, two-Yi Bingchunan etc.), boric acid or the alkali metal borate of polyvalent alcohol such as glycerine and sorbyl alcohol, alkoxyl alcohol, dialkyl sugar ether, polyvalent alcohol and multifunctional aliphatic amide used in suggestion once.The enzyme stabilization technique is open extraly and example by following document: United States Patent (USP) 4,261,868, United States Patent (USP) 3,600,319, European patent application publication No. 0,199,405, application number 862005866.5.Non-boric acid and borate stablizer are preferred.Enzyme stabilization system is also at United States Patent (USP) 4,261, has been described in 868,3,600,319 and 3,519,570.

Other suitable detergent ingredients that can be added into is the oxydasis scavenging agent that is described in the common unsettled European Patent application No.92870018.6 that submitted on January 31st, 1992.The example of this kind of enzyme oxidation scavengers is ethoxyquin four ethylidene polyamine.

Particularly preferred detergent ingredients is to be used in combination with a kind of technology of color protection benefit that can provide.The example of these technologies is the cellulases that use for color protection recovery process, and/or the catalyzer of peroxidase and/or metal replacement.

Another kind of optional ingredients is a froth suppressor, illustrates with the mixture of siloxanes and silicon-dioxide-siloxanes.Siloxanes usually can be represented by alkyl silicon polyoxy alkane, and silicon-dioxide usually is used in the fine form of separating, and is example with various aerosils, xerogel and water drain silica.These materials as particle can be infiltrated water-soluble or water dispersible, substantially in the not saturating carrier of non-surface active washing composition, and froth suppressor is beneficial to release therein.In addition, froth suppressor can be dissolved or be dispersed in the liquid vehicle, uses by being sprayed onto on one or more other compositions.

A kind of preferred silicone foam control agent has been disclosed in the United States Patent (USP) 3,933,672 of Bartollota etc.Other special useful froth suppressor is half emulsive siloxane foams inhibitor, describes among the disclosed German patent application DTOS 2 646 126 on April 28th, 1977.An example of this compound is DC-544, and it is the multipolymer of a siloxanes-glycol, can buy from Dow Corning.Particularly preferred Foam Control is a kind of froth suppressor system that comprises silicone oil and 2-alkyl-alkanol mixture.Suitable 2-alkyl-alkanol is 2-butyl-octanol, can buy trade(brand)name Isofol 12 R on the market.

In the common unsettled European Patent Application No. 92870174.7 that 10 months November in 1992 submitted to this foam inhibition system has been described.

Special excellent silicone foam control agent has been described in common unsettled European Patent Application No. 92201649.8.

Said composition can comprise a kind of and imporosity silicon-dioxide such as AerosilR bonded siloxanes/silica mixture.

Above-mentioned froth suppressor add-on generally account for composition heavy 0.01% to 2%, preferably account for 0.01% to 1%.

Other component that is used for detergent composition can be used, such as soil-suspending agent, soil releasing agent, white dyes, abrasive, sterilant, the inhibitor that frosts, tinting material, non-encapsulate and encapsulated fragrances.

Here suitable antiredeposition and soil-suspending agent comprise derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose and Natvosol, and the homopolymerization of poly carboxylic acid and salt thereof or multipolymer.This polymkeric substance comprises aforesaid polyacrylate and toxilic acid-acrylic acid multipolymer as washing assistant, and maleic anhydride is with the multipolymer of ethene, ethylene methacrylic ether or different vinylformic acid, and maleic anhydride, they have constituted the 20mol% at least of multipolymer.These materials generally account for composition heavy 0.5% to 10%, preferably account for 0.75% to 8%, optimally account for 1% to 6%.

Preferred white dyes is negatively charged ion in nature, the example is 4,4 '-two-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(2-morpholino-4-anilino-S-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-S-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4 '; 4 "-two-(2,4-hexichol amido-S-triazine-6-base is amino) stilbene-2-sulfonic acid list sodium, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-S-triazine-6-base is amino) stilbene-2,2 '-disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl)-stilbene-2,2 '-disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-triazine-6-base is amino) stilbene-2,2 '-disulfonic acid disodium and 2-(diphenylethyllene-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2, the 3-triazole)-2 "-sodium sulfonate.

Other useful polymkeric substance is a polyoxyethylene glycol, and particularly those molecular weight are between 1000-10000, and more excellent is molecular weight is between 2000 to 8000, and optimum molecular weight is about 4000.These material consumptions account for about composition heavy 0.20% to 5%, more excellent accounts for 0.25% to 2.5%.These polymkeric substance and aforesaid multi-carboxylate are for improving whiteness weather resistance, fabric ash deposition and extremely valuable to the cleaning performance proteinic and oxidable dirt under clay, the transition metal impurity existence.

Useful soil releasing agent is conventional terephthalic acid and ethylene glycol and/or propylene glycol unit multipolymer or the terpolymer under various arrangements in composition of the present invention.The example of this polymkeric substance the common US Patent Nos.4116885 that transfers the possession of and 4711730 and European Published Patent ApplicationNo.0272033 in be disclosed.A kind of particularly preferred polymkeric substance has following molecular formula among the EP-A-0 272 033:

(CH ₃(PEG) ₄₃) _0.75(POH) _0.25[T-PO) _2.8(T-PEG) _0.4]T(PO-H) _0.25((PEG) ₄₃CH ₃) _0.75

Wherein PEG is-(OC ₂H ₄) O-, PO is (OC ₃H ₆O) and T be (pcOC ₆H ₄CO)

The polyester of improvement also is very useful, the randomcopolymer of the more following materials of picture: dimethyl terephthalate (DMT), sulfo group iso-phthalic acid dimethyl ester, ethylene glycol and 1-2-propylene glycol, mainly by the sulfosalicylic acid ester, the end base that inferior strategic point is made up of the monoesters of ethylene glycol and/or propylene glycol.Purpose is to obtain the polymkeric substance that there is the sulfosalicylic acid ester group at two ends, " mainly ", and most of herein here said multipolymers are all covered endways by the sulfosalicylic acid ester group., some multipolymers are not by whole covering, so their end group can be by ethylene glycol and/or 1, and the monoesters of 2-propylene glycol constitutes and forms " next " kind of this compound.

Here in the polyester of Xuan Zeing, comprise the terephthalic acid dimethyl ester that accounts for gross weight about 46%, account for about 16% 1, the 2-propylene glycol, account for the sulfoisophthalic acid of sulfosalicylic acid dimethyl ester, the anharmonic ratio about 15% of about 10% ethylene glycol, anharmonic ratio about 13%, molecular weight is about 3000.Polyester and preparation method thereof is described in detail in EPA 311 342.

Detergent composition of the present invention can be aqueous, pulpous state, gel or granular.Granular composition of the present invention also can be " conc forms ", and promptly they can have higher density than conventional granular washing composition, promptly from 550 to 950g/l; In this case, granular detergent composition of the present invention contains " mineral filler " lacked than the conventional granular washing composition; Typical filling salt is the vitriol and the muriate of alkaline-earth metal, typically is sodium sulfate; " concentrating " washing composition typically comprises and is no more than 10% filling salt.Liquid composition of the present invention also can have " conc forms ", and in this case, liquid detergent composition of the present invention comprises the water than traditional liquid washing agent less amount.Typically, the water-content of concentrated liquid detergent is lower than 30% of detergent composition weight, more preferably is lower than 20%, optimally is lower than 10%.

The invention still further relates to the method that the dyestuff that runs in a kind of washing process of colored fabric, suppress dissolved and suspension shifts to another kind of fabric from a kind of fabric.

This method comprises that the foregoing fabric that makes contacts with a kind of washing soln.

Method of the present invention is carried out in washing process at an easy rate.Washing process is preferably at 5 ℃ to 75 ℃, carry out under 20 ℃ to 60 ℃ especially, but polymkeric substance is just effective under 95 ℃ even higher temperature.The pH of treatment soln preferably 7 to 11, are 7.5 to 10.5 especially.

Method and composition of the present invention also can be used as the detergent additives product.This additive product is in order to replenish or strengthen the effect of conventional washing agent composition.Detergent composition of the present invention comprises Substrate, be used to clean composition, for example hard-surface cleaning composition (containing or do not contain abrasive), laundry detergent composition, the automatic and non-automatic dish composition of washing such as fabric, fiber, crust, skin etc.

Following Example is to be used for illustrating composition of the present invention, but might not mean restriction or define scope of invention, and said scope is to determine by following claim.

Made a kind of liquid detergent composition with following composition:

With total detergent composition weight % is benchmark

C _12-14Alkyl-sulphate 21

C _13-15Alkyl ethoxy (3EO) vitriol 3

Fatty Alcohol(C12-C14 and C12-C18) C _12-14B-oxide (7EO) 6

C ₁₂N-methyl glucose amide 9

Lipid acid 14

Citric acid 3.5

Monoethanolamine 11

Propylene glycol 8

Ethanol 6

Diethylenetriamine pentamethylene phosphonic acids 1.9

NaOH is to pH7.8

Water and micro substance to 100%

Table I

Example I

A washing test is carried out under the following conditions: 60 ℃ of temperature, product consumption 75mls, municipal water, dirty sample.

Product A is a kind of detergent composition that does not comprise polyamine N-oxide pllymers according to Table I.

Product B is that a kind of to comprise 0.3% molecular-weight average according to Table I be that about 50,000, amine is 1: 4 poly 4 vinyl pyridine N-oxide compound to the amine n-oxide ratio.The result: the judge paper potential difference is (cotton) not

B is to A

Tea+0.8 (S)

Coffee+0.5 (S) example II

Prepared a kind of liquid detergent composition of the present invention, it has following component:

With total detergent composition weight % is benchmark

C _13-15Alkyl ethoxy (3EO) vitriol 19

Fatty Alcohol(C12-C14 and C12-C18) C _12-14B-oxide (7EO) 6

C ₁₂N-methyl glucose amide 9

Lipid acid 9

Citric acid 6

Monoethanolamine 12

Propylene glycol 10

Ethanol 2

Diethylenetriamine pentamethylene phosphonic acids (DTPMP) *

Poly 4 vinyl pyridine N-oxide compound *

NaOH is to pH7.8

Water and micro substance to 100% ^*Be defined as follows:

The composition that has prepared three kinds of example II comprises DTPMP and PVNO respectively and does not all have (A), 1%4-PVNO (B) and 1%DTPMP (C), tests in launderometer under the following conditions: temperature: 60 ℃, and 20min.Washing hard water.Each launderometer beaker comprises 200mls washing soln (0.67%), adds some cotton quarrel artificial contaminations' fabric with tea and coffee dirt.

Each water washing is handled and is carried out four replicate(determination)s.The decontamination percentage is estimated with the reflectivity of washing after stain fabric before measuring washing.

The result:

Handle A B C

4-PVNO 0％ 1％ 0％

Diethylenetriamine pentamethylene phosphonic acids 0% 0% 1%

The decontamination percentage

Tea 17 33 25

Coffee 12 16 14

Grape wine 47 59 61

Example III (A/B/C/D)

Prepared liquid detergent composition of the present invention with following composition

A B C D

Linear alkylbenzene sulfonate 18-6-

C _12-15Alkyl-sulphate-16.0--

C _12-15Alkyl ethoxyquin vitriol-11.0 4.0 25.0

C _12-14N-methyl glucose amide-7.0 9.0 9.0

C _12-14Aliphatic alcohol ethyl oxide 12.0 5.0 6.0 6.0

C12-C16 lipid acid 9.0 6.8 14.0 14.0

Lipid acid 10 10 10 10

Oleic acid 4444

Citric acid 1111

Diethylenetriamine pentamethylene phosphonic acids 0.2 0 1.5 1

Propylene glycol 1.5 1.5 1.5 1.5

Ethanol 10 10 10 10

Ethoxyquin tetracthylene pentamine 0.7 0.7 0.7 0.7

Thermamyl 0.13 0.13 0.13 0.13

Carezyme 0.014 0.014 0.014 0.014

FN-Base 1.8 1.8 1.8 1.8

Lipase 0.14 0.14 0.14 0.1

Endo-dextranase A 0.53 0.53 0.53 0.53

Suds suppressor (ISOFOL ^r) 2.5 2.5 2.5 2.5

Poly-(4-vinylpridine)-N-oxide compound 0.3 0.3 0.3 0.3

Water and micro substance to 100

NaOH and/or MEA transfer pH to 7.8 example IV (A/B/C/D)

Prepared according to the concentrated granular detergent composition with following prescription of the present invention:

With total detergent composition weight % is benchmark

A B C D

Polyhydroxy fatty acid amide 10---

Alkyl alkoxide vitriol-9 99

Alkyl-sulphate 4.80 4.80 4.80 4.80

C _14-157 times of b-oxides 4.00 4.00 4.00 4.00 of alcohol

11 times of b-oxides 1.8 1.8 1.8 1.8 of tallow alcohol

Dispersant 0.07 0.07 0.07 0.07 siloxanes fluids 0.80 0.80 0.80 0.80 trisodium citrate 14.00 14.00 14.00 14.00 citric acids 3.00 3.00 3.00 3.00 zeolites 25.00 20.00 20.00 32.50 maleic acid acrylic copolymers 5.00 5.00 5.00 5.00Carezyme T-granulate 0.2 0.5 0.15 0.3Alcalase T-granulate 0.60 0.60 0.20 0.5Lipolase T-granulate 0.20 0.10 0.25 0.40Termamyl T-granulate 0.3 0.3 0.3 0.3 sodium metasilicate 2.00 2.00 2.00 2.00 sodium sulphate 3.50 3.50 3.50 3.50 SODIUM PERCARBONATEs--20-sodium perborate 15 15--TAED-5 5-encapsulated fragrances 0.2---spices 0.3 0.2 0.3 0.2 P4VP N-oxides 0.3 0.3 0.3 0.3 micro substances to 100

Claims (13)

1. comprise the unitary polyamine N-oxide pllymers of structural formula (I) and remove the usage of pigment stain:

Wherein, P is a polymerizable unit, and the N-O group can be linked above it, and perhaps wherein the N-O group constitutes the part of this polymerizable unit; A is

-O-,-S-,-N-; X is 0 or 1;

R is aliphatic, aromatic, the heterocycle or the alicyclic group of aliphatic, ethoxyquin, and the nitrogen of N-O group can be linked above it, and perhaps wherein the nitrogen of N-O group is the part of these groups.

2. according to the usage of claim 1, wherein P is a polymerizable unit, and wherein the N-O group is linked above it, and R be selected from fragrance or heterocyclic group.

3. according to the usage of claim 2, wherein the nitrogen of N-O group constitutes the part of R-group.

4. according to the usage of claim 3, wherein the R-group is selected from pyridine, pyrroles, quinoline, acridine, imidazoles and derivative thereof.

5. according to claim 1,2 usage, wherein the nitrogen of N-O group is linked on the R-group.

6. according to the usage of claim 5, wherein R is a phenyl.

7. according to the usage of claim 1, wherein P is a polymerizable unit, and the N-O group constitutes the part of this polymerizable unit, and wherein R be selected from fragrance or heterocyclic group.

8. according to the usage of claim 7, wherein the nitrogen of N-O group constitutes the part of R-group.

9. according to the usage of claim 8, wherein the R-group is selected from pyridine, pyrroles, quinoline, acridine, imidazoles and derivative thereof.

10. according to the usage of claim 1-9, wherein polymer backbone is from the polyvinyl polymeric groups.

11. according to the usage of claim 1-10, wherein amine is 2: 3 to 1: 1000000 to the ratio of amine n-oxide, preferred 1: 4 to 1: 1000000, and most preferably 1: 7 to 1: 1000000.

12. a detergent composition that comprises the polyamine N-oxide of molecular formula (I), wherein said polyamine N-oxide pllymers molecular-weight average is 30,000-50,000.

13. the detergent composition according to claim 12, it is a kind of non-dusting particle or liquid detergent additives.