CN1066192C

CN1066192C - Detergent compsn. inhibiting dye transfer

Info

Publication number: CN1066192C
Application number: CN95191288A
Authority: CN
Inventors: A·弗雷; A·D·韦利; J·P·庄士敦; F·E·哈迪; C·A·J·K·托恩
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-01-19
Filing date: 1995-01-13
Publication date: 2001-05-23
Anticipated expiration: 2015-01-13
Also published as: WO1995020032A1; EP0664332B1; CA2179265C; JPH09508164A; CN1138875A; EP0664332A1; DE69419715T2; DE69419715D1

Abstract

A dye transfer inhibiting composition comprising a mixture of polyamine N-oxide polymers having a low and high oxidation degree, said polyamine N-oxide polymers containing units having structural formula (I), 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 0 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 suppresses dye transfer

The field of the invention

The present invention relates to stop in the fabric washing process a kind of composition and the method thereof of dye transfer.Especially, the present invention relates to comprise the inhibition dye transfer compositions of mixture of the polyamine N-oxide pllymers of a kind of polyamine N-oxide pllymers of suboxide degree and a kind of high oxidation degree.

Background of the present invention

Occur in the modern fabrics washing process the most lasting and one of the problem of trouble be that some colored fabrics are easy to released dye and enter in the washing liquid.Dyestuff is transferred on other fabric that is being washed again then.

One of ways of addressing this issue is before this not permanent dye that is washed down from DYED FABRICS has an opportunity to be attached to other article that are in the suds, and complexing or absorption are fallen them.

Polymkeric substance has been used in and has stoped dye transfer in the detergent composition.EP-A-O102 923 has described the application that contains the polymkeric substance of carboxyl in the waterborne compositions.DE-A-2 814 329 discloses the application of N-Yi Xi oxazolidinone polymkeric substance, and FA-A-2 144 721 discloses the Polyvinylpyrolidone (PVP) of 15-35% and the application of vinylformic acid nitrile or maleic anhydride copolymers in the washing powder.

EP-265 257 has described the detergent composition of the carboxymethyl cellulose that comprises a kind of basic metal carboxyl salt, a kind of vinyl pyrrolidone polymer and a kind of polycarboxylate polymer.

Now people are surprised to find, and the special combination body of polyamine N-oxide pllymers that has suboxide degree and high oxidation degree respectively is very effective to the transfer of eliminating various dissolvings or suspension dyestuff.This discovery can be made into the composition that multiple dyestuff is shown the performance of good its transfer of inhibition.

Another embodiment of the invention also provides a kind of method of washing colored fabric.

Summary of the present invention

The present invention relates to comprise the inhibition dye transfer compositions of the mixture of polyamine N-oxide pllymers with the different oxidisabilities of height.

Detailed description of the present invention

Composition of the present invention comprises the mixture of low gasification degree polyamine N-oxide pllymers (" LOPAO ") and high oxidation degree polyamine N-oxide pllymers (" HOPAO ").

Here " suboxide degree polyamine N-oxide pllymers " is meant that amine wherein is from 1000: 1 to 1: 1 to the ratio of amine n-oxide, and reasonable is from 100: 1 to 1: 1, the polyamine N-oxide pllymers that best is from 10: 1 to 1: 1.

Here " high oxidation degree polyamine N-oxide pllymers " is meant that amine wherein is from 2: 3 to 1: 1000000 to the ratio of amine n-oxide, reasonable is from 1: 4 to 1: 1000000, the polyamine N-oxide pllymers that best is from 1: 7 to 1: 1000000.

The amount of amine oxide group can change according to suitable interpolymerization or suitable N-oxidisability in said polyamine N-oxide pllymers.

Polyamine N-oxide pllymers comprises the unit with following structure:

Wherein P is a polymerizable unit, and the N-O group can be linked a part top or wherein N-O group formation polymerizable unit or the two all has.

X is 0 or 1; R is aliphatic series, aliphatic, the aromatic series of ethoxylation, heterocycle or alicyclic group or any its binding substances, and the nitrogen that the nitrogen in the N-O group is connected in top or the N-O group is the part of these groups.

The N-O group can be represented by following general structure:

R wherein ₁, R ₂, R ₃Aliphatic group, aromatic series, heterocycle or aliphatic group or its binding substances, X or/and Y or/and Z is 0 or 1, wherein the nitrogen on the N-O group can be connected on these groups or the binding substances or the nitrogen on the N-O group forms the part of these groups.

The N-O group can be the part of polymerizable unit (P), perhaps can be linked on the polymer backbone, perhaps the combination of the two.

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

The said polyamine N-oxide of one class comprises that the nitrogen in the N-O group wherein forms the polyamine N-oxide group of the part of R-group.Preferred polyamine N-oxide compound be those wherein R be a heterocyclic group, for example material of pyridine, pyrroles, imidazoles, Pyrrolidine, piperidines, quinoline, acridine and its derivative.

Another kind of said polyamine N-oxide comprises that the nitrogen in the N-O group wherein linked 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.The preferred kind of these polyamine N-oxide is that general formula is the polyamine N-oxide of (I), and R wherein is an aromatic series, heterocycle family or alicyclic group, and wherein the nitrogen in the N-O functional group is the part of said R group.These examples of types are that wherein R is for example polyamine oxide compound of pyridine, pyrroles, imidazoles and their derivative of a heterogeneous ring compound.

Another kind of preferred polyamine N-oxide compound is that general formula is the polyamine N-oxide of (I), and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen in the N-O functional group is connected on the said R group.These examples of types are that wherein the R group can be an aromatic series, for example the polyamine oxide compound of phenyl.

As long as the amine oxide polymkeric substance that forms is water miscible, and have the dye transfer of prevention performance, any polymer backbone can use.The example of suitable polymers skeleton is polyvinyl, polyalkylene, polyester, polyethers, polyamine, polyimide, polyacrylic ester and composition thereof.

In fact polymkeric substance of the present invention comprises at random or segmented copolymer, and one of them monomer type is a kind of amine n-oxide and another monomer type is amine ammonia N-oxide compound or is not.The amine oxide unit PK of polyamine oxide compound _a＜10, PK preferably _a＜7 better PK _a＜6.

The polyamine oxide compound can almost obtain on any polymerization degree.If raw material has required water-soluble and dye suspension ability, the polymerization degree is unimportant.

Typically, molecular-weight average is 500 to 1,000, between 000; Preferably molecular weight is from 1,000 to 50,000; More preferably molecular weight is 2,000 to 30,000; Optimally molecular weight is between 3,000 to 20,000.

Polyamine N-oxide of the present invention typically accounts for and stops 0.001 to 10% of dye transfer composition weight, preferably accounts for 0.01 to 2%, optimally accounts for 0.05 to 1%.

This composition can be used the additive of the conventional washing agent composition that acts on the washing purposes easily.The present invention also comprises and contains detergent ingredients, therefore can be used as the inhibition dye transfer compositions of detergent composition.

Make the method for polyamine N-oxide:

The production of polyamine N-oxide can be by the polymeric amine monomer, and then the polymkeric substance that obtains with a kind of suitable oxygenant oxidation result is finished, and perhaps amine oxide monomer itself can be aggregated and obtains polyamine N-oxide.

The synthetic synthetic example that can polyvinylpyridine N-oxide compound of polyamine N-oxide.

To gather 4-vinylpyridine (mw.50,000,5.0g 0.0475mole) is dissolved in the 50ml acetate in advance, and by transfer pipet with the peracetic acid solution (H of 25g glacial acetic acid, 6.4g volume ratio 30% ₂O ₂Solution, several H ₂SO ₄Obtain the 0.0523mol peracetic acid) handle.Mixture (32 ℃) at ambient temperature stirred more than 30 minutes, then with mixture with oil bath be heated to 80-85 ℃ 3 hours, placement is spent the night.The polymers soln that obtains then under agitation mixes with 11ml acetone.The pale brown look that forms in the bottom that the result obtains is stained with the stickiness jelly and is washed with 11ml acetone, obtains a kind of light coloured crystalline shape solid.Solid is leached by gravity, use washing with acetone, use P then ₂O ₅Dry.

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

Detergent additives:

The kinds of surface promoting agent can be used in the detergent composition.The United States Patent (USP) 3,664,961 that was distributed to Norris on May 23rd, 1972 has provided the kind of the typical negatively charged ion of row, nonionic, amphoteric and zwitterionics and these tensio-active agents.

The mixture of anion surfactant is particularly useful for this, particularly when sulfonate and sulfate surfactant weight ratio be during from 5: 1 to 1: 2, preferably from 3: 1 to 2: 3, more preferably be from 3: 1 to 1: 1.Preferred sulfonate comprises there are 9 to 15 in the alkyl, and the alkylbenzene sulfonate of 11 to 13 carbon atoms is arranged especially; And α-sulfonic group fatty acid methyl ester, wherein lipid acid is by C ₁₂-C ₁₈The fat raw material is preferably from C ₁₆-C ₁₈The fat raw material obtains.In each example, positively charged ion is basic metal, preferably sodium.Preferred sulfate surfactant is the alkyl-sulphate that 12 to 18 carbon atoms are arranged in the alkyl, perhaps with in the alkyl has 10 to 20,10 to 16 carbon atoms preferably, and average degree of ethoxylation is that 1 to 6 ethoxy sulfate mixes.Here the example of preferred alkyl-sulphate is a tallow alkyl sulfate, coconut alkyl-sulphate and C _14-15Alkyl-sulphate.Positively charged ion or alkali metal cation, preferably sodium in each example.

The useful in the present invention nonionogenic tenside of one class is the condenses of the oxyethane of band hydrophobic part, provide a kind of hydrophile-lyophile balance (HLB) value between 8 to 17, preferably between 9.5 to 13.5, the tensio-active agent between 10 to 12.5 more preferably.Hydrophobic (oleophylic) part can be aliphatic series or aromatic series in nature, can can easily be regulated with the length of the ethylene oxide group of any special hydrophobic grouping condensation, be obtained a kind of water-soluble cpds with the quality of balance between desirable hydrophilic and hydrophobic units.

The particularly preferred nonionogenic tenside of this kind is the C that contains every mol of alcohol 3-8 moles of ethylene oxide ₉-C ₁₅The primary alconol b-oxide especially contains the C of every mol of alcohol 6-8 moles of ethylene oxide ₁₄-C ₁₅Primary alconol and the C that contains every mol of alcohol 3-5 moles of ethylene oxide ₁₂-C ₁₄Primary alconol.

Another kind of ionic surfactant pack contains the alkyl polyglycoside compound, and its general formula is:

RO(C _nH _2nO) _tZ _x

Wherein Z is an integral part that obtains from glucose; R is the saturated hydrophobic alkyl group that contains 12 to 18 carbon atoms; T is 0 to 10, and n is 2 or 3; X is 1.3 to 4, and compound also 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 they in detergent application at EP-B 0 070 077, open in 0 075 996 and 0 094 118.

The following poly hydroxy fatty acid of molecular formula acidamide surfactant also is suitable for use as nonionogenic tenside.

R wherein ¹Be H, perhaps R ¹Be C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxyl n-propyl or its mixture, R ²Be C _5-31Hydroxyl, Z be a kind of have have the polyhydroxy alkyl of directly linking at least 3 hydroxyls on the chain on linear hydrocarbyl chain, the chain, perhaps a kind of its alkoxy derivative.Preferably, R ₁Be methyl, R ²Be the C of a straight chain _11-15The alkyl or alkenyl chain, as coconut alkyl or its mixture, Z is by reducing sugar, obtains in reductive amination process as glucose, fructose, bud sugar, lactose etc.

Composition of the present invention also comprises a kind of builder system.All traditional builder systems all are applicable to this, comprise silico-aluminate material, silicate, multi-carboxylate and lipid acid, such as the material of edetate, such as the metal ion chelation agent of amido Tripyrophosphoric acid fat, especially diamines tetramethylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acids.Though because environmental protection is former thereby seem not too preferred, phosphate builders also can be with here.

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

Another kind of suitable inorganic builders material is stacked silicate, for example SKS-6 (Hoechst).SKS-6 is a kind of by metso (Na ₂Si ₂O ₅) the stacked silicate of crystalloid formed.

At Belgian patent Nos.831, the disclosed suitable multi-carboxylate who contains a carboxyl comprises lactic acid, glycol acid and its ether derivant in 368,821,369 and 821,370.At German Offenlegenschrift2,446,686 and 2,446, in 687 and the multi-carboxylate who contains two carboxyls who describes in the U.S. Patent number 3,935,257 comprise the water-soluble salt of following material: succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, connection oxyacetic acid, tartrate, tartronic acid and fumaric acid, and their ether carboxylate and at the thionyl carboxylate salt described in the Belgian patent 840,623.The multi-carboxylate who contains three carboxyls comprises, especially, in British Patent No. 1,379, water-soluble citric acid, equisetic acid and citraconate and amber derivative such as the carboxy methoxy-succinic acid described in 241, the newborn oxygen base succsinic acid of in Netherlands patent application 7205873, describing and in British Patent No. 1,387, many carboxylics of oxidation ester salt of describing 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-hexanaphthene-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 first machine 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 50KDa, and 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 PharmaceuticalCo.Ltd., Nagoya, and Japan has bought, and brand is lipase P " Amano ", hereinafter referred to as " Amano-P ".Specially suitable lipase is M1 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 InternationApplication WO89/099813 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 Aerosil ^RBonded 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-pair-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) stilbene-2: 2 '-disulfonic acid disodium, 4,4-pair-(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)-the 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.

Prepared a kind of detergent composition of the present invention, its component is as follows:

With total detergent composition weight % is benchmark linear alkylbenzene sulfonate 10 alkyl-sulphates 4 Fatty Alcohol(C12-C14 and C12-C18) (C ₁₂-C ₁₅) b-oxide 12 lipid acid 10 oleic acid 4 citric acid 1NaOH 3.4 propylene glycol 1.5 ethanol 10 tables 1

The degree of dye transfer is measured with Hunter Colour method of masurement.Hunter Colour system is by representing Hunter a, and the DC value of the variation of b value is evaluated the color of fabric sample, Hunter a, and the b value is recorded by the spectrophotometry of reflection.The DC value is defined by following equation: Dc={ (a _f-a _i) ²+ (b _f-b _i) ²} ^1/2

Subscript i and f represent respectively in the presence of the bleeding fabric, wash before and wash after the Hunter value.Least significantly difference is in 1 of 95% confidence level.

Example 1

The degree of dye transfer is tested and is studied with the launder-O-meter of 30 minutes cycles of washing of a simulation between the fabric of different colours.The Launder-O-meter beaker contains colored fabric and multiple fiber swatch as bleeding dyestuff tracer of the detergent solution of 200ml, a 10cm * 10cm.The bleeding dyestuff is made up of a part of sun blue 90, a part of sun blue 112 and a part direct purple 47.Multiple fiber swatch is cotton.

Experiment condition

pH=7.8

A: do not contain the detergent composition that any dye transfer suppresses system by table 1 a kind of.

B: contain the detergent composition of 10ppm PVNO (poly-(4-7 thiazolinyl pyridine-N-oxide)) by table 1 a kind of, wherein the PVNO molecular-weight average is about 10,000, and amine is 1: 10 (HOPAO) to the amine n-oxide ratio.

C: contain the detergent composition of 10ppm PVNO (poly-(4-vinylpridine-N-oxide compound)) by table 1 a kind of, wherein the PVNO molecular-weight average is about 30,000, and amine is 1: 1 (LOPAO) to the amine n-oxide ratio.

D: by a kind of detergent composition that contains 5ppm PVNO (poly-(4-vinylpridine-N-oxide compound)) of table 1, wherein the PVNO molecular-weight average is about 30,000, amine is 1: 10 to the amine n-oxide ratio, and the detergent composition that contains 5ppm PVNO (poly-(4-vinylpridine-N-oxide compound)), the molecular-weight average of PVNO is about 30,000, and amine is 1: 1 (HOPAO+LOPAO) to the amine n-oxide ratio.

Result: the DC value of cotton tracer

Example II (A/B/C/D)

Prepared liquid detergent composition with following component by the present invention:

A B C D linear alkylbenzene sulfonate 18-6-C ₁₂-C ₁₅Alkyl-sulphate-16.0--C ₁₂-C ₁₅Alkyl ethoxyquin vitriol-11.0 4.0 25.0C ₁₂-C ₁₄N-methyl glucose amide-7.0 9.0 9.0C ₁₂-C ₁₄Aliphatic alcohol ethyl oxide 12.0 5.0 6.0 6.0C ₁₂-C ₁₆Aliphatic acid 9.0 6.8 14.0 14.0 aliphatic acid 10 10 10 10 oleic acid 4444 citric acid 1111 diethylenetriamines-1,5-pentylidene phosphonic acids 1.5 1.5 1.5 1.5 propane diols 1.5 1.5 1.5 1.5 ethanol 10 10 10 10 ethoxyquin TEPNs 0.7 0.7 0.7 0.7 poly 4 vinyl pyridines-N-oxide (HOPAO) 0.3 0.3 0.3 0.3 poly 4 vinyl pyridines-N-oxide (LOPAO) 0.3 0.3 0.3 0.3Thermamyl, 0.13 0.13 0.13 0.13Carezyme 0.014 0.014 0.014 0.014FN-Base, 1.8 1.8 1.8 1.8 lipase 0.14 0.14 0.14 0.14 endo-dextranase A, 0.53 0.53 0.53 0.53 foam inhibitor (ISOFOLr) 2.5 2.5 2.5 2.5 water and micro substance add to 100NaOH and/or MEA transfers pH to prepare the concentrated granular detergent composition with following prescription by the present invention to 7.8 example III (A/B/C/D):

With total detergent composition weight % is benchmark

A B C D polyhydroxy fatty acid amide 10---4.80 4.80 4.80 4.807 times of ethoxyquin C of alkyl alkoxide vitriol-9 99 alkylsulfonate _4-15 4.00 4.00 4.00 4.0011 1.8 1.80 1.8 1.8 0.07 0.07 0.07 0.07 0.80 0.80 0.80 0.80 14.00 14.00 14.00 14.00 3.00 3.00 3.00 3.00 25.00 20.00 20.00 32.501,5- 0.6 0.6 0.6 0.6 5.00 5.00 5.00 5.00T-Carezyme 0.2 0.5 0.15 0.3T-Alcalase 0.60 0.60 0.20 0.50T-Lipolase 0.20 0.10 0.25 0.40T-Termamyl 0.3 0.3 0.3 0.3 2.00 2.00 2.00 2.00 3.50 3.50 3.50 3.50--20- 15 15--TAED-5 5- 0.2--- 0.3 0.2 0.3 0.2 ( 4- ) N- ( HOPAO ) 0.3 0.3 0.3 0.3 ( 4- ) N- ( LOPAO ) 0.3 0.3 0.3 0.3 100

Claims

1. detergent composition that suppresses dye transfer, comprise that having of 0.001-10 weight % is low and the high oxidation degree, molecular-weight average is 500 to 1,000, the polyamine N-oxide pllymers mixture of 000 scope, described polyamine N-oxide pllymers contains the unit with following structural formula

P-A _x-R wherein P is a polymerizable unit, and the N-O group can be linked above it, or wherein the N-O group constitutes the part of polymerizable unit; A be NC=O, C (=O) O, C=O ,-O-,-S-,-N-; X is 0 or 1; R is selected from pyridine, pyrroles, quinoline, acridine, imidazoles, and wherein the nitrogen on the N-O group constitutes the part of R group; The amine that has with the polyamine N-oxide pllymers of wherein said suboxide degree and the ratio of amine n-oxide are for from 1000: 1 to 1: 1, and the amine that the polyamine N-oxide pllymers of described high oxidation degree has and the ratio of amine n-oxide are from 2: 3 to 1: 1,000,000.

2. according to the detergent composition of claim 1, wherein polymer backbone is derived from the polyvinyl polymeric groups.

3. according to the detergent composition of claim 1 or 2, for a kind of no dust granular or aqueous.