CN1150816A - Detergent compositions - Google Patents

Abstract

There is provided a detergent composition containing (a) a heavy metal ion sequestrant; and (b) an enzyme wherein a means is provided for delaying the release to a wash solution of said enzyme relative to the release of said heavy metal ion sequestrant. Preferably said composition additionally contains (c) a water soluble builder wherein a means is provided for delaying the release to a wash solution of said enzyme relative to the release of said water soluble builder. A pretreat wash method is also provided.

Description

Detergent composition

The present invention relates to contain the detergent composition of heavy metal ion chelating agent and enzyme, wherein provide a kind of means to make described enzyme for described heavy metal ion chelating agent, can postpone to be discharged in the washing soln.

Removing the dirt/spot of enzyme sensitivity such as blood, egg, chocolate, gravy on the matrix of being stain/having spot satisfactorily is a special challenge for being used for washing methods as the makers-up of the detergent composition of laundry or machine wash up method.

Usually, by using enzyme component, proteolytic enzyme, amylase, cellulase and lipolytic enzyme just can remove this class dirt/spot.

A problem that produces along with using this fermentoid in the washing methods is the influence that this fermentoid is subjected to other detergent component of existing in the washing soln easily.Enzyme be subjected to for example bleaching the effect of component and take place the degraded may become a special problem.

The applicant has found that the existence of heavy metal ion in the washing soln may quicken the degraded of enzyme.

Though improve the influence that the level that joins the enzyme in the washing soln can be offset the degraded of enzyme to a certain extent, this comprises the scrubbed component of extra use costliness.

Yet, the applicant has now found that, if use the composition that not only contains heavy metal ion chelating agent but also contain enzyme, and wherein provide a kind of means to make enzyme can postpone to be discharged in the washing soln for the heavy metal ion inner complex, then the problem of enzyme liberating just may be resolved.Therefore, need not to improve enzyme level and just can obtain the effect that enhanced is removed stain with the influence of offsetting enzyme liberating.

The applicant also finds, when contaminated matrix before with the enzyme-containing detergent washing with containing heavy metal ion chelating agent, and the solution of the water soluble detergency promoter of choosing wantonly just can obtain to remove the effect of stain when carrying out pre-treatment.

Therefore, an object of the present invention is to provide be applicable to laundry and machine wash up method, need not to use high-level enzyme just to have the composition of enhancing clean effect.

A relevant purpose of the present invention provides a kind of method for pretreating of stain, is included in the solution with the water soluble detergency promoter that contains heavy metal ion chelating agent and choose wantonly before the enzyme-containing detergent washing contaminated matrix is carried out pre-treatment.

Summary of the invention

The invention provides a kind of containing:

(a) a kind of heavy metal ion chelating agent; With

(b) a kind of detergent composition of enzyme, wherein provide a kind of means to make described enzyme for described heavy metal ion chelating agent, can postpone to be discharged in the washing soln, make required time of 80% the concentration that in T80 test method as herein described, reaches described heavy metal ion chelating agent ultimate density less than 60 seconds, and reach the required time of 80% concentration of described enzyme ultimate density greater than 90 seconds.

According to a particularly preferred aspect of the present invention, described composition also contains:

(c) a kind of water soluble detergency promoter wherein provides a kind of means to make described enzyme can postpone to be discharged in the washing soln for described water soluble detergency promoter, makes required time of 50% the concentration that reaches described water soluble detergency promoter ultimate density in T50 test method as herein described less than 60 seconds.

According to another aspect of the present invention, a kind of washing methods is provided, comprise the following steps:

(1) the no enzyme solution that will contain the composition of heavy metal ion chelating agent is applied on the contaminated matrix;

(2) allow described solution and described pollution matrix keep in touch one period effective timed interval;

(3) employing comprises that the washing methods that uses enzymatic detergent compositions washs described contaminated matrix.

Heavy metal ion chelating agent

Detergent composition of the present invention contains a kind of heavy metal ion chelating agent.So-called heavy metal ion chelating agent means the composition of the effect that can play the chelating heavy metal ion at this.These compositions also can have calcium and magnesium sequestering power, but they preferentially demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

Heavy metal ion chelating agent generally exist level be said composition 0.005～20%, better 0.1～10%, be more preferably 0.25～7.5%, best be 0.5～5% (weight).

It is acid in nature, for example the heavy metal ion chelating agent of phosphoric acid or carboxylic functionality is arranged, both can exist, also can be used as with a kind of suitably to positively charged ion such as alkalimetal ion or alkaline-earth metal ions, ammonium ion or the ammonium ion of replacement is arranged or the title complex of its any mixture/salt exists with its sour form.Be preferably, any salt/title complex all is water miscible.Described mol ratio to positively charged ion and this heavy metal ion chelating agent better is at least 1: 1.

Be suitable for heavy metal ion chelating agent used herein and include organic phosphonates, for example amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt.

More than be preferably diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), 1,6-hexanediamine four (methylene phosphonic acid salt) and hydroxyl ethylidene-1,1-diphosphonate in the various sequestrants.

Other is suitable for heavy metal ion chelating agent used herein and comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as ethylenediamine tetraacetic acid (EDTA), and the ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid, or its any salt.

That good especially is quadrol-N, N '-disuccinic acid (EDDS) or its an alkali metal salt, alkaline earth salt, ammonium salt, the ammonium salt that replacement is arranged or its mixture.The EDDS compound is free acid form and sodium salt or magnesium salts or title complex preferably.This type of preferably the example of EDDS sodium salt comprise Na ₂EDDS and Na ₃EDDS.This type of preferably the example of EDDS magnesium complex comprise MgEDDS and Mg ₂EDDS.

Other is suitable for heavy metal ion chelating agent used herein is iminodiacetic acid derivatives, EP-A-317 for example, 542 and EP-A-399,2-hydroxyethyl iminodiethanoic acid described in 133 or glyceryl iminodiethanoic acid.

EP-A-516, the iminodiethanoic acid described in 102-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are suitable at this.EP-A-509, the Beta-alanine-N described in 382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable for.

RP-A-476,257 described be suitable for, based on the sequestrant of amino.EP-A-510,331 have described from collagen protein, Keratin sulfate or casein derived suitable sequestrant.EP-A-528,859 have described a kind of suitable alkyl imino oxalic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is suitable for.G-NH2-N, N '-disuccinic acid (GADS) also is suitable for.

Enzyme

This composition contains a kind of enzyme.The enzymatic material that is suitable for comprises commercially available lipase (enzyme that promptly has lipolytic activity), amylase (enzyme that promptly has amylolytic activity), neutral and Sumizyme MP (enzyme that promptly has proteolytic activity), esterase, cellulase (promptly having the enzyme of separating cellulolytic activity), polygalacturonase (promptly have and separate the active enzyme of pectin), Sumylact L (promptly having the enzyme of separating lactose activity) and the peroxidase that often adds in the detergent composition.United States Patent (USP) 3,519 has been discussed the enzyme that is suitable in 570 and 3,533,139.

Commercially available preferably proteolytic enzyme comprises those that Novo Industries A/S (Denmark) sells with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase, those that Gist-Brocades company sells with trade(brand)name Maxatase, Maxacal and Maxapem, those that those that Genencor international corporation sells and Solvay Enzymes company sell with trade(brand)name Opticlean and Optimase.Proteolytic enzyme can be 0.0001～4% (weight) organized enzyme of said composition according to the level of mixing in the composition of the present invention.

Amylase comprises such as GB-1 preferably, among 269,839 (Novo) in greater detail, the α-Dian Fenmei that obtains from a kind of special B lichenoid form bacterial strain.Commercially available preferably amylase comprises, for example, and those that those that Gist-Brocades company sells with trade(brand)name Rapidase and NovoIndustries A/S company sell with trade(brand)name Termamyl and BAN.Amylase is at 0.0001～2% organized enzyme (weight) that can be said composition according to the level of mixing in the composition of the present invention

Lipolytic enzyme (lipase), in active lipolytic enzyme, it exists level to can be 0.0001～2% (weight) of said composition, better 0.001～1% (weight), best 0.001～0.5% (weight).

Lipase can be that to come from fungi also can be to come from bacterium, for example be obtained from the yielding lipase bacterial strain of humic Pseudomonas (Humicola sp.), the mould Pseudomonas of high temperature (Thermomyces sp.) or Rhodopseudomonas (Pseudomonas sp.), comprise pseudomonas pseudoalcaligenes (Pseudomonas pseudoalcaligens) or pseudomonas fluorescens (Pseudomonasfluorescens).Also can use from the chemical modification mutant of these bacterial strains or the lipase of gene modification mutant generation at this.

A kind of lipase preferably produces from pseudomonas pseudoalcaligenes (Pseudomonaspseudoalcaligenes), grants among European patent EP-B-0218272 and describes.

Here another kind preferably lipase be to have the gene clone of fetal hair humic bacterium (Humicolalanuginosa) by oneself and in aspergillus oryzae (Aspergillusoryza), this genetic expression is obtained by making as the host, see European patent application EP-A-0258068 for details, can trade(brand)name Lipolase available from Novo Industries A/S company (Denmark's Buswell).This lipase also can be consulted United States Patent (USP) 4,810,414 that announced on March 7th, 1989, people such as Huge-Jensen.

Enzyme stabilization system

Here contain enzyme composition preferably and can comprise about 0.001～about 10%, better about 0.005～about 8%, best about 0.01～about 6% (weight) enzyme stabilization system.This kind of enzyme stable system can be any can with the stable system of detergent enzyme compatibility.Such stable system can comprise calcium ion, boric acid, propylene glycol, short chain carboxy acid, boronic acid and composition thereof.Such stable system also can comprise the irreversible enzyme inhibitor, as reversible protease inhibitors.

The composition here can further comprise 0～about 10%, better about 0.01～about 6% (weight) chlorine bleach scavenging agent, and its interpolation is especially to attack enzyme and make it inactivation under alkaline condition for the chlorine kind that prevents to exist in many feedwater.Though level of chlorine may be very low in the water, its scope typically is about 0.5ppm～about 1.75ppm, and the available chlorine that contacts with this enzyme in total volume of water during washing is a lot of usually; Therefore, enzyme stability in use may be problematic.

The chlorine scavenger negatively charged ion that is suitable for extensively can get, and can contain the salt of ammonium cation or sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc. and be illustrated for example.Oxidation inhibitor such as carbamate, ascorbate salt etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and composition thereof can use equally.Other scavenging agent commonly used such as hydrosulfate, nitrate, muriate, hydrogen peroxide cource such as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, maleate, salicylate etc. and composition thereof, if be ready, also can use.

Relative release dynamics

A basic sides of the present invention provides a kind of means and makes enzyme for heavy metal ion chelating agent, can postpone to be discharged in the washing soln.

Described means can comprise and are used for making enzyme to postpone to be discharged into the means of washing soln.

Perhaps, alternatively, described means can comprise the means that are used to improve the speed that heavy metal ion chelating agent discharges to this solution.

Postpone rate of release-means

Postponing the release means can comprise with a kind of containing and aim to provide the Drug coating that postpones release or any being suitable for of Drug coating mixture becomes to assign to coat enzyme.Therefore, this Drug coating can be such as comprising a kind of poorly water soluble material, or one deck has the dressing of adequate thickness, makes the dissolution kinetics of this thick coatings that controlled release speed can be provided.

This coating material can utilize the whole bag of tricks to use.Any coating material typically all is 1: 99～1: 2, is preferably 1: 49～exist at 1: 9 with the weight ratio of coating material and SYNTHETIC OPTICAL WHITNER.

The coating material that is suitable for comprises triglyceride level (for example vegetables oil of partial hydrogenation, soybean oil, oleum gossypii seminis), monoglyceride or diester, microcrystalline wax, gelatin, Mierocrystalline cellulose, lipid acid, and any mixture.

Other suitable coating material can comprise the vitriol of basic metal and alkaline-earth metal, and silicate and carbonate comprise lime carbonate.

Coating material is SiO preferably ₂: Na ₂O ratio is 1.6: 1～3.4: 1, better 2.8: 1 water glass, uses with aqueous solution form, to provide the level by percarbonate weight 2～10% (common 3～5%) silicate solid.Also can comprise Magnesium Silicate q-agent in this Drug coating.

Any inorganic salt coating material can make up with organic binding material, so that complex inorganic salt catalyst/organic binder bond coatings to be provided.Suitable binding agent comprises that every mol of alcohol contains the C of 5～100 moles of ethylene oxide ₁₀～C ₂₀Alcohol ethoxylate is more preferably the C that every mol of alcohol contains 20～100 moles of ethylene oxide ₁₅～C ₂₀Primary alcohol ethoxylate.

Other preferably binding agent comprise some polymer materials.Molecular-weight average is that 12,000～700,000 Polyvinylpyrolidone (PVP) and molecular-weight average are 600～10,000 polyoxyethylene glycol (PEG), is exactly the example of this type of polymer materials.The multipolymer of maleic anhydride and ethene, ethylene methacrylic ether or methacrylic acid, wherein maleic anhydride accounts at least 20% (mole) of this polymkeric substance, is the further example that can be used as the polymer materials of binding agent.These polymer materialss can use like this, also can with solvent such as water, propylene glycol and above-mentioned every mole of C that contains 5～100 moles of ethylene oxide ₁₀～C ₂₀Alcohol ethoxylate is used in combination.The further example of binding agent comprises C ₁₀～C ₂₀-glyceryl ether and two glyceryl ethers also comprise C ₁₀～C ₂₀Lipid acid.

Derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, Type 3U and Natvosol, and homopolymerization or copolymerization polycarboxylic acid or its salt are to be suitable for other examples of adhesives used herein.

A kind of method of using coating material relates to nodulizing.Agglomeration process comprises the above-described any organic binder material of use preferably.Any cyclone agglomerator/mixing machine commonly used be can use, tray type, Barrate type and vertical fusion type included but not limited to.Melt coating agent composition also can or by being poured into or spray atomization is used to the moving-bed of SYNTHETIC OPTICAL WHITNER.

Other means that provide required delay to discharge comprise that the physical features that changes any enzyme containing granule is to control the mechanical means of its solubleness and rate of release.Suitable scheme can comprise compress, mechanical injection, manual injection and adjust the solubleness of SYNTHETIC OPTICAL WHITNER compound by the granularity of selecting any granular composition.

Though granularity is selected both to have depended on that the composition of granular composition also depended on the wish that satisfies desired delay release dynamics, it is desirable to, granularity should be greater than 500 microns, and better average particulate diameter is 800～1200 microns.

Any other composition that provides other schemes that postpone the release means to comprise suitable selection detergent composition matrix makes the ionic strength environment that is provided therein when introducing said composition in the washing soln that needed delay release dynamics is reached.

Improve rate of release-means

The means that all raising heavy metal ion chelating agents are discharged into the speed in the solution all are susceptible to.

The means that raising discharges can comprise any component that is fit to that designs the coating that is used to provide raising release that contains of coating.Therefore, this coating can comprise for example high or middle effervesce water-soluble material.

Other means that provide desired raising to discharge comprise and are used for changing the heavy metal ion chelating agent physical property to improve the mechanical means of its solubleness and rate of release.

A suitable scheme can comprise that careful selection contains the granularity of the component of any heavy metal ion chelating agent.The selection of granularity will be according to the composition of granular component, again according to the requirement that adapts to required raising release dynamics.It is desirable for granularity should be less than 1200 micron, and preferred median size is the 1100-500 micron.

Provide the other scheme that postpones the release means to comprise any other component in the suitable selection cleaning composition, or contain any granular component of heavy metal ion chela agent, make the ionic strength environment that when said composition joins in the washing soln, is wherein provided that desired raising release dynamics is reached.

Relative release rate-kinetic parameter

The release of peroxy acid bleach component from enzyme is such with respect to the release of heavy metal ion chelating agent component, make in T80 test method as herein described, reach the required time of 80% concentration of described heavy metal ion integrated agent ultimate density less than 60 seconds, better less than 50 seconds, better less than 40 seconds, and reach the required time of 80% concentration of described enzyme ultimate density, be preferably 90～240 seconds greater than 90 seconds, more preferably 100～200 seconds, be preferably 120～180 seconds.

The final wash concentration of heavy metal ion chelating agent is generally 0.0001%-0.05% (weight), but better greater than 0.001%, better greater than 0.002%.

When used enzyme was a kind of proteolytic enzyme, its final content in typical washing soln was 0.1-100KNPU, but is preferably 0.5-50KNPU, and more preferably 3-30KNPU is preferably 6-30KNPU.

When used enzyme was a kind of amylase, its final content in typical washing soln was 1-200KNU, but is preferably 10-100KNU, more preferably 40-80KNU.

When employed enzyme was a kind of cellulase, its final content in washing soln was generally 1.0-1200CEVU, but is preferably 50-1000CEVU, more preferably 80-500CEVU.

Postpone release-test method

The delay release dynamics here is at " TA test method " definition, and this method is measured the time of measuring the A% that reaches this composition ultimate density/level when a kind of composition that contains certain composition dissolves according to the standard conditions of present proposition.

Standard conditions comprise a 1L glass beaker, and the 120 ℃ of distilled water of 1000ml of packing into are to wherein adding the 10g composition.The content of this beaker stirs with the magnetic stir bar that is set in 100rpm.Magnetic stir bar is pea/ovum pearl shape, and its overall dimension is 1.5cm, and minimum size is 0.5cm.Ultimate density/the level of getting is the concentration/level that reached in 10 minutes after said composition adds in the dress water beaker.

Select to be suitable for analytical procedure, make can after said composition is added in the water of this beaker, measure reliably some time concentration and the ultimate density of the composition of paying close attention in solution.

Such analytical procedure can comprise those can continuous monitoring the method for these constituent concentration levels, comprising such as photometry and conductometry.

In addition, can also adopt the method that comprises the following step: press setting-up time and from this solution, take out the titration sample at interval, the temperature that for example reduces this titration sample with proper method rapidly stops dissolution process, uses for example concentration of this composition of chemical titration in this titration sample of any means then.

Under appropriate situation, can adopt suitable graphic method, comprise curve-fitting method, so that can calculate the TA value from the original analysis result.

For measuring the character that specific analytical method that this constituent concentration selects will depend on this composition, also depend on the character of the composition that contains this composition.

Water soluble detergency promoter (synergistic agent) compound

Detergent composition of the present invention can contain the water soluble detergency promoter compound as utmost point preferred ingredient, and its content is generally the 1%-80% of composition weight, is preferably 2%-60%, more preferably 2%-40%.

Of the present invention one very preferred aspect, also provide a kind of means to make the bleaching component for preferred water soluble detergency promoter component, can postpone to be discharged in the washing soln.Described means can comprise that described here being used to reaches the equivalent manners that foregoing bleaching component postpones any delay release means of release.

Described delay discharges means better to be selected like this, so that make required time of 50% the concentration that reaches described water soluble detergency promoter ultimate density in T50 test method as herein described less than 60 seconds, better less than 50 seconds, better less than 40 seconds.

The final wash concentration of water soluble detergency promoter is generally 0.0005%-0.4%, is preferably 0.005%-0.35%, more preferably 0.01%-0.3%.

The water soluble detergency promoter compound that is suitable for comprises water-soluble monomer multi-carboxylate or its sour form, homopolymerization or copolymerization poly carboxylic acid or its salt, wherein poly carboxylic acid comprises at least two carboxyls that are separated from each other by no more than two carbon atoms, carbonate, supercarbonate, borate, phosphoric acid salt, silicate and above-mentioned any mixture.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomeric or oligomeric on type, although be the monomer multi-carboxylate owing to the reason of cost and performance is general better.

The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and ether derivant thereof.The multi-carboxylate of containing two carboxylic groups comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing three carboxylic groups comprises water-soluble citrate, aconitate and citraconate and succinate derivative, particularly as English Patent No.1, carboxymethyl oxydisuccinic acid salt described in 379,241, English Patent No.1, aminosuccinic acid salt described in lactoyl oxydisuccinic acid salt described in 389,732 and the Netherlands patent applications 7205873, with oxygen multi-carboxylate material, as English Patent No.1, the 2-oxa--1 described in 387,447,1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxylic groups comprises English Patent No.1, disclosed oxygen disuccinate in 261,829,1,1,2,2-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 English Patent No.1,398,421 and No.1,398,422 and U.S. Patent No. 3,936,448 in disclosed sulfo-succinic acid salt derivative, with English Patent No.1, the Citrate trianion of the sulfonation thermo-cracking described in 439,000.

Aliphatic series ring and heterocyclic multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-the tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane hexacarboxylic acid salt and polyvalent alcohol such as Sorbitol Powder, mannitol and Xylitol.Aromatic multi-carboxy acid's salt comprises English Patent No.1, disclosed mellitic acid, petroleum benzene pregnancy acid and phthalic acid derivatives in 425,343.

In the above-claimed cpd, the multi-carboxylate is that per molecule contains the nearly hydroxycarboxylate of three carboxylic groups preferably, more particularly, is Citrate trianion.

The mixture of the parent acid of monomer or oligomeric multi-carboxylate's sequestrant or they and its salt as citric acid or Citrate trianion/citric acid mixture, also is expected as useful washing assistant composition.

The borate washing assistant, and contain washing composition store or wash conditions under can produce the washing assistant of boratory borate generation material, also can use but be not better being lower than about 50 ℃, especially being lower than about 40 ℃ wash conditions.

The example of carbonate builders is alkaline-earth metal and alkaline carbonate, comprises the German patent application No.2 that publish November in 1973 15, in 321,001 disclosed yellow soda ash and concentrated crystal soda and with the mixture of calcium carbonate superfine powder.

The specific examples of water-soluble phosphate washing assistant is the tripolyphosphate an alkali metal salt, trisodium phosphate, potassium and ammonium, and sodium orthophosphate and potassium, its polymerization degree scope is about 6～21 the salt that gathers inclined to one side/sodium phosphate and phytinic acid.

The silicate that is suitable for comprises water-soluble metasilicate, its SiO ₂: Na ₂O ratio is 1.0～2.8, and ratio is 1.6～2.4 preferably, and best ratio is 2.0.This type of silicate both can be the form of anhydrous salt, also can be the form of salt hydrate.SiO ₂: Na ₂O ratio is that 2.0 water glass is best silicate.

Silicate is more preferably 10～40% (weight) better being 5～50% (weight) of composition according to the level that exists in the detergent composition of the present invention.

The additional detergent composition

Detergent composition of the present invention also can contain the additional detergent composition.The exact nature of these supplementary components and the level of mixing thereof will depend on the physical form of composition, and the character that will use the clean-out operation of said composition.

For example, composition of the present invention can be mixed with craft and machine laundry detergent composition, and comprise laundry additive composition and be suitable for the pretreated composition of spot fabric, and the machine dishwashing compositions.

When being mixed with the composition that is suitable for machine-washing method such as machine clothes washing method and machine wash up method, composition of the present invention better contains one or more and is selected from following additional detergent composition: tensio-active agent, washing assistant, the organic polymer compounds, SYNTHETIC OPTICAL WHITNER, froth suppressor, lime soap dispersing agent, dirt suspends and anti redeposition agent, and corrosion inhibitor.Laundry composition also can contain the tenderizer as the additional detergent composition.

Tensio-active agent

Detergent composition of the present invention can contain the tensio-active agent as additional cleaning ingredients, and this can be selected from anionic, cationic, non-ionic type, amphoteric ionic surfactant and composition thereof.

Tensio-active agent typically exists with the level of 0.1～60% (weight).Better the tensio-active agent level of mixing is 1～35% (weight), and best is 1～20% (weight).

Tensio-active agent better prepared can with any enzyme component compatibility of existing in the said composition.In aqueous or gel-form composition, preferably tensio-active agent is prepared to such an extent that make it to improve or do not reduce at least the stability of any enzyme in these compositions.

The typical list of anionic, non-ionic type, amphoteric ion type classification and the form of these tensio-active agents can be consulted the United States Patent (USP) 3,929,678 of granting Laughlin and Heuring on December 30th, 1975.Further example can be consulted " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch work).Granted the inventory that has provided suitable cationic surfactant in the United States Patent (USP) 4,259,217 of Murphy on March 31st, 1981.

Under situation about existing, amphoteric ion type (Cmpholytic, amphoteric and zwitteronic) tensio-active agent generally is used in combination with one or more anionics and/or nonionic surface active agent.

Aniorfic surfactant

Any basically aniorfic surfactant that can be used for washing purpose can be included in the composition.These can comprise anionic vitriol, sulfonic acid, carboxylate salt and sarcosinate surfactant salt (comprise such as sodium salt, sylvite, ammonium salt and ammonium salt that replacement is arranged, as one, two and triethanolamine salt).

Other aniorfic surfactant comprises isethionate such as acyl isethinate; the N-acyl taurine salt, the fatty acid amide of methyl tauride, alkyl succinate and sulfosuccinate, the monoesters of sulfosuccinate (especially saturated and undersaturated C ₁₂～C ₁₈Monoesters), the dibasic acid esters of sulfosuccinate (especially saturated and undersaturated C ₆～C ₁₄Dibasic acid esters), N-acyl sarcosinate.Resinous acid and hydrogenation resin acid also are suitable for, and for example exist in rosin, hydrogenation rosin and the tallow oil or from its deutero-resinous acid and hydrogenation resin acid.

The anionic sulfate surfactant

Be suitable for anionic sulfate surfactant used herein and comprise line style and cladodification primary alkyl sulphates, alkyl ethoxy sulfate, fatty oleoyl glycerine vitriol, alkylphenol oxygen Vinyl Ether vitriol, C ₅～C ₁₇Acyl group-N-(C ₁～C ₄Alkyl) and-N-(C ₁～C ₂Hydroxyalkyl) glucosamine sulfate, and the vitriol of alkyl polysaccharide are as the vitriol of alkyl polyglucoside (described herein non-ionic type non-sulfuric acid salt compound).

Alkyl ethoxy sulfate surfactant better is selected from by each molecule and has carried out the C of ethoxylation with about 0.5～about 20 moles of ethylene oxide ₆～C ₁₈This group that alkyl-sulphate is formed.Be more preferably, alkyl ethoxy sulfate surfactant be each molecule with about 0.5～about 20, better about 0.5～about 5 moles of ethylene oxide have been carried out the C of ethoxylation ₆～C ₁₈Alkyl-sulphate.

The anionic sulfosalt surfactant

Be suitable for anionic sulfosalt surfactant used herein and comprise C ₅～C ₂₀Linear alkyl benzene sulfonate salt, alkane sulfonated ester, C ₆～C ₂₂Uncle or secondary sulfonated alkane, C ₆～C ₂₄Sulfonated alkene, the salt of sulfonation polycarboxylic acid, alkyl glycerol sulfonic acid oil, fatty acyl glycerol sulfonate, fatty oleoyl glycerol sulfonate, and any mixture.

The anionic carboxylate surface active agent

Be suitable for anionic carboxylate surface active agent used herein and comprise alkyl ethoxy carboxylate, many oxyethyl groups of alkyl multi-carboxylate's tensio-active agent and soap class (" alkyl carboxyl "), the secondary soap of especially described here some.

Be suitable for better alkyl ethoxy carboxylate used herein and comprise that those general formulas are RO (CH ₂CH ₂O) xCH ₂COO ^-M ⁺Carboxylate salt, R is C in the formula ₆～C ₁₈Alkyl group, x scope are 0～10, and ethoxylate distribute to make that x by weight is that 0 quantity of material is less than about 20%, and that x is less than greater than 7 quantity of material is about 25%, when average R is C ₁₃Or average x is about 2～4 when following, and when average R greater than C ₁₃Shi Pingjun x is about 3～10, and M is a positively charged ion, better is selected from basic metal, alkaline-earth metal, ammonium, one, two and triethanol ammonium, preferably be selected from sodium, potassium, ammonium and with the mixture of magnesium ion.Alkylethoxylate is that its R is C preferably ₁₂～C ₁₈The alkyl group person.

Be suitable for many oxyethyl groups of alkyl multi-carboxylate tensio-active agent used herein and comprise that those have general formula R O (CHR ₁-CHR ₂-O)-R ₃The person, R is a C in the formula ₆～C ₁₈Alkyl group, x are 1～25, R ₁And R ₂Be selected from one group that forms by hydrogen, methyl acidic group, amber acidic group, hydroxyl amber acidic group and composition thereof, at least one R in the formula ₁And R ₂Be amber acidic group or hydroxy succinic acid base, and R ₃Be selected from by hydrogen, by 1～8 carbon atom by replacing or not having one group that substituted hydrocarbon radical and composition thereof is formed.

The secondary soap surfactant of anionic

Soap surfactant is that those contain a unitary secondary soap surfactant of the carboxyl that is connected with secondary carbon preferably.This, carbon can be in a ring structure second month in a season, for example in to the octyl group phenylformic acid, or at the cyclohexane carboxylic acid salt that has alkyl to replace.Secondary soap surfactant better not ether-containing key, do not contain ester bond, non-hydroxyl group.More fortunately should there be nitrogen-atoms on the head group (amphiphilic moieties).Secondary soap surfactant contains 11～15 carbon atoms altogether usually, although can allow many slightly (as reaching 16) carbon atom, as to the octyl group phenylformic acid.

Following formula further specifies some secondary preferably soap surfactants:

A. the highly preferred secondary soap of a class comprises formula R ³CH (R ⁴) the secondary carboxylic sill of COOM, R in the formula ³Be CH ₃(CH ₂) x and R ⁴Be CH ₃(CH ₂) y, y can be 0 or 1～4 integer in the formula, x is 4～10 integer, and (x+y) and be 6～10, better 7～9, preferably 8.

B. another kind of secondary preferably soap comprises the carboxylic compound of those carboxyl substituents on a cyclic hydrocarbon radical unit, and promptly general formula is R ⁵-R ⁶The secondary soap of-COOM, R in the formula ⁵Be C ⁷-C ¹⁰, better be C ⁸-C ⁹Alkyl or alkenyl, and R ⁶Be a ring structure, as benzene, pentamethylene and hexanaphthene.(annotate: R ⁵Can be with respect to ortho position, a position or the contraposition of carboxyl on ring.)

C. also have another kind of secondary preferably soap to comprise general formula CH ₃(CHR) _k-(CH ₂) _m-(CHR) _n-CH (COOM) (CHR) _o-(CH ₂) _p-(CHR) _q-CH ₃Secondary carboxylic compound, each R is C in the formula ₁～C ₄Alkyl, k, n, o, q are that scope is 0～8 integer in the formula, prerequisite is that the scope of carbon atom (comprising carboxyl) sum is 10～18.

In each formula of above general formula A, B and C, plant M and can be any suitable, water solubilising especially to ion.

Can good especially as used herein secondary soap surfactant be to be selected from one group the water-soluble member who is made up of following: 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-be sad and the water-soluble salt of 2-amyl group-1-enanthic acid.

The basic metal sarcosinate surfactant

Other aniorfic surfactant that is suitable for is that general formula is R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, R is C in the formula ₅～C ₁₇Line style or cladodification alkyl or kiki alkenyl group, R ¹Be C ₁～C ₄Alkyl group, M are alkalimetal ions.Example is myristyl and the oil base methyl sarcosinate that is its sodium-salt form preferably.

Nonionic surface active agent

Can comprise any basically nonionic surface active agent that can be used for washing purpose in this composition.Below enumerate several classes as an example, nonrestrictive available nonionic surface active agent.

The non-ionic type polyhydroxy fatty acid amide surfactant

Being suitable for polyhydroxy fatty acid amide used herein is that its structural formula is R ²CONR ¹Z person, R in the formula ¹Be H, C ₁～C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture are preferably C ₁～C ₄Alkyl is more preferably C ₁Or C ₂Alkyl, that best is C ₁Alkyl (being methyl); And R ²Be C ₅～C ₃₁Alkyl is preferably straight chain C ₅～C ₁₉Alkyl or alkenyl are more preferably straight chain C ₉～C ₁₇Alkyl or alkenyl, best is straight chain C ₁₁～C ₁₇Alkyl or alkenyl, or its mixture; And Z a kind ofly has a line style hydrocarbyl chain and at least 3 hydroxyls is arranged and the direct-connected polyhydroxy alkyl of this chain, or its alkoxy derivative (better being ethoxylation or propoxylation).Z better is from a kind of reducing sugar deutero-with reductive amination process; Be more preferably, Z is a sugar alcohol base (glycityl).

The non-ionic type condenses of alkylphenol

Be suitable for polyoxyethylene, polyoxypropylene and the polyoxy croton condensation thing that alkylphenol is arranged used herein.In general, be preferably the polyoxyethylene condenses.These compounds include one and contain 6～about 18 carbon atoms of having an appointment, are the alkylphenol of alkyl group of linear configuration or cladodification chain configuration and the condensation product of oxyalkylene.

The non-ionic type ethoxylated alcohol surfactant

The alkyl ethoxylated condensation product of fatty alcohol and about 1～about 25 moles of ethylene oxide is suitable for using here.The alkyl chain of this fatty alcohol can be straight chain also can be cladodification, can be uncle's chain also can be secondary chain, and generally contain 6～22 carbon atoms.Especially good is the alcohols of an alkyl that contains 8～20 carbon atoms and the condensation product of about 2～about 10 moles of ethylene oxide of every mol of alcohol.

The non-ionic type ethoxylated/propoxylated fatty alcohol surfactant

Ethoxylation C ₆～C ₁₈. Fatty Alcohol(C12-C14 and C12-C18) and C ₆～C ₁₈Mixed ethoxylated/propoxylated fatty alcohol is to be suitable for tensio-active agent used herein, and is especially true under water miscible situation.Be preferably, ethoxylized fatty alcohol is that ethoxylation degree is 3～50 C ₁₀～C ₁₈Ethoxylized fatty alcohol, best is that these Fatty Alcohol(C12-C14 and C12-C18) are that ethoxylation degree is 3～40 C ₁₂～C ₁₈Ethoxylized fatty alcohol.Be preferably, the alkyl chain length of mixed ethoxylated/propoxylated fatty alcohol is 10～18 carbon atoms, and ethoxylation degree is 3～30, and the propoxylation degree is 1～10.

The condenses of non-ionic type EO/PO and propylene glycol

The condensation product of oxyethane and a kind of hydrophobic base that generates by propylene oxide and propylene glycol condensation is suitable for using here.Better have an appointment 1500～about 1800 molecular weight of the hydrophobic part of these compounds, and demonstrate water-insoluble.The example of this type compound comprises that BASF AG puts on market, commercial some Pluronic that gets ^TMTensio-active agent.

The condensation product of non-ionic type EO and propylene oxide/ethylenediamine adduct

Oxyethane is suitable for using here with condensation product from the product of propylene oxide and reacting ethylenediamine generation.The hydrophobic part of these products is reaction product of quadrol and excessive propylene oxide.Its molecular weight is generally about 2500～about 3000.The example of such nonionic surface active agent comprises that BASF AG puts on market, commercial some TetronicTM compound that gets.

The non-ionic type alkyl polysaccharide surfactant

Be suitable for alkyl polysaccharide used herein and be disclosed in the United States Patent (USP) 4 of granting Llenado on January 21st, 1986,565, in 647, its hydrophobic grouping contains 6～about 30 carbon atoms of having an appointment, better contain 10～about 16 carbon atoms of having an appointment, and polysaccharide such as glycan glycosides hydrophilic radical contain have an appointment 1.3～about 10, better about 1.3～about 3, best about 1.3～about 2.7 sugar units.Can use any reducing sugar that contains 5 or 6 carbon atoms,, and can partly replace the glucosyl part with galactosyl as glucose, semi-lactosi.(randomly, hydrophobic grouping is connected on the positions such as 2-, 3-, 4-, thereby provides a kind of glucose or the semi-lactosi opposite with glucoside or galactoside.) these mutual sugared keys can be between 2-, 3-, 4-and/or 6-position such as a position that adds sugar unit and preceding sugar unit.

APG has following general formula preferably

R ²O (C _nH _2nO) _t(glycosyl) _xR in the formula ²Be selected from one group that is made up of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein alkyl group contains 10～18, better 12～14 carbon atoms; N is 2 or 3; T is 0～10, better be 0, x is 1.3～8, better 1.3～3, best 1.3～2.7.Glycosyl better is from the glucose deutero-.

The non-ionic type fatty acid amide surfactant

Be suitable for fatty acid amide surfactant used herein and be those person: R that has the following formula ⁶CON (R ⁷) ₂, R in the formula ⁶Be one and contain 7～21, the alkyl of better 9～17 carbon atoms, R ⁷Be selected from by hydrogen, C ₁～C ₄Alkyl, C ₁～C ₄Hydroxyalkyl and-(C ₂H ₄O) _xOne group of forming of H, the scope of x is 1～3 in the formula.

Amphoterics

Be suitable for amphoterics used herein and comprise amine oxide surfactant and alkyl both sexes carboxylic acid.

The example that is suitable for alkyl both sexes dicarboxylic acid used herein is Miranol (TM) the C2M Conc. that Miranol (N.J. Dayton) makes.

Amine oxide surfactant

The amine oxide that can here use comprises the compound that those have following general formula: R ³(OR ⁴) _xNO (R ⁵) ₂, R in the formula ³Be selected from alkyl, hydroxyalkyl, acyl group amidopropyl and the alkyl phenyl group or its mixture that contain 8～26 carbon atoms, better 8～18 carbon atoms; R ⁴It is alkylidene group or hydroxyl alkylidene group or its mixture that contains 2～3 carbon atoms, better 2 carbon atoms; X is 0～5, better 0～3; Each R ⁵Be one and contain 1～3, the alkyl or the hydroxyalkyl group of better 1～2 carbon atom, or one contains 1～3, the polyoxyethylene group of better 1 ethylene oxide group.Two R ⁵Group can form a ring structure such as being connected to each other by a Sauerstoffatom or nitrogen-atoms.

These amine oxide surfactants especially comprise C ₁₀～C ₁₈Alkyl-dimethyl amine oxide and C ₈～C ₁₈Alkoxyl oxygen alkyl ethyl two (hydroxyethyl) amine oxide.The example of this type of material comprises dimethyl octyl group amine oxide, diethyl decyl amine oxide compound, two (2-hydroxyethyl) dodecyl amine oxide, dimethyl dodecyl amine oxide, dipropyl tetradecyl amine oxide, methylethyl hexadecyl amine oxide, laurylamide base propyl group dimethylamine oxide compound, hexadecyl dimethylamine oxide compound, stearyl dimethylamine oxide compound, tallow dimethylamine oxide compound, and dimethyl-2-hydroxyl octadecyl amine oxide.Be preferably C ₁₀～C ₁₈Alkyl-dimethyl amine oxide, and C ₁₀～C ₁₈Acyl group amido alkyl dimethylamine oxide compound.

Amphoteric ionic surfactant

Amphoteric ionic surfactant also can mix in the detergent composition here.These tensio-active agents roughly can be described as the derivative of secondary amine and tertiary amine, the derivative of heterocyclic secondary and tertiary amine, or the derivative of quaternary ammonium, season or uncle's sulfonium compound.Trimethyl-glycine and sultaine (sultaine) tensio-active agent is an amphoteric ionic surfactant example as used herein.

Beet alkali surface activator

Here the available trimethyl-glycine is those compounds that following general formula is arranged: R (R ¹) ₂N ⁺R ²COO ^-, R is a C in the formula ₆～C ₁₈Alkyl better is a C ₁₀～C ₁₆Alkyl or C ₁₀～C ₁₆The acyl group amido alkyl, each R ¹C typically ₁～C ₃Alkyl, better be methyl, R ²Be a C ₁～C ₅Alkyl, better be a C ₁～C ₃Alkylidene group, be more preferably a C ₁～C ₂Alkylidene group.The trimethyl-glycine example that is suitable for comprises cocoyl amidopropyl dimethyl betaine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C ₁₂～C ₁₄The acyl group amido propyl betaine; C ₈～C ₁₄Acyl group amido-ethyl diethyl betaines; 4[C _14-16Acyl group methyl nitrosourea base diethyl ammonium]-1-carboxyl butane; C _16-18Acyl group amide group dimethyl betaine; C _12-16Acyl group amide group pentane diethyl betaines; C _12-16Acyl group methyl nitrosourea base dimethyl betaine.Trimethyl-glycine is C preferably _12-18Dimethylammonium guanidine-acetic acid salt and C _10-18Acyl group amide group propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The title complex beet alkali surface activator also is suitable for using here.

Sultaine (Sultaine) tensio-active agent

Sultaine is the compound that following general formula is arranged as used herein: R (R ¹) ₂N ⁺R ²SO ₃ ^-, R is C in the formula ₆-C ₁₈Alkyl better is C ₁₀-C ₁₆Alkyl is more preferably C ₁₂-C ₁₃Alkyl, each R ¹C typically ₁-C ₃Alkyl, better be methyl, and R ²Be C ₁-C ₆Alkyl better is C ₁-C ₃Alkylidene group, or better be the hydroxyl alkylidene group.

The amphotericeledrolyte tensio-active agent

Amphotericeledrolyte (ampholytic) tensio-active agent can mix the detergent composition here.These tensio-active agents roughly can be described as the aliphatic derivatives of secondary amine or tertiary amine, or the aliphatic derivatives of heterocyclic secondary and tertiary amine, and wherein aliphatic group can be that straight chain also can be a cladodification.

Cationic surfactant

Cationic surfactant also can be used for the detergent composition here.The cationic surfactant that is suitable for comprises and is selected from single C ₆-C ₁₆, better C ₆-C ₁₀The quaternary ammonium type tensio-active agent of N-alkyl or alkenyl ammonium surfactant, wherein all the other positions on the N have methyl, hydroxyethyl or hydroxypropyl group to replace.

Solvable or the soluble washing-aid compound of part

Detergent composition of the present invention can contain the solvable or insoluble washing-aid compound of a kind of part, and it is 1～80% (weight) of composition that there is level in its typical case, is preferably 10～70% (weight), is preferably 20～60% (weight).

The example of part water soluble detergency promoter comprises the silicate of crystallization stratification.

The washing assistant example that the water-insoluble degree is big comprises sodium aluminium silicate.

The general formula of crystallization stratification water glass is

NaMSi _xO _2x+ 1yH ₂M is sodium or hydrogen in the O formula, and x is 1.9～4 number, and y is 0～20 number.Such crystallization stratification water glass is disclosed in EP-A-0164514, and its preparation method then is disclosed in DE-A-3417649 and DE-A-3742043.For the present invention's purpose, the value of x is 2,3 or 4 in the above general formula, and is preferably 2.Best material is δ-Na ₂Si ₂O ₅, can be available from Hoechst AG company, its commodity are called NaSKS-6.

Crystallization stratification water glass material better is present in the granular detergent composition as the uniform mixing composition granule with a kind of solid, water soluble ionizable material.This solid, water soluble ionizable material is selected from organic acid, organic and inorganic acid salt and composition thereof.

The unit structure cell chemical formula of the aluminosilicate zeolites that is suitable for is Na _z[(AlO ₂) _z(SiO ₂) y] XH ₂Z and y are 6 at least in the O formula; The mol ratio of z and y is 1.0～0.5, and x is 5 at least, is preferably 7.5～276, is more preferably 10～264.This aluminosilicate material is hydrate forms, better is crystalline, contains 10～28%, is more preferably the water of 18～22% combining forms.

This aluminosilicate ion exchange material can be the natural material that exists, but better is synthetic deutero-.Trade(brand)names such as the synthesising crystal aluminium silicate ion-exchange material can zeolite A, zeolite B, zeolite P, X zeolite, zeolite MAP, zeolite HS and composition thereof have been bought.The chemical formula of zeolite A is Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂X is 20～30, particularly 27 in the O formula.The chemical formula of X zeolite is

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆]·276H ₂O。

The organic peroxide acid bleach system

A principal feature of the present invention is a kind of organic peroxide acid bleach system, and in a preferred embodiment, this bleach system comprises a kind of hydrogen peroxide cource and a kind of organic peroxide acid bleach precursor compound.Organic peroxide acid produces by this precursor and hydrogen peroxide cource situ reaction.Preferred hydrogen peroxide cource comprises inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER.In an alternative preferred embodiment, preformed organic peroxide acid is directly joined in the said composition.Containing the organic peroxy acid precursor of hydrogen peroxide cource and the composition of preformed organic peroxide acid also is susceptible to.

The organic peroxide acid bleach system better also possesses a kind ofly makes its delay be put into means in the washing soln, thereby make in the T50 test method, reach the required time of 50% the concentration of ultimate density of this peroxy acid bleach component greater than 180 seconds, better greater than 240 seconds.The means that any acquisition described here postpones to discharge all can be used.Have now found that this delay discharges that fading is good for preventing " patch shape " (promptly irregular) that fabric is in the suds.

Inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER

Inorganic perhydrate salts is preferred hydrogen peroxide cource, this class salt is normally with an alkali metal salt, the form of particular certain cancers is added, the interpolation level be said composition 1～40% (weight), be more preferably 2～30% (weight), best be 5～25% (weight).

The example of the inorganic perhydrate salts that is suitable for comprises perborate, percarbonate, superphosphate, persulphate and persilicate and any mixture thereof.Inorganic perhydrate salts is an alkali metal salt normally.Inorganic perhydrate salts can need not supplementary protection with the crystalline solid forms interpolation.Yet for some perhydrate salt, the better manufacture method of this type of granular composition is utilized the dressing form of this material, and this provides better package stability for the perhydrate salt in this granulated product.

Sodium peroxoborate can be nominal formula NaBO ₂H ₂O ₂Monohydrate form or tetrahydrate NaBO ₂H ₂O ₂3H ₂The O form.

Alkali metal percarbonate, especially SPC-D is the preferred perhydrate that is used for being included in the present composition.Have been found that in the presence of tensio-active agent and water contain the composition of percarbonate and compare with the composition that similarly contains perborate, its tendency that forms undesirable gel is less.It is believed that this is normally because percarbonate has lower surface area and lower porosity than perborate monohydrate.This low surface area and low porosity play the fine particle that prevents with surfactant aggregates cogelled effect take place, thereby are harmless for disperseing.

SPC-D promptly according to a kind of better perhydrate that present invention resides in the composition, is that a kind of corresponding chemical formula is 2Na ₂CO ₃3H ₂The addition compound of O can be crystalline solid forms and buy from the market.This percarbonate preferably is incorporated in such composition with the dressing form that product stability can be provided.

Can provide the suitable coating material of product stability to comprise the mixing salt of water-soluble alkali vitriol and carbonate.Such dressing and art for coating thereof were existing in the past to be described, and sees and grants the GB-1 of Interox, 466,799 on March 9th, 1977.The weight ratio scope of this mixing salt coating material and percarbonate is 1: 200 to 1: 4, is more preferably 1: 99 to 1: 9, and best is 1: 49 to 1: 19.Be preferably, this mixing salt is the mixing salt of sodium sulfate and yellow soda ash, and its general formula is Na ₂SO ₄HnNa ₂CO ₃, wherein n is 0.1～3, and being preferably n is 0.3～1.0, and best is that n is 0.2～0.5.

Contain other dressing of silicate (separately or with borate or boric acid or other inorganics), wax class, oils, fat soap, also can in the present invention, advantageously be used.

The peroxide Potassium peroxysulfate is the another kind of inorganic perhydrate salts that can use in detergent composition of the present invention.

Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that can produce peroxy acid in the reaction of peroxidation hydrogenolysis with hydroperoxidation.In general, peroxyacid bleach precursor can be expressed as

L is a leavings group in the formula, thereby the structure of the peroxy acid that is produced when the peroxidation hydrogenolysis is

The level of mixing of such peroxyacid bleach precursor compound, better be detergent composition 0.5～20% (weight), be more preferably 1～15% (weight), best be 1.5～10% (weight).

The peroxyacid bleach precursor compound that is suitable for typically contains one or more N-or O-carboxyl groups, and these precursors can be selected from far-ranging classification.The classification that is suitable for comprises the acylated derivatives of acid anhydride, ester, imide, lactan and imidazoles and oxime.The example of available materials has been disclosed in GB-A-1586789 in these classifications.The ester that is suitable for is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386.

The applicant finds that the damage of " patch shape " may be special relevant with the peroxyacid bleach precursor compound, and the latter provides a kind of peroxy acid when the peroxidation hydrogenolysis, promptly

(i) a kind of peroxybenzoic acid, or the derivative of its non-cationic type replacement; Or

(ii) a kind of cationic peroxy acid.

Found that also benzoxazine is responsive especially to this problem.

Leavings group

Leavings group to call the L group in the following text, must be enough active, so that the reaction of peroxidation hydrogenolysis can take place in Best Times scope (as a wash(ing)cycle).Yet if L is too active, this activator will be difficult to stablize to such an extent that can be used in the bleaching composition.

The L group is selected from one group that is made up of following preferably:

And composition thereof, R in the formula ¹Be alkyl, aryl or the alkaryl that contains 1～14 carbon atom, R ³Be the alkyl chain that contains 1～8 carbon atom, R ⁴Be H or R ³, and Y is H or solubilizing group.R ¹, R ³And R ⁴In any one group can be replaced by any functional group in principle, comprise, for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, amides and ammonium or alkyl ammonium group.

Solubilizing group is-SO preferably ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ⁺And O＜-N (R ³) ₃, and best be-SO ₂ ^-M ⁺With-CO ₂ ^-M ⁺, R in the formula ³Be the alkyl chain that contains 1～4 carbon atom, M is that an energy provides deliquescent positively charged ion to this bleach-activating agent, provides deliquescent negatively charged ion and X is an energy to this bleach-activating agent.Be preferably, M is a kind of basic metal, ammonium or the ammonium cation that replacement is arranged, and best is sodium and potassium, and X is halogenide, oxyhydroxide, Methylsulfate or acetate negatively charged ion.

Peroxybenzoic acid and derivative precursor thereof

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when the peroxidation hydrogenolysis.

The O-acidylate peroxybenzoic acid precursors compound that is suitable for include replacement with do not have the benzoyl oxygen benzene sulfonate that replaces, comprising such as benzoyl oxygen benzene sulfonate:

The benzoylation product that also has Sorbitol Powder, glucose and all carbohydrates and benzozlating agent generation that is suitable for, comprise such as:

Ac=COCH ₃The Bz=benzoyl

The peroxybenzoic acid precursors compound of imide-type comprises N-benzoyl succinimide, and four benzoyl quadrols and N-benzoyl have the urea of replacement.The imidazole type peroxybenzoic acid precursors that is suitable for comprises N-benzoyl imidazoles and N-benzoyl benzoglyoxaline, and the N-acyl group peroxybenzoic acid precursors that contains that other is useful comprises N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

Other peroxybenzoic acid precursors comprises the benzoyl diacyl peroxide, the compound of benzoyl four acyl peroxides and following general formula: Tetra hydro Phthalic anhydride is the another kind of peroxybenzoic acid precursors compound that is suitable among the present invention:

The N-acylated lactams peroxybenzoic acid precursors that is suitable for has following general formula: In the formula n be 0～about 8, better be 0～2, and R ⁶Be aryl, alkoxy aromatic yl or the alkylaryl group that contains 1-12 carbon atom, or contain the phenyl group of the replacement of 6-18 carbon atom, preferred benzoyl group.

Peroxybenzoic acid derivative precursor

Physical efficiency provides the peroxybenzoic acid of replacement before the peroxybenzoic acid derivative when the peroxidation hydrogenolysis.

The peroxybenzoic acid derivative precursor that replacement is arranged that is suitable for comprises any peroxybenzoic acid precursors disclosed by the invention; wherein there is any basically non-positive polarity (being the non-cationic type) functional group to replace on the benzoyl group, comprises such as alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl and amide group.

Have in the peroxybenzoic acid precursors compound of replacement one preferably classification be the acid amides substitution compound of following general formula: R in the formula ¹Be aryl or the alkaryl that 1～14 carbon atom is arranged, R ²Be arylidene or the alkarylene that 1～14 carbon atom is arranged, R ⁵Be H or alkyl, aryl or the alkaryl that 1～10 carbon atom is arranged, L can be any basically leavings group.R ¹Better contain 6～12 carbon atoms.R ²Better contain 4～8 carbon atoms.R ¹Can be to contain cladodification, replacement or aryl that both have both at the same time, substituted aryl or alkaryl are arranged, and can come from or synthetic source or natural source, comprise such as beef fat.R ²Also allow similar structural changes.Replacement can comprise alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group group or organic compound.R ⁵Better be H or methyl.R ¹And R ⁵Should not contain more than 18 carbon atoms altogether.Bleach activating immunomodulator compounds such, that have acid amides to replace can be consulted EP-A-0170386.

Cationic peroxyacid precursor

Cationic peroxyacid precursor compound produces cationic peroxy acid when the peroxidation hydrogenolysis.

Typically say, cationic peroxyacid precursor be by make a kind of peroxy acid that is applicable to the peroxyacid precursor compound partly have a positively charged functional group as ammonium or alkane ammonium, better be that second ammonium or first ammonium replace and generate.

The peroxyacid precursor compound that will carry out cationic replacement like this can be that above-described a kind of peroxybenzoic acid or its have the derivative precursor compound of replacement.In addition, the peroxyacid precursor compound can be alkyl peroxycarboxylic acid precursors compound of the following stated or the alkyl peroxy acids precursor that the acid amides replacement is arranged.

Cationic peroxyacid precursor can be consulted United States Patent (USP) 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.1,382,594; EP475,512,458,396 and 284,292; And JP 87-318,332.

The example of cationic peroxyacid precursor can be consulted UK Patent Application No.9407944.9 and U.S. Patent application No.08/298903,08/298650,08/298904 and 08/298906 preferably.

The cationic peroxyacid precursor that is suitable for comprises following any: a hexanolactam and a benzoyl tetrem acyl glucose benzoyl peroxide that alkyl that ammonium or alkane ammonium replace or benzoyl oxygen benzene sulfonate, N-acidylate are arranged.

Preferably, the benzoyl oxygen benzene sulfonate of cationic replacement being arranged is 4-(TMA (TriMethylAmine)) methyl-derivatives of benzoyl oxygen benzene sulfonate:

Preferably, have the alkyl oxygen benzene sulfonate of cationic replacement to have following chemical formula:

The better cationic peroxyacid precursor of N-acidylate hexanolactam class comprises three alkane ammonium methylene radical benzoyl caprolactam, especially TMA (TriMethylAmine) methylene radical benzoyl caprolactams:

Other better cationic peroxyacid precursor of N-acidylate hexanolactam class comprises three alkane ammonium methylene radical hexanolactams: N is 0-12 in the formula.

The cationic preferably peroxyacid precursor of another kind is carbonic acid (chlorination 2-(N, N, N-TMA (TriMethylAmine)) ethyl ester) (4-(sodium sulfo group) phenyl ester).

Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor generates percarboxylic acids when the peroxidation hydrogenolysis.Such better precursor produces peracetic acid when the peroxidation hydrogenolysis.

The better alkyl peroxycarboxylic acid precursors compound of imide type comprises N, N, and N ', N '-tetrem acidylate Alkylenediamine, wherein alkylidene group contains 1～6 carbon atom, and especially those its alkylidene groups contain the compound of 1,2 and 6 carbon atom.That good especially is tetraacetyl ethylene diamine (TAED).

Other preferably the alkyl peroxycarboxylic acid precursors comprise 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (different-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.

The alkyl peroxy acids precursor that acid amides replaces

The alkyl peroxy acids precursor compound that acid amides replaces also is suitable for, and comprises the acid amides substitution compound of following general formula:

R in the formula ¹Be the alkyl group that 1～14 carbon atom is arranged, R ²Be the alkylidene group that contains 1～14 carbon atom, R ⁵Be H or the alkyl group that contains 1～10 carbon atom, L can be any basically leavings group.R ¹Better contain 6～12 carbon atoms.R ²Better contain 4～8 carbon atoms.R ¹Can be to contain branching, replacement or straight or branched alkyl that both have both at the same time, and can come from or synthetic source or natural source, comprise such as beef fat.R ²Also allowing similar structures changes.Replacement can comprise alkyl, halogen, nitrogen, sulphur and other typical substituting group group or organic compound.R ⁵Better be H or methyl.R ¹And R ⁵Add up to and should not contain more than 18 carbon atoms.Such acid amides substituted bleach activator compound can be consulted EP-A-0170386.

Benzoxazine organic peroxy acid precursor

Be disclosed in for example EP-A-332, the benzoxazine type precursor compound in 294 and EP-A-482,807 particularly has general formula Those compounds, comprise that the benzoxazine compound of the replacement of following formula shown type also is suitable for:

R wherein ₁Be H, alkyl, alkaryl, aryl, aralkyl, and R wherein ₂, R ₃, R ₄And R ₅Can be identical or different H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, the COOR of being selected from ₆(R wherein ₆Be H or alkyl) and the substituting group of carbonyl.

A particularly preferred precursor in the benzoxazine type is:

The preliminary shaping organic peroxide acid

In the organic peroxide acid bleach system except containing a kind of organic peroxide acid bleach precursor compound, perhaps as a kind of surrogate, also can contain a kind of preformed organic peroxide acid, its content is generally the 1%-15% of composition weight, is preferably 1%-10%.

A preferred class organic peroxy acid compound is the compound that the acid amides shown in the following general formula replaces: R wherein ¹Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R ²Be alkylidene group, arylidene and the alkarylene that contains 1-14 carbon atom, R ⁵Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom.R ¹Better contain 6-12 carbon atom.R ²Better contain 4-8 carbon atom.R ¹Can be the straight or branched alkyl, have side chain, substituting group, or the both substituted aryl or the alkaryl that have, and can derive from synthetic source or natural source, comprise for example butter fat.For R ², similar structural changes allows.Substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferred H or methyl.R ¹And R ⁵Contained the total number of carbon atoms can not be above 18.The organic peroxy acid compound that such acid amides replaces is disclosed in EP-A-0170386.

Other organic peroxide acid comprises diacyl and four acyl peroxides, and especially two mistake dodecandioic acids, two are crossed dodecane dicarboxylic acids and two and crossed tetradecane dicarboxylic acids.Single and two nonane diacid, list and two brassylic acid and N-O-phthalic amido crossed crossed caproic acid and here also is suitable for.

Chlorine bleach

Composition of the present invention better is a chlorine bleaching agent not.

Bleaching catalyst

The present invention also comprises the composition that contains catalytically effective amount bleaching catalyst such as water-soluble manganese salt.

Bleaching catalyst is used for composition of the present invention with catalytically effective amount.So-called " catalytically effective amount " means and adopting the bleaching that all is enough to one or more interesting on intensifier target matrix spots under which kind of comparison test condition and the quantity of removal.Therefore, in the fabric washing operation, target matrix has the fabric that stains such as various food stain typically.For automatic dishwashing, target matrix can be all porcelain cup or dishes if any the tea stain, or the polyethylene pan that has tomato soup to stain.Test conditions will be different because of used scrubber type and user's custom.For example, the front-loading washing machine of the Europe type that adopts is compared with roof-mounted American version washing machine, generally uses less water and higher detergent concentration.The wash(ing)cycle of some washing machines is more much longer than other washing machine.Some users like using very hot water; Other users use warm water or even cold water in the fabric washing operation.Certainly, the catalytic performance of bleaching catalyst can be subjected to this type of and consider influence, and the bleaching catalyst level of using in full formula washing composition and bleaching composition can suitably be adjusted.As a practical problems, and be not so as to restriction, composition here and technology can be adjusted, and so that the active bleaching catalyst kind of 1/10,000,000 (0.1ppm) order of magnitude to be provided in aqueous cleaning solution, and better will provide about 1ppm～about 200ppm catalyzer kind in washing liquid.For further specifying this point, under the European condition of using perborate and bleach precursor (as benzoyl caprolactam), at 40 ℃ and pH10, about 3 micromole's Mn catalysts are effective.Under U.S.'s condition, may need to make concentration to improve 3～5 times and just can reach effect same.Otherwise bleach precursor and Mn catalyst use with perborate, can make the makers-up just can reach equal bleaching in the perborate consumption level lower than the product of no Mn catalyst.

The bleach catalyst agent material here can comprise free acid or be the form of any suitable salt.

A kind of bleaching catalyst type is a catalyst system that comprises following ingredients: the active heavy metal cation of certain bleach catalyst is arranged, as copper, iron or manganese positively charged ion; Have slight or do not have the active assistant metal positively charged ion of bleach catalyst, as zinc or aluminium cations; With the sequestrant that catalytic metal positively charged ion and assistant metal positively charged ion is had certain stability constant, especially ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and water-soluble salt thereof.United States Patent (USP) 4,430,243 disclose such catalyzer.

Other bleaching catalyst type comprises United States Patent (USP) 5,246,621 and United States Patent (USP) 5,244,594 in disclosed manganese basigamy compound.The better example of these 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) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃, and composition thereof.Other example can be consulted european patent application communique No.549,272.Be suitable for other part used herein and comprise 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4, the 7-7-triazacyclononane, and composition thereof.

About being suitable for the example of bleaching catalyst, see also United States Patent (USP) 4,246,612 and United States Patent (USP) 5,227,084.Also see also United States Patent (USP) 5,194,416, this patent disclosure monokaryon manganese (IV) title complex, as Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃-(PF ₆).United States Patent (USP) 5,114, disclosed another kind of again bleaching catalyst type is manganese (II), (III) and/or (IV) and a kind of water-soluble complexes of part in 606, this part is a kind of non-carboxylation polyols that at least three the adjacent C-OH of company groups are arranged.Preferably part comprise Sorbitol Powder, iditol, dulse sugar alcohol, mannitol, Xylitol, arabitol, adonitol, meso tetrahydroxybutane, meso-inositol, lactose, and composition thereof.

United States Patent (USP) 5,114,611 disclose a kind of bleaching catalyst, comprise the title complex that transition metal comprises Mn, Co, Fe or Cu and a kind of non-(greatly) ring part.The general formula of described part is: R in the formula ¹, R ², R ³And R ⁴Each can be selected from H, the alkyl and the aromatic yl group of replacement are arranged, and makes each R ¹-N=C-R ²With R ³-C=N-R ⁴Can form one five yuan or six-ring.Described ring can have further replacement.B is a bridged group, is selected from O, S, CR ⁵R ⁶, NR ⁷And C=O, R in the formula ⁵, R ⁶And R ⁷Each can be H, alkyl or aryl group, includes group replacement or that do not have replacement.Part comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring preferably.Randomly, described ring can have substituting groups such as alkyl, aryl, alkoxyl group, halogen and nitro to replace.Especially good is 2,2 '-bipyridyl amine ligand.Bleaching catalyst comprises bipyridyl methane and the bipyridyl amine complex of Co, Cu, Mn, Fe preferably.Extraordinary catalyzer comprises Co (2,2 '-bipyridyl amine) Cl ₂, two (isothiocyanato) bipyridyl amine-cobalt (II) is crossed chloric acid three (bipyridyl amine)-cobalt (II), Co (2,2 '-bipyridyl amine) ₂O ₂ClO ₄, cross chloric acid two (2,2 '-bipyridyl amine) copper (II), cross chloric acid three (two-2-pyridyl amine) iron (II), and composition thereof.

Other example comprises glyconic acid Mn, Mn (CF ₃SO ₃) ₂, Co (NH ₃) ₅Cl and the double-core Mn that cooperates with four-N-dentate and two-N-dentate part comprise N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺((bipyridyl amine) ₂Mn ^III(u-O) ₂Mn ^IV(bipyridyl amine) ₂)-(ClO ₄) ₃

Bleaching catalyst also can prepare like this: make a kind of water soluble ligand and a kind of water-soluble manganese salt chemical combination in water medium, with method of evaporation formed mixture is concentrated.Any water-soluble manganese salt easily all can use at this.Manganese (II), (III), (IV) and/or (V) be easy on market, buy.In some cases, can in washings, there be the manganese of capacity, but in general, be preferably a Mn positively charged ion and adds in the composition, exist with catalytically effective amount to guarantee it.For example, the sodium salt of this part with from by MnSO ₄, Mn (ClO ₄) ₂Or MnCl ₂A member of selecting in one group that (relative importance value is minimum) formed is at neutrality or slight alkalinity pH, and be about 1: 4～4: 1 part with scope: Mn salt mol ratio is dissolved in the water.This water can select and boil deoxidation, cools off with nitrogen purging then.Formed solution evaporation (if be ready, can be at N ₂Carry out under the atmosphere), resulting solid is used for bleaching and detergent composition here, need not to be further purified.

Another kind of mode is, water-soluble manganese source such as MnSO ₄Add in bleaching/cleaning compositions, or add in the aqueous bleaching/cleaning bath that contains this part.Obviously generate certain type title complex on the spot, also ensured the bleachability that improves.In a kind of like this technology on the spot, be to use part easily than the quite big molar excess of manganese, and the mol ratio of part: Mn be typically 3: 1～15: 1.Unnecessary part also plays the effect of removing variable metal ion such as iron and copper, thereby prevents this SYNTHETIC OPTICAL WHITNER decomposition.European patent application communique No.549 has described a kind of this possible type systematic in 271.

Though do not illustrate the structure of the manganese complex of some energy catalytically bleachings described here as yet, can infer that they comprise by the carboxyl of part and inner complex or other hydration coordinate complex of nitrogen-atoms and manganese positively charged ion interaction generation.Equally, the cationic, oxidized attitude of manganese also is unascertained during the catalytic process, may be (+II), (+III), (+IV) or (+V) valence state.Because these parts have six possible tie points to the manganese positively charged ion, thereby can reasonably infer and in the aqueous bleaching medium, may have multinuclear form and/or " cage " shape structure.Regardless of the physical presence form of active Mn part form, it all works with obvious catalytic way, the spot of stubbornness such as tea, tomato juice, coffee, blood stains etc. is provided the bleachability of improvement.

Other bleaching catalyst can be consulted, for example, and european patent application communique No.408,131 (cobalt complex catalyzer), european patent application communique No.384,503 and 306,089 (metal leaf quinoline catalyzer), United States Patent (USP) 4,728,455 (manganese/polygamy position ylidene ligands catalyzer), United States Patent (USP) 4,711,748 and european patent application communique No.224,952 (being absorbed in the Mn catalyst on the aluminosilicate), United States Patent (USP) 4,601,845 (the aluminosilicate supporters that manganese and zinc or magnesium salts are arranged), United States Patent (USP) 4,626,373 (manganese/ligand catalysts), United States Patent (USP) 4,119,557 (high ferro composition catalysts), German Patent communique 2,054,019 (cobalt sequestrant catalyzer), Canadian Patent 866,191 (salt that contain transition metal), United States Patent (USP) 4,430,243 (sequestrant and manganese positively charged ion and on-catalytic metallic cations), with United States Patent (USP) 4,728,455 (managanese gluconate catalyzer).

The organic polymer compounds

The organic polymer compounds is according to composition good especially in the detergent composition of the present invention.So-called organic polymer compounds means any basically polymerizable organic compound that is usually used in the detergent composition as dispersion agent and antiredeposition and soil-suspending agent.

The typical case of organic polymer compounds in detergent composition of the present invention mixes level, be said composition 0.1～30%, better 0.5～15%, best 1～10% (weight).

The organic polymer examples for compounds comprises water-soluble organic homopolymerization or copolymerization poly carboxylic acid or its salt, and wherein poly carboxylic acid comprises at least two each other by no more than two carboxyls that carbon atom separates.One type the polymkeric substance in back is GB-A-1, and is disclosed in 596,756.The example of this type of salt be molecular weight 2000～5000 polyacrylate and with the multipolymer of maleic anhydride, the molecular weight of this analog copolymer is 20,000～100,000, especially 40,000～80,000.

Other suitable organic polymer compounds comprises the polymkeric substance of acrylamide and acrylate, and its molecular weight is 3,000～100,000, and acrylate/fumarate multipolymer, and its molecular weight is 2,000～80,000.

The polyamino compound also can use at this, comprises from those aspartate-derived compounds, for example those disclosed among EP-A-305282, EP-A-305283 and the EP-A-351629.

The terpolymer that contains the monomeric unit of from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, selecting, especially those molecular-weight average is arranged is 5,000～10,000 terpolymer, also be suitable at this.

Other organic polymer compounds that is suitable for mixing the detergent composition here comprises derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose and Natvosol.

Further available organic polymer compounds is a polyoxyethylene glycol, especially molecular weight 1000～10000, be more preferably 2000～8000, best be those polyoxyethylene glycol of about 4000.

The lime soap dispersing agent compound

The present composition can contain a kind of lime soap dispersing agent compound, its by with undefined calcium soap dispersive power (LSDP) for being not more than 8, better being not more than 7, preferably being not more than 6.This lime soap dispersing agent compound exist level better be said composition 0.1～40% (weight), be more preferably 1～20% (weight), best be 2～10% (weight).

Lime soap dispersing agent is that a kind of an alkali metal salt, ammonium salt or amine salt of lipid acid of preventing is by calcium or the sedimentary material of magnesium ion.The numerical measure of the validity of lime soap dispersing agent is provided by calcium soap dispersive power (LSDP), is can will (J.AM.Oil.Chem.Soc.) the 27th roll up the calcium soap distributed test mensuration described in one piece of article delivering on the 88-90 page or leaf (1950) with H.C.Borghetty and C.A.Bergman at the american petroleum chemistry.This calcium soap distributed test method is extensive use of by the expert in present technique field, for example, can consult following survey article: W.N.Linfield, tensio-active agent science series (Surfactant Science Series), the 7th volume page 3; W.N.Linfield, the 159th～161 page (1990) of tensio-active agent and washing composition (Tenside Surf.Det.) the 27th volume; With M.K.Nagarajan, W.F.Masler, makeup and sanitary product (Cosmetics and Toiletries) the 104th volume 71-73 page or leaf (1989).LSDP makes the 0.025g sodium oleate at 30ml 333ppm CaCO ₃(Ca: Mg=3: 2) the calcium soap settling that generates in the water of equivalent hardness disperses the weight percent of needed dispersion agent and sodium oleate.

There is the tensio-active agent of good lime soap dispersing agent ability to comprise some amine oxide, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylation alcohols.

The tensio-active agent example that LSDP is not more than 8, meet purposes of the present invention comprises C ₁₆-C ₁₈Dimethylamine oxide compound, average degree of ethoxylation are 1～5 C ₁₂-C ₁₈Alkyl ethoxy sulfate, the especially C of ethoxylation degree about 3 ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant (LSDP=4) and average degree of ethoxylation are the C of 12 (LSDP=6) or 30 ₁₃-C ₁₅Ethoxylated alcohol is that BASF AG (BASF GmbH) sells with trade(brand)name Lutensol AO12 and Lutensol AO30 respectively.

Being suitable for polymkeric substance lime soap dispersing agent used herein has description in the article of M.K.Nagarajan and W.F.Masler, see makeup and sanitary product (Cosmetics andToiletries) the 104th volume 71-73 page or leaf (1989).The example of this base polymer lime soap dispersing agent comprises vinylformic acid, methacrylic acid or its mixture and a kind of acrylamide or some water-soluble salt of the multipolymer of substituted acrylamide arranged, the molecular weight of this base polymer typically 5,000～20,000.

Foam inhibition system

Detergent composition of the present invention when when being used for the machine-washing composition and preparing, better comprises a kind of foam inhibition system, its exist level be said composition 0.01～15%, better 0.05～10%, best 0.1～5% (weight).

Be suitable for foam inhibition system used herein and can comprise any basically known defoaming compounds, comprise such as siloxanes defoaming compounds, 2-alkyl chain triacontanol class defoaming compounds.

So-called defoaming compounds means here and can play such as suppressing by a kind of solution of detergent composition, the especially any compound of a kind of like this effect of foam of generation or the mixture of compound in the presence of the stirring of this solution.

Being suitable for used herein, good especially defoaming compounds is the siloxanes defoaming compounds that is defined as any defoaming compounds here, comprises a kind of silicone component.Such siloxanes defoaming compounds also typically comprises a kind of silica composition.Here the quite high polymkeric substance of various molecular weight that contains siloxane unit and all kinds alkyl contained in " siloxanes " this term that generally uses and in this industry.The siloxanes defoaming compounds is a siloxanes preferably, and the unitary polydimethylsiloxane of trimethyl silyl end-blocking is especially arranged.

Other suitable defoaming compounds comprises mono carboxylic lipid acid and soluble salt thereof.These materials see the Wayne st.John United States Patent (USP) of announcing September 27 nineteen sixty 2,954,347 for details.The hydrocarbyl chain that mono carboxylic lipid acid that uses as froth suppressor and salt thereof typically have 10～about 24 carbon atoms, better 12～18 carbon atoms.The salt that is suitable for comprises an alkali metal salt such as sodium salt, sylvite and lithium salts and ammonium salt and pure ammonium salt.

Other suitable defoaming compounds comprises, for example, and high molecular fatty ester (as fatty acid triglycercide), the fatty acid ester of monohydroxy-alcohol, aliphatic C ₁₈-C ₄₀Ketone (stearone), N-alkylation aminotriazine contains two～tetraalkyl diamine chlorotriazine that the reaction product of the primary amine of 1～24 carbon atom or secondary amine generates, propylene oxide, distearyl acid acid amides and a stearyl two basic metal (as sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester as three～six alkyl melamines or as cyanuric chloride and 2～3 moles.

The multipolymer of oxyethane and propylene oxide, especially alkyl chain length be 10～16 carbon atoms, ethoxylation degree be 3～30 and the propoxylation degree be mixed ethoxylated/propoxylated fatty alcohol of 1～10, also be to be suitable for defoaming compounds used herein.

Be suitable for 2-alkyl chain triacontanol class defoaming compounds used herein existing description in DE 4021265.Being suitable for 2-alkyl chain triacontanol class used herein is a kind of C that has terminal hydroxyl ₆-C ₁₆Alkyl chain, described alkyl chain have a C on alpha position ₁～C ₁₀Alkyl chain replaces.The mixture of 2-alkyl chain triacontanol can be used for according to composition of the present invention.

A kind of foam inhibition preferably system comprises

(a) defoaming compounds better is the siloxanes defoaming compounds, and preferably a kind of siloxanes defoaming compounds comprises in the combination

(i) polydimethylsiloxane, its fusion level is 50～99% of this siloxanes defoaming compounds, better is 75～95% (weight); With

(ii) silicon-dioxide, its fusion level be this siloxanes/silicon-dioxide defoaming compounds 1～50%, better be 5～25% (weight);

The fusion level of wherein said silica/silicon oxygen alkane defoaming compounds is 5～50%, better 10～40% (weight);

(b) a kind of compound dispersing agent, preferably include a kind of siloxane glycol rake formula multipolymer, its polyoxy alkylidene content be 72～78% and the ratio of oxyethane and propylene oxide be 1: 0.9～1: 1.1, the fusion level is 0.5～10%, better 1～10% (weight); Such a kind of good especially siloxane glycol rake formula multipolymer is DCO544, is that Dao Kening (DOWCorning) company sells with trade(brand)name DCO544;

(c) a kind of inert support fluid compound preferably includes a kind of C ₁₆-C ₁₈Ethoxylated alcohol, its ethoxylation degree be 5～50%, better 8～15%, its fusion level is 5～80%, be preferably 10～70% (weight);

Can the foam inhibition system of a kind of as used herein particulate state preferably comprise the alkylation siloxanes of above disclosed type and the mixture of solid silica.

This solid silica can be the silica particle that the flue gas method forms, the silicon-dioxide that the precipitator method form, or the silicon-dioxide made from the gel formation technology.The mean particle size of the silica dioxide granule that is suitable for is 0.1～50 μ m, better 1～20 μ m, and its specific surface area is 50m at least ²/ g.These silica dioxide granules can be by with dialkyl group silyl-group and/or trialkylsilyl group or make it to be bonded directly on this silicon-dioxide or by means of a kind of silicone resin it is handled and make it to have hydrophobicity.Being preferably to adopt a kind ofly makes its particle have hydrophobic silicon-dioxide with dimethyl and/or trimethyl silyl group.A kind of defoaming compounds of particulate state preferably that is used for mixing according to detergent composition of the present invention can suitably contain a certain amount of silicon-dioxide, makes that the weight ratio of silicon-dioxide and siloxanes is in 1: 100～3: 10, better 1: 50～1: 7 scope.

The representative of the another kind of foam inhibition system of particulate state that is suitable for is a kind of hydrophobic silaneization (preferably trimethyl silicone hydride) silicon-dioxide, and its size range is 10～20 nanometers, and specific surface area is greater than 50m ²/ g, with molecular weight ranges be about dimethyl silicone fluids thorough mixing of 500～about 200,000, the weight ratio of siloxanes and silanized silica is about 1: 1～about 1: 2.

The foam inhibition system of a kind of highly preferred particulate state is described in EP-A-0210731, comprise a kind of siloxanes defoaming compounds and a kind of melting range and be 50～85 ℃ organic support material, wherein organic support material comprises glycerine and a kind of a kind of monoesters that the lipid acid of the carbochain that contains 12～20 carbon atoms is arranged.EP-A-0210721 discloses other foam inhibition system of particulate state preferably, and wherein organic support material is a kind of a lipid acid or an alcohol that contains the carbochain of 12～20 carbon atoms to be arranged, or its mixture, and its fusing point is 45～80 ℃.

Other foam inhibition system of highly preferred particulate state sees for details with P﹠amp; The european patent application 91870007.1 that G company (Procterand Gamble Company) name proposes, examining, these systems comprise siloxanes defoaming compounds, a kind of solid support material, a kind of organic coating material and glycerine, glycerine: the weight ratio of siloxanes defoaming compounds is 1: 2～3: 1.The european patent application of examining 91201342.0 also discloses the foam inhibition system of highly preferred particulate state, wherein comprise siloxanes defoaming compounds, a kind of solid support material, a kind of organic coating material and crystallization or amorphous aluminosilicate, aluminosilicate: the weight ratio of siloxanes defoaming compounds is 1: 3～3: 1.In above-mentioned two kinds of highly preferred granular foam control agents preferably solid support material be starch.

The example of the foam inhibition system of a kind of particulate state used herein is a kind of particulate state agglomerate composition made from agglomeration process (agglomeration process), wherein contains with array mode

(i) 5～30%, better 8～15% (weight) siloxanes defoaming compounds composition, better contain polydimethylsiloxane and silicon-dioxide with array mode;

(ii) 50～90%, better 60～80% (weight) solid support material composition, better be starch;

(iii) 5～30%, better 10～20% (weight) agglomerate binder compound composition, in this case, here such compound can be any compound or its mixture that typically is used as the agglomerate binding agent, best is that described agglomerate binder compound comprises that a kind of ethoxylation degree is 50～100 C ₁₆-C ₁₈Ethoxylated alcohol; With

(iv) 2～15%, better 3～10% (weight) C ₁₂-C ₂₂Hydrogenation lipid acid.

The polymeric dye transfer inhibitor

The detergent composition here also can comprise 0.01～10%, better 0.05～0.5% (weight) polymeric dye transfer inhibitor.

These polymeric dye transfer inhibitors better are selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its combination of polyamines N-oxide polymer, N-vinyl pyrrolidone and N-vinyl imidazole.

A) polyamines N-oxide polymer

Be suitable for the unit that polyamines N-oxide polymer used herein contains following structural formula: P is a polymerizable unit in the formula, can connect the R-N-O group on it, or wherein the R-N-O group constitutes the integral part of this polymerizable unit, or both have both at the same time; A is

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

R is aliphatic group, ethoxylation aliphatic group, aromatic group, heterocyclic group or alicyclic group, or its any combination, can connect the nitrogen of N-O group on it, or wherein the nitrogen of N-O group is the integral part of these groups.

The N-O group can be represented with following general structure: R in the formula ₁, R ₂And R ₃Be aliphatic group, aromatic group, heterocyclic group or alicyclic group or its combination, x and/or y and/or z are 0 or 1, and wherein can connect the nitrogen of N-O group, or wherein the nitrogen of N-O group constitutes the integral part of these groups.The N-O group can be the integral part of this polymerizable unit (P), also can be connected on the main polymer chain, or both haves both at the same time.

Its N-O group constitutes the suitable polyamines N-oxide compound of this polymerizable unit integral part, comprises that its R is selected from the polyamines N-oxide compound of aliphatic group, aromatic group, alicyclic group or heterocyclic group.The described polyamines N-of one class oxide compound comprises such one group of polyamines N-oxide compound, and wherein the nitrogen of N-O group constitutes the integral part of R-group.Polyamines N-oxide compound is that its R is those of heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof preferably.

In addition-and the described polyamines N-of class oxide compound comprises such one group of polyamines N-oxide compound, wherein the nitrogen of N-O group is connected on the R-group.

Other polyamines N-oxide compound that is suitable for is that its N-O group is connected to those polyamine oxidase things on this polymerizable unit.

These polyamines of class N-oxide compound is those polyamines N-oxide compounds with general formula (I) preferably, and wherein R is aromatic group, heterocyclic group or an alicyclic group, and wherein the nitrogen of N-O functional group is the integral part of described R-group.The example of these classifications is that its R is the polyamine oxidase thing of a kind of heterogeneous ring compound such as pyridine, pyrroles, imidazoles and derivative thereof.

The another kind of N-of polyamines preferably oxide compound is those polyamine oxidase things with general formula (I), and wherein R is aromatic group, heterocyclic group or alicyclic group, and wherein the nitrogen of N-O functional group is connected on the described R group.The example of these classifications is polyamine oxidase things that its R group can be aromatic group such as phenyl.

Any main polymer chain can use, as long as the amine oxide polymkeric substance that is generated is water miscible and has the dye transfer rejection.The example of suitable polymers main chain is polyethylene base class, polyalkenes class, polyester, polyethers, polymeric amide, polyimide, polyacrylate and composition thereof.

The ratio that amine n-oxide polymkeric substance of the present invention typically has amine and this amine n-oxide is 10: 1～1: 1000000.Yet the amount of amine oxide can be by suitable copolymerization or by appropriate N-oxidation change in this polyamine oxidase thing polymkeric substance.Be preferably, amine is 2: 3～1: 1000000 with the ratio of amine n-oxide.Be more preferably 1: 4～1: 1000000, best is 1: 7～1: 1000000.In fact polymkeric substance of the present invention contains random or segmented copolymer, and wherein a kind of monomer type is an amine n-oxide, another kind of monomer type or amine n-oxide or be not.The amine oxide unit of polyamines N-oxide compound has PKa＜10, better PKa＜7, is more preferably PKa＜6.

These polyamine oxidase things can be with almost any polymerization degree acquisition.The polymerization degree is unimportant, as long as this material has desirable water-soluble and dye suspension ability.Say that typically average molecular weight range is 500～1000,000; Be preferably 1,000～50,000, be more preferably 2,000～30,000, best is 3,000～20,000.

B) multipolymer of N-vinyl pyrrolidone and N-ethene imidazoles

Better polymkeric substance used herein can comprise a kind of polymkeric substance of the N-of being selected from vinyl imidazole N-vinylpyrrolidone copolymer, and the average molecular weight range of wherein said polymkeric substance is 5,000～50,000, be more preferably 8,000～30,000, best is 10,000～20,000.In the N-vinyl imidazole N-vinylpyrrolidone copolymer, the mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1～0.2, is more preferably 0.8～0.3 preferably, and best is 0.6～0.4.

C) Polyvinylpyrolidone (PVP)

The detergent composition here also can utilize Polyvinylpyrolidone (PVP) (" PVP "), and its molecular-weight average is 2,500～400,000, is preferably 5,000～200,000, is more preferably 5,000～50,000, and best is 5,000～15, and 000.The Polyvinylpyrolidone (PVP) that is suitable for can be available from ISP company (New York, New York and Montreal, CAN city), name of product is that (molecular-weight average is 10 to PVPK-15,000), (molecular-weight average is 40 to PVPK-30,000), (molecular-weight average is 160 to PVPK-60,000) and PVP K-90 (molecular-weight average is 360,000).PVP K-15 also can be available from ISP company.Can comprise Sokalan HP165 and Sokalan HP 12 available from other suitable polyethylenes base pyrrolidone of BASF (BASF) company.

Polyvinylpyrolidone (PVP) can mix the detergent composition here, its mix level for 0.01～5% (weight), better 0.05～3% (weight) of this washing composition, be more preferably 0.1～2% (weight).The Polyvinylpyrolidone (PVP) quantity that provides in washing soln is preferably 0.5～250ppm, is more preferably 2.5～150ppm, best be 5～100ppm.

D) Ju Yi Xi oxazolidinone

The detergent composition here also can utilize Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidinone is 2,500～400,000, be preferably 5,000～200,000, be more preferably 5,000～50,000, best be 5,000～15,000.

In the detergent composition incorporation of Ju Yi Xi oxazolidinone can be 0.01～5% (weight), better be 0.05～3% (weight), be more preferably 0.1～2% (weight).The Ju Yi Xi oxazolidinone quantity that provides in the washing soln typically 0.5～250ppm, better be 2.5～150ppm, be more preferably 5～100ppm.

E) polyvinyl imidazol

The detergent composition here also can utilize polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazol is preferably 2,500～400,000, be more preferably 5,000～50,000, best be 5,000～15,000.

The incorporation of polyvinyl imidazol can be 0.01～5% (weight), is preferably 0.05～3% (weight), is more preferably 0.1～2% (weight) in the detergent composition.The polyvinyl imidazol quantity that provides in the washing is 0.5～250ppm, is preferably 2.5～150ppm, is more preferably 5～100ppm.

Optical whitening agent

The detergent composition here also can randomly contain some the type hydrophilic optical whitening agent of 0.005～5% (weight) of having an appointment, and they also provide the dye transfer restraining effect.If use, the composition here better will comprise about 0.01～1% (weight) this type of optical whitening agent.

Can be used for hydrophilic optical whitening agent of the present invention is that those have following structural formula person:

R in the formula ₁Be selected from anilino, N-2-dihydroxy ethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-dihydroxy ethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; And M is a kind of salt-forming cation such as sodium or potassium.

R in following formula ₁Be anilino, R ₂When being a positively charged ion such as sodium for N-2-dihydroxy ethyl and M, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-dihydroxy ethyl)-S-triazine-2-yl) amino]-2,2 '-disulfonic acid and disodium salt.This specific whitening agent form is that Ciba-Geigy company puts on market with trade(brand)name Tinopal-UNPA-GX.Tinopal-UNPA-GX is the better hydrophilic optical whitening agent that can be used for detergent composition of the present invention.

R in following formula ₁Be anilino, R ₂When being a positively charged ion such as sodium for N-2-hydroxyethyl-N-2-methylamino and M, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-S-triazine-2-yl) amino]-2,2 '-disulfonic acid disodium salt.This specific whitening agent form is that Ciba-Geigy company puts on market with trade(brand)name Tinopal 5BM-GX.

R in following formula ₁Be anilino, R ₂When being a positively charged ion such as sodium for morpholino and M, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-S-triazine-2-yl) amino]-2,2 '-disulfonic acid sodium salt.This particular brightener form is that Ciba-Geigy company puts on market with trade(brand)name Tinopal AMS-GX.

For being used for the particular optical whitening agent form that the present invention selects,, can provide especially effectively dye transfer rejection benefit when when described polymeric dye transfer inhibitor through selecting is used in combination before this.Combination of this type of polymer materials (as PVNO and/or PVPVI) through selecting and this type of optical whitening agent (as Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) through selecting can provide when any one uses separately in these two kinds of detergent composition compositions significantly good dye transfer restraining effect in water washing solution.Though bound by theory is not believed, why this type of whitening agent has this effect, is because they have high affinity to fabric in washing soln, thereby can quite promptly be deposited on these fabrics.The degree that whitening agent deposits on the fabric in washing soln can define with a parameter that is called " exhaustion coefficient ".Exhaust coefficient and generally be expressed as sedimentary whitening agent material and b on a) fabric) ratio of whitening agent starting point concentration in the washings.There is the whitening agent of higher relatively exhaustion coefficient to be suitable for suppressing within the scope of the present invention dye transfer most.

Certainly, what know is that the compound of other optical whitening agent type commonly used also can randomly be used to provide (brightness) benefit of common fabric " whiteness " in the present composition, and does not have real dye transfer retarding effect.Such purposes is common, also is that the washing composition makers-up is well-known.

Softening agent

In according to laundry detergent composition of the present invention, also can mix fabric softener.These softening agents can be inorganic type, also can be organic types.The example of inorganic softening agent is a disclosed smectic clays among the GB-A-1400898.The organic fabric softening agent comprises disclosed water-insoluble tertiary amine among GB-A-1514276 and the EP-B-0011340.

The horizontal extent of smectic clays is generally 5～15%, is more preferably 8～12% (weight), and this material is to add in the rest part of this prescription as the dry blending composition.The fusion level of organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides materials is 0.5～5% (weight), is generally 1～3% (weight), and the interpolation level of high molecular polyoxy ethylidene material and water-soluble cationic material is 0.1～2%, is generally 0.15～1.5% (weight).

Other optional components

Other optional components that is suitable for mixing in the present composition comprises flavouring agent, color and filling salt, and sodium sulfate is filling salt preferably.

The form of composition

Detergent composition of the present invention can be mixed with any ideal form, as powder, particle, paste, liquid and gel.Granular composition is preferred.

Liquid composition

Detergent composition of the present invention can be mixed with liquid detergent composition.Such liquid detergent composition typically contains 94～35% (weight), better 90～40% (weight), best 80～50% (weight) liquid vehicle such as water, better is the mixture of water and organic solvent.

Gelatinous composition

Detergent composition of the present invention also can be gel form.Such composition is that about polyalkylene polyether of 750,000～about 4,000,000 is prepared with molecular weight typically.

Solids composition

Detergent composition of the present invention better is solid form, as powder and particle.

Better should make no more than 5% particle diameter greater than 1.4mm according to the granularity of each composition of granular composition of the present invention, and no more than 5% particle diameter is less than 0.15mm.

Tap density according to granular detergent composition of the present invention is typically, and tap density is 450g/l at least, more generally be 600g/l at least, be more preferably 650～1200g/l.

Tap density is measured by means of a kind of simple funnel-measuring cup device, it consists of a conical hopper, be fixed on the pedestal, and provide a hanging valve bottom, place this funnel below, axially aligned cylinder measuring cup so that the content of this funnel can all enter one at it.The upper and lower end face of this funnel (diameter) is respectively 130mm and 40mm.During installation, make 140mm place above this pedestal upper surface, its lower surface.The overall height of measuring cup is 90mm, and internal height is 87mm, and internal diameter is 84mm.Its nominal volume is 500ml.

When measuring, this funnel impouring method is by hand filled powder, and hanging valve is opened, and allows powder excessively be full of this measuring cup.The measuring cup of filling powder is taken out from framework, wipe its upper edge with a kind of straight flange utensil off as a cutter and go up unnecessary powder to remove this glass.The measuring cup that to fill powder is weighed then, and resulting powder weight numerical value multiply by 2, obtains the tap density of representing with g/l.Carry out replicate measurement on request.

Manufacture craft-granular composition

In general, can make of various methods, mix comprising doing, spraying drying, agglomeration and granulation according to granular detergent composition of the present invention.

Washing methods

Composition of the present invention can be used for any basically washing or purging method, comprises machine clothes washing method and wash up method.

Machine wash up method

A kind of wash up of machine preferably method comprises: will be selected from the dirt article of pottery, glassware, hollow utensil and sharp weapon (cutter, sword etc.) and composition thereof, with a kind of liquid, aqueous processing according to machine dishwashing compositions of the present invention of dissolving therein or having disperseed significant quantity.The machine dishwashing compositions of so-called significant quantity typically means in the washing soln of 3～10L volume dissolving or disperses 8～60g product, as typical products dosage and washing soln volume commonly used in common machines wash up method.

The machine clothes washing method

The machine clothes washing method here comprises: the clothing of dirt will be arranged, in washing machine with a kind of aqueous cleaning solution-treated according to machine laundry detergent composition of the present invention of dissolving therein or having disperseed significant quantity.Washing composition can or add in the washing soln by washing machine material feeder sucker or with a feeding device.The detergent composition of so-called significant quantity typically means in the washing soln of 5～65L volume dissolving or disperses 40～300g product, as typical products dosage and washing soln volume commonly used in the common machines clothes washing method.

In a kind of better washing methods here, be before beginning wash(ing)cycle, in the rotary drum of washing machine (better being front-loading washing machine), to introduce a feeding device that contains the significant quantity Betengent product.

This feeding device is a kind of Betengent product container, is used for this product is directly sent in the rotary drum of washing machine.Its volume capacity should make it to hold enough Betengent products that will use usually in this washing methods.

In case put into clothing in this washing machine, the feeding device that just will fill Betengent product is put rotary drum inside into.When begin the wash(ing)cycle of washing machine, water is introduced in this rotary drum, and rotary drum is regularly rotated.The design of feeding device should make it can hold the dry detergent product, but is immersed in result in the washing water because of its stirring action that produces with drum rotating and as it then during wash(ing)cycle, can discharge this product.

In order to discharge Betengent product during washing, this device can have many perforates that this product can pass through.In addition, this device also can be made of a kind of material that allows liquid infiltration but can not allow solid phase prod see through, thereby can discharge the dissolved product.Be preferably, Betengent product discharged rapidly at the very start in wash(ing)cycle, thus the instantaneous high local concentrations that in the rotary drum of this stage of wash(ing)cycle, provides water soluble detergency promoter and heavy metal ion chelating agent to become to grade composition at washing machine.

Feeding device is reusable preferably, and can both keep a kind of like this mode of container integrity to design at dried state with during wash(ing)cycle.For according to purposes of the present invention, especially good feeding device is existing the description in following patent: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.One piece of article that J.Bland delivers on the 41-46 page or leaf at " manufacturing chemistry man " (Manufacturing Chemist) in November, 1989 has also been described and can have been used the feeding device granular laundry product, good especially that is commonly referred to " small-particle " type.

Good especially feeding device is disclosed among european patent application communique No.0343069 and the No.0343070.The application in back discloses a kind of device, comprises a soft cover of bag shape, stretches from a support ring that limits sack to form, assemble this sack and be in the washing process of in this bag, packing into one wash(ing)cycle required adequate prod.The part washing medium sack of flowing through enters in the bag, makes this product dissolving, and this solution outwards enters in the washing medium by sack then.A kind of configuration of sheltering is provided for this support ring, overflows to prevent wetting not molten product, this configuration typically comprises the circumferentially extending wall that extends from the center hub of spoke wheel configuration, or the helical similar structures of its wall.

The pre-treatment washing methods

In a pre-treatment washing methods of the present invention, with significant quantity contain heavy metal ion chelating agent but the preprocessing solution that do not contain the enzyme component is handled the matrix that dirt/spot is arranged.This solution can randomly contain other non-enzyme detergent component, as tensio-active agent, washing assistant and soil release polymer.Be preferably, this solution also contains water soluble detergency promoter.

The content of heavy metal ion chelating agent is generally 0.0005%-1% in the described preprocessing solution, and is preferably greater than 0.05%.

Allow preprocessing solution and pollution matrix keep in touch one period effective timed interval.The described timed interval was generally 10 seconds-1800 seconds, was preferably 60 seconds-600 seconds.

Adopt suitable washing methods to wash described pollution matrix then, wherein use enzyme-containing detergent.Washing methods can be do washing any in these two kinds of washing methodss of machine wash up for example described here or machine.

In these detergent composition, the component identification of breviary has following meanings: XYAS: C _1x-C _1yAlkyl sulfuric ester sodium 25EY: with the C of average Y moles of ethylene oxide condensation _12-15With line style be

Main primary alconol XYEZ: with the C of average Z moles of ethylene oxide condensation _1x-C _1yWith line style

Be main primary alconol XYEZS: every mole of average condensation the C of Z moles of ethylene oxide _1x-C _1y

Alkyl sulfuric ester sodium TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide silicate: amorphous sodium silicate (SiO ₂: Na ₂O ratio=2.0) NaSKS-6: chemical formula δ-Na ₂Si ₂O ₅Crystallization stratification silicate carbonate: the anhydrous sodium carbonate multi-carboxylate: molecular-weight average is about 80,000,1: 4 toxilic acid/acrylic acid

Multipolymer zeolite A: hydrated aluminum silicate, chemical formula is

Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O, its primary particle size scope

Be 1～10 μ m Citrate trianion: citrate trisodium dihydrate percarbonate (immediate-release granules): anhydrous SPC-D SYNTHETIC OPTICAL WHITNER, empirical formula is

2Na ₂CO ₃3H ₂O ₂, have one deck chemical formula to be

Na ₂SO ₄NNa ₂CO ₃The mixing salt dressing, wherein

N is 0.29, and wherein percarbonate and mixing salt weight ratio

Be 39: 1 percarbonate (slow-releasing granules): anhydrous SPC-D SYNTHETIC OPTICAL WHITNER has one deck water glass (Si ₂O:

Na ₂O ratio=2: 1) dressing, percarbonate and water glass

Weight ratio be 39: 1TAED: tetraacetyl ethylene diamine TAED (slow-releasing granules): TAED is with the polyoxyethylene glycol of citric acid and molecular weight 4,000

(PEG) with TAED: the composition of citric acid: PEG is heavy

Amount has one deck than being the particle that agglomeration in 75: 10: 15 forms

Citric acid external coating (EC) dressing, agglomerate: the citric acid dressing

Weight ratio is 95: 5 benzoyl caprolactams: benzoyl caprolactam (BzCl) with the polyoxyethylene glycol (PEG) of citric acid and molecular weight (slow-releasing granules) 4,000 with BzCl: lemon

Acid: the weight ratio of constituents of PEG is that agglomeration in 63: 21: 16 forms

Particle, one deck citric acid external coating (EC) dressing is arranged, agglomerate:

The weight ratio of citric acid dressing is 95: 5TAED (immediate-release granules): TAED with part neutral multi-carboxylate with TAED: many carboxylics

The ratio of hydrochlorate is the particle that agglomeration in 93: 7 forms, and has one deck many

Carboxylate salt external coating (EC) dressing, agglomerate: the weight ratio of dressing

Be 96: 4EDDS (immediate-release granules): EDDS MgSO ₄Weight ratio spraying drying shape with 26: 74

The granule protein enzyme that becomes: Novo Industries A/S company is with trade(brand)name Savinase

The proteolytic enzyme of selling, its activity is 13 KNPU/g proteolytic enzyme (slow-releasing granules): Novo Industries A/S company is with trade(brand)name Savinase

A kind of enzyme granulate that contains proteolytic enzyme of selling, it is lived

Property is 13KNPU/g, and one deck water glass (SiO is arranged ₂: Na ₂O is than=2: 1)

Dressing, dressing content are 5%.Amylase: Novo Industries A/S company is with trade(brand)name Termamyl

The amylolytic enzyme that 60T sells, its activity is 300 KNU/g cellulases: the cellulase that Novo Industries A/S company sells, its

Activity is 1000 CEVU/g lipase: Novo Industries A/S company is with trade(brand)name Lipolase

The fat hydrolase of selling, its activity is 165 KLU/gCMC: Xylo-Mucine HEDP: 1,1-hydroxyl ethane disulfonic acid EDDS: quadrol-N, N '-disuccinic acid, [S, S] isomer is

Sodium-salt form PVNO: poly-(the 4-ethene of vinyl imidazole and vinyl pyrrolidone

Yl pyridines)-and the N-oxide block copolymer, molecular-weight average is

10,000 particulate state froth suppressor: 12% siloxanes/silicon-dioxide, 18% stearyl alcohol, 70%

Starch is particle form non-ionic type: C ₁₃-C ₁₅Mixed ethoxylated/propoxylated fatty alcohol, flat

All ethoxylation degree is 3.8, and average propoxylation degree is 4.5,

By BASF (BASF) company with trade(brand)name Plurafac LF

404 sell (low bubble) metasilicate: Starso (SiO ₂: Na ₂O is than=1.0) phosphoric acid salt: tripoly phosphate sodium STPP 480N: vinylformic acid/Sipacril 2739OF of 3: 7, mean molecule

Measure about 3,500PB1: anhydrous sodium perborate monohydrate-be closely knit granular form, use

The cationic lactan of release in the delay hydrogen peroxide: trialkyl ammonium methylene radical C5 alkyl hexanolactam and tosylate

The positively charged ion peracid bleach precursor salt DETPMP that forms: diethylenetriamine five (methylene radical phosphoric acid), all public by Meng Shan

Bismuth trinitrate is sold with trade(brand)name Deqest 2060 by department: Bismuth trinitrate salt paraffin: sold with trade(brand)name Winog 70 by Wintershall company

Paraffin oil BSA: by the shallow lake of the A/S of Novo industrial with trade(brand)name LE 17 sale

Powder lytic enzyme (about 1% enzymic activity) vitriol: anhydrous sodium sulphate pH: at 20 ℃ with 1% measured in solution in distilled water

Example 1

Prepare following laundry detergent composition, numerical value is the percentage ratio that accounts for composition weight: composition A is a Comparative composition, and composition B-D is according to composition of the present invention:

	????A	????B	????C	????D
45AS/25AS(3∶1)	????9.1	????9.1	????9.1	????9.1
					35AE3S	????2.3	????2.3	????2.3	????2.3
24E5	????4.5	????4.5	????4.5	????4.5
					TFAA	????2.0	????2.0	????2.0	????2.0
Zeolite A	????13.2	????13.2	????13.2	????13.2
					NaSKS-6/ citric acid (79: 21)	????15.6	????15.6	????15.6	????15.6
Carbonate	????7.6	????7.6	????7.6	????7.6
					TAED (immediate-release granules)	????6.3	????-	????-	????-
TAED (slow-releasing granules)	????-	????5.0	????-	????2.3
					Benzoyl caprolactam (slow-releasing granules)	????-	????-	????8.0	????2.7
Percarbonate (immediate-release granules)	????22.5	????-	????-	????22.5
					Percarbonate (slow-releasing granules)	????-	????22.5	????22.5	????-
DETPMP	????-	????-	????0.5	????0.8
					EDDS (immediate-release granules)	????0.6	????0.6	????-	????-
Proteolytic enzyme	????0.55	????-	????-	????-
					Proteolytic enzyme (slow-releasing granules)	????-	????0.60	????0.55	????1.27
Lipase	????0.15	????0.15	????0.15	????0.15
					Cellulase	????0.28	????0.28	????0.28	????0.28
Amylase	????0.27	????0.27	????0.27	????0.27
					The multi-carboxylate	????5.1	????5.1	????5.1	????5.1
CMC	????0.4	????0.4	????0.4	????0.4
					PVNO	????0.03	????0.03	????0.03	????0.03
The particulate state froth suppressor	????1.5	????1.5	????1.5	????1.5
					Minor constituent/other, complement to 100%

Following T80 numerical value (second) is measured separately product A-D and is obtained.

????T80	????A	????B	????C	????D
					Proteolytic enzyme	??＜60	??＞90	??＞90	??＞90
Heavy metal ion chelating agent (DETPMP or EDDS)	??＜60	??＜60	??＜60	??＜60

Simultaneous test

The removal of test method-spot

The preparation of cloth specimen

3 calico sheets are carried out prewashing in the heavy-duty laundry detergent that does not contain abiotic SYNTHETIC OPTICAL WHITNER.Cut out 6 groups of test cloth specimens that are of a size of 6 centimetres of 6 cm x down from every calico.On each group cloth specimen, coat spot equably.

Also used the cloth specimen of studying resulting pre-preparation from EMPA in addition.

In a word, use following several groups of cloth specimens:

The spot that can bleach

EMPA blood;

Wine;

The grease spot

Makeup;

The particle spot

Clay;

These a few tissue substance cloth specimens are washed one-period in automatic washing machine.Evaluate cloth specimen greasiness removal degree by panel of experts with four-point Scheffe rule then.List comprehensive each group average result in pairs relatively below, and with the composition A of prior art as common reference.

More detailed theory, use be Miele 698 WM automatic washing machines, and select 40 ℃ of short period.Use 12 ° of Deutschland hardness (Ca: Mg=3: water 1).With 75 gram washing composition, disperse by the particulate decollator that is placed on the load middle part.Getting piece of cloth sample for every type washs with cover (family used for 1 week) the ballast load of 2.7 kilograms of light contaminations.

Simultaneous test-greasiness removal

According to top greasiness removal test method, more once the difference of the T80 value of the EDDS of proteolytic enzyme be 60 seconds composition B with as the prior art composition A of benchmark in the efficient of removing aspect the dissimilar spots.

The gained result is as follows:

The spot type	Greasiness removal benefit (PSU)
		EMPA blood	????+1.6*
Wine	????+1.4
		Makeup	????+1.1
Clay	????+1.2

* remarkable benefit when the 95% reliability limit.

Example 2

Prepare the following machine dishwashing compositions (weight part) of bleaching component that contains according to the present invention.

	?????A	??????B	?????C	??????D	??????E	??????F	?????G
								Citrate trianion	????15.0	????15.0	????15.0	????15.0	????15.0	????15.0	????-
480N	????6.0	????6.0	????6.0	????6.0	????6.0	????6.0	????-
								Carbonate	????17.5	????17.5	????17.5	????17.5	????17.5	????17.5	????-
Phosphoric acid salt	????-	????-	????-	????-	????-	????-	????38.0
								Silicate is (with SiO 2Meter)	????8.0	????8.0	????8.0	????8.0	????8.0	????8.0	????14.0
Metasilicate is (with SiO 2Meter)	????1.2	????1.2	????1.2	????1.2	????1.2	????1.2	????2.5
								PB1	????1.2	????1.2	????1.5	????1.5	????1.5	????2.2	????1.2
TAED (slow-releasing granules)	????2.2	????2.2	????2.2	????3.5	????-	????2.2	????2.2
								The positively charged ion lactan	????-	????-	????-	????-	????3.3	?????-	????-
Paraffin	????0.5	????0.5	????0.5	????0.5	????0.5	????0.5	????0.5
								Bismuth trinitrate	????-	????0.2	????0.2	????0.2	????0.3	????0.	????0.2
Proteolytic enzyme	????2.0	????2.0	????2.0	????2.0	????2.0	????2.0	????2.0
								Amylase	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5	????-
BSA	????-	????-	????-	????-	????-	?????-	????1.5
								DETPMP	????0.13	????0.13	????0.13	????0.13	????0.13	????0.13	????-

HEDP	????1.0	????1.0	????1.0	????1.0	????1.0	????1.0	????-
								Nonionic	????2.0	????2.0	????2.0	????2.0	????2.0	????2.0	????1.5
Vitriol	????23.0	????22.8	????22.4	????22.7	????22.2	????21.5	????0.3
								All the other are water
PH (1% solution)	????10.7	????10.7	????10.7	????10.7	????10.7	????10.7	????11.0

Claims (14)

1. one kind contains:

(a) a kind of heavy metal ion chelating agent; With

(b) a kind of detergent composition of enzyme, wherein provide a kind of means to make described enzyme for described heavy metal ion chelating agent, can postpone to be discharged in the washing soln, make required time of 80% the concentration that in T80 test method as herein described, reaches described heavy metal ion chelating agent ultimate density less than 60 seconds, and reach the required time of 80% concentration of described enzyme ultimate density greater than 90 seconds.

2. according to the detergent composition of claim 1, wherein in the T80 test method, 80% the required time of concentration that reaches described enzyme ultimate density is 90-240 second.

3. according to the detergent composition of claim 1 or 2,80% the required time of concentration that wherein reaches described enzyme ultimate density is 100-200 second.

4. according to any one detergent composition among the claim 1-3, wherein also comprise:

(c) a kind of water soluble detergency promoter, wherein provide a kind of means to make described enzyme for described water soluble detergency promoter, can postpone to be discharged in the washing soln, made required time of 50% the concentration that in T50 test method as herein described, reaches described water soluble detergency promoter ultimate density less than 60 seconds.

5. according to any one detergent composition among the claim 1-4, wherein said enzyme comprises the enzyme of amylases.

6. according to any one detergent composition among the claim 1-5, wherein comprise organic peroxyacid bleach system, wherein provide a kind of means to make described organic peroxide acid postpone to be discharged in the washing soln, make required time of 50% the concentration that in the T50 test method, reaches this organic peroxide acid ultimate density greater than 180 seconds, be preferably greater than 240 seconds.

7. according to the detergent composition of claim 6, wherein said organic peroxide acid bleach system comprises the combination of following ingredients:

(i) a kind of hydrogen peroxide cource; With

(ii) a kind of peroxyacid bleach precursor compound.

8. according to the detergent composition of claim 7, wherein said peroxyacid bleach precursor compound is selected from can provide the peroxyacid bleach precursor of peroxy acid compound when hydrogen peroxide is separated, and described peroxy acid is:

(i) a kind of peroxybenzoic acid, or the derivative of its non-cationic replacement; Or

(ii) a kind of positively charged ion peroxy acid.

9. according to the detergent composition of claim 7, wherein said peroxyacid bleach precursor compound is a tetraacetyl ethylene diamine.

10. according to the detergent composition of claim 7, wherein said hydrogen peroxide cource is a kind of inorganic perhydrate salts, the preferred as alkali percarbonate.

11., wherein also contain a kind of following bleaching catalyst that is selected from according to any one detergent composition among the claim 1-10:

Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (OCH ₃) ₃-(PF ₆); Co (2,2 '-bipyridyl amine) Cl ₂Two (isothiocyanato) bipyridyl amine-cobalt (II); Cross chloric acid three (bipyridyl amine)-cobalt (II); Co (2,2 '-bipyridyl amine) ₂O ₂ClO ₄Cross chloric acid two (2,2 '-bipyridyl amine) copper (II); Cross chloric acid three (two-2-pyridyl amine) iron (II); The Mn gluconate; Mn (CF ₃SO ₃) ₂Co (NH ₃) ₅Cl; Double-core Mn with four-N-dentate and two-N-dentate part cooperate comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺((bipyridyl amine) ₂Mn ^III(u-O) ₂Mn ^IV(bipyridyl amine) ₂)-(ClO ₄) ₃And composition thereof.

12. according to any one detergent composition among the claim 1-11, chlorine bleaching agent not wherein.

13. according to any one the purposes of detergent composition in the clothes washing methods in the claim 1～12, wherein this detergent composition is to offer washing soln by means of the feeding device of introducing in the washing machine rotary drum before the washing beginning.

14. a washing methods comprises the following steps:

(1) the no enzyme solution that will contain the composition of heavy metal ion chelating agent is applied on the contaminated matrix;

(2) allow described solution and described pollution matrix keep in touch one period effective timed interval;

(3) adopt and to comprise and use the washing methods that contains the enzyme cleaning composition to wash described contaminated matrix.