CN1100136C

CN1100136C - Detergents containing builder and delayed release enzyme

Info

Publication number: CN1100136C
Application number: CN95193616A
Authority: CN
Inventors: J·杰弗里; J·S·帕克; B·施托达特
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-04-13
Filing date: 1995-04-03
Publication date: 2003-01-29
Anticipated expiration: 2015-04-03
Also published as: EP0755434B1; EP0755434A4; CN1150817A; DE69534078T2; EP0755434A1; ES2239320T3; WO1995028469A1; GB9407299D0; DE69534078D1; CA2187437C; CA2187437A1; JPH09512291A; ATE291074T1

Abstract

There is provided a detergent composition containing: (a) a water-soluble builder; 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 water-soluble builder. A pretreat wash method is also provided.

Description

The washing composition that comprises washing assistant and slowly-releasing enzyme

The present invention relates to comprise the detergent composition of water soluble detergency promoter and enzyme, the release with respect to water soluble detergency promoter wherein is provided, postpone the mode that described enzyme discharges in washing soln.

For prescription Shi Eryan for the detergent composition that in washing methods, uses as laundry or machine wash up method, can be satisfactorily get on to dezymotize responsive dirt/spot from the basic thing of pollution/contamination, as blood, egg, chocolate, gravy, be a special difficult task.

Usually, this class dirt/spot can be removed enzyme such as proteolytic enzyme, amylase, lipase and cellulase by using the enzyme component.

The applicant has now found that, uses the composition that comprises water soluble detergency promoter and enzyme, and wherein said composition provides the release with respect to water soluble detergency promoter, postpones the mode that described enzyme discharges in washing soln, can obtain enhanced and remove dirt/spot ability.

The applicant also finds in addition, before the washing methods lotion that uses the enzyme-containing detergent product, pollutes basic thing with the solution pre-treatment that contains water-soluble washing assistant, thereby can better be removed the stain effect.

Therefore, one aspect of the present invention provide be adapted at doing washing and machine wash up method in use and have a composition that strengthens soil removability.

Another related fields of the present invention provide dirt/spot pretreatment process, and this method comprises polluted basic thing before washing with the enzyme-containing detergent product, earlier with the solution pre-treatment that contains water-soluble washing assistant.

Summary of the invention

The invention provides and comprise (a) water soluble detergency promoter; (b) detergent composition of enzyme, release with respect to described water soluble detergency promoter wherein is provided, postpone the mode that described enzyme discharges in washing soln, so that in the described T50 test method of the application, the time that reaches 50% described water soluble detergency promoter ultimate density is lower than 60 seconds, and the time that reaches 50% described enzyme ultimate density was greater than 90 seconds.

Another aspect of the present invention has provided washing methods, and the method comprising the steps of:

(1) uses the no enzyme solution that contains water-soluble washing assistant to polluting basic thing;

(2) make described solution keep contacting one period working lipe with the basic thing of described pollution;

(3) employing comprises that the washing methods that uses enzyme-containing detergent compositions washs the basic thing of described pollution. The water soluble detergency promoter compound

Detergent composition of the present invention can contain the water soluble detergency promoter compound, and its amount is generally 1% to 80% of composition weight, and is preferred 10% to 70%, most preferably 20% to 60% (weight).

Suitable water soluble detergency promoter compound comprises the water-soluble monomer multi-carboxylate, or their sour form, poly carboxylic acid or its salt all-or multipolymer, wherein poly carboxylic acid comprises any mixture of at least two carboxyl, carbonate, supercarbonate, borate, phosphoric acid salt, silicate and aforesaid compounds that separated by no more than two carbon atoms each other.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligomer form, but since cost and aspect of performance, general preferred monomers multi-carboxylate.

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 carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, carboxy methoxy-succinic acid salt described in No. 1379241, aconitate and citraconate and succinate derivative such as the English Patent, English Patent 1,389, aminosuccinic acid salt described in the newborn acyloxy succinate described in 732, No. 7205873, Netherlands patent applications, and the 2-oxa--1 described in No. 1387447, oxygen connection multi-carboxylate's thing such as the English Patent, 1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls comprises oxygen di-succinate (open in the English Patent 1261829), 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 1,398,421 and 1,398,422 and USP3936448 in disclosed sulfo-succinic acid salt derivative, and the sulfonation pyrolysis Citrate trianion described in the GB1439000.

Alicyclic and heterocycle multi-carboxylate comprises pentamethylene-cis, cis, cis-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt (cyclopentadienide pentacarboxylates), 2,3,4,5-tetrahydrofuran (THF)-cis, cis, cis-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-cis-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, described alcohol such as Sorbitol Powder, mannitol and Xylitol.Aromatic multi-carboxy acid's salt comprises mellitic acid, 1,2,4, disclosed phthalic acid derivative among 5-pyromellitic acid and the GB1425343.

In the above-claimed cpd, preferred multi-carboxylate is contained the hydroxycarboxylate of three carboxyls of as many as, more preferably Citrate trianion for per molecule.

The mixture of the parent acid of monomer or oligomerization multi-carboxylate sequestrant or they and its salt, as citric acid or Citrate trianion/citric acid mixture, also can be by with as suitable builder component.

Also can use the borate washing assistant, and contain the washing assistant that can form borate substance (they washing composition store or wash conditions under can produce borate) but be lower than 50 ℃, particularly be lower than under about 40 ℃ wash conditions, their right and wrong are preferred.

The carbonate builders example comprises alkaline-earth metal and alkali-metal carbonate, comprises the mixture of yellow soda ash and sesquicarbonate and they and calcium carbonate superfine powder, referring to DE2321001 (on November 15th, 1973 is open).

The specific examples of water-soluble phosphate washing assistant comprises tripolyphosphate an alkali metal salt, trisodium phosphate, potassium and ammonium, trisodium phosphate and potassium and ammonium, sodium orthophosphate and potassium, poly-partially/sodium phosphate, wherein the polymerization degree in 6 to 21 scopes, and phytate.

Suitable silicate is for having SiO ₂: Na ₂The O ratio is 1.0 to 2.8, and is preferred 1.6 to 2.4, most preferably those water-soluble metasilicates of 2.0.Silicate can be anhydrous salt or salt hydrate form.Most preferred silicate is for having SiO ₂: Na ₂O is than the water glass that is 2.0.

In the detergent composition of the present invention, the amount of silicate is preferably 5% to 50% of detergent composition weight, more preferably 10% to 40% (weight).Enzyme

Detergent composition of the present invention comprises enzyme.Suitable enzyme thing comprise can buy on the market and be admixed to lipase, amylase, neutrality and Sumizyme MP, esterase, cellulase, polygalacturonase, Sumylact L and peroxidase in the detergent composition usually.Suitable enzyme is seen USP3, and 519,570 and 3,533,139 is interior described.

Preferred proteolytic enzyme available on the market comprises that Novo Industries A/S (Denmark) is with trade(brand)name Alcalase, Savinase, Primae, Durazym, with those enzymes that Esperase sells, Gist-Brocades is with trade(brand)name Maxatase, those enzymes that Maxacal and Maxapem sell, those proteolytic enzyme that Genencor International sells, and SolvayEnzymes is with those proteolytic enzyme of Opticlean and the sale of Optimase trade(brand)name.Proteolytic enzyme can account for the amount of composition weight 0.0001% to 4% organized enzyme and mix in the composition of the present invention.

Preferred amylase comprises, the α-Dian Fenmei that obtains by extraordinary B lichenoid form bacterial strain for example, and details are referring to GB-1269839 (Novo).Preferred amylase available on the market comprises those amylase that those amylase sold with the Rapidase trade(brand)name as Gist-Brocades and NovoIndustries A/S sell with Termamyl and BAN trade(brand)name.Amylase can account for the amount of composition weight 0.0001% to 2% organized enzyme and mix in the present composition.

Lipase can account for composition weight 0.0001% to 2%, and is preferred 0.001% to 1%, and most preferably the amount of 0.001% to 0.5% (weight) active lipase exists.

Lipase can be to come from as producing the fungi or the bacterium of lipase, and as the Humicola bacterial strain, hot Pseudomonas (Thermomyces sp.) bacterial strain or Rhodopseudomonas comprise the bacterial strain of pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.The lipase that is obtained by the chemistry or the genetic modification mutant of these bacterial strains also is fit to the present invention.

Preferred lipase is obtained seeing by pseudomonas pseudoalcaligenes described in the European patent EP-B-0218272 of mandate.

Another kind of preferred lipase be by clone dredge erion look humicola lanuginosa (HumicolaLanuginosa) and in as host's aspergillus oryzae expressing gene obtain (as seeing described in the EP-A-0258068), this lipase can be from Novo Industri A/S, Bagsvaerd, Denmark buys with the Lipolase trade(brand)name.This lipase is also seen described in the USP4810414 (people such as Huge-Jensen, on March 7th, 1989 authorized).

When enzyme was proteolytic enzyme, its maximum in typical washing soln was 0.1 to 100KNPU, but preferred 0.5 to 50KNPU, and more preferably 3 to 30KNPU, and most preferably 6 to 30KNPU.

When enzyme was amylase, its maximum in typical washing soln was 1 to 200KNU, but is preferably 10 to 100KNU, and more preferably 40 to 80KNU.

When enzyme was lipase, its maximum in typical washing soln was 1 to 300KLU, but preferred 10 to 200KLU, more preferably 10 to 100KLU.

When enzyme was cellulase, its maximum in washing soln was generally 10 to 1200CEVU, but preferred 50 to 1000CEVU, and more preferably 80 to 500CEVU. The enzyme stabilising system

Preferred the present invention contains enzyme composition can comprise about 0.001% to about 10%, preferred about 0.005% to about 8%, and most preferably from about 0.01% to about 6% weight enzyme stabilising system.The enzyme stabilising system can be and the compatible any stabilising system of detergency enzymes.This stabilising system can comprise calcium ion, boric acid, propylene glycol, short chain carboxy acid, boronic acid and their mixture.This class stabilising system also can comprise the irreversible enzyme inhibitor, as reversible protease inhibitors.

The present composition can further comprise 0 to about 10%, preferred about 0.01% to about 6% weight chlorine bleach scavenging agent, adding this scavenging agent is to be used for preventing many destruction and fermentoids that are present in the chlorine class SYNTHETIC OPTICAL WHITNER of supplied water to enzyme, particularly under alkaline condition.Although cl content may be very low in the water (generally at about 0.5ppm to about 1.75ppm scope), the chlorine that exists in the cumulative volume of the water that contacts with enzyme in washing process is normally huge; Therefore, enzyme stability may have problems in the use.

Suitable chlorine scavenger negatively charged ion can extensively obtain, and can be illustrated by the salt that contains ammonium cation or sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Oxidation inhibitor such as carbamate (salt), xitix etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA), and their mixture equally also can use.Other conventional scavenging agent 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, tartrate, salicylate, Deng, and their mixture also can be used (if desired). Relative release dynamics

Main aspect of the present invention has provided the release with respect to water soluble detergency promoter, postpones the mode that enzyme discharges in washing soln.

Described mode comprises the mode that enzyme discharges that postpones in washing soln.

On the other hand, described mode can comprise the mode of the speed that the increase water soluble detergency promoter discharges in washing soln. The mode that postpones rate of release

Postpone delivery mode and can comprise that the coating thing that is used to provide delay to discharge coats the enzyme with any suitable component.Therefore, the coating thing can comprise the material as poorly water-soluble, and perhaps for having the coating thing of adequate thickness, the dissolution kinetics characteristic of this thick coating thing provides sustained release speed.

Described coating thing can make the coating that ins all sorts of ways.Any coating thing is general all to press 1: 99 to 1: 2 with enzyme, and preferred 1: 49 to 1: 9 weight ratio exists.

Suitable coating thing comprises triglyceride level (as partially hydrogenated vegetable oil, soya-bean oil, Oleum Gossypii semen) single acid or Diglyceride, Microcrystalline Wax, gelatin, Mierocrystalline cellulose, lipid acid and their any mixture.

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

Preferred coating thing is SiO ₂: Na ₂The ratio of O is 1.6: 1 to 3.4: 1, preferred 2.8: 1 water glass, and with the coating of aqueous solution form, its level of solids is 2% to 10% (being generally 3% to 5%) of percarbonate weight.Also can comprise Magnesium Silicate q-agent in the coating thing.

Any inorganic salt coating thing all can combine with the organic binder bond material, obtains compound inorganic salt/organic binder bond coating thing.Suitable tackiness agent comprises the C that contains 5-100 moles of ethylene oxide/mol of alcohol ₁₀-C ₂₀Alcohol ethoxylate, and more preferably contain the C of 20-100 moles of ethylene oxide/mol of alcohol ₁₅-C ₂₀Primary alcohol ethoxylate.

Other preferred adhesive comprises some polymkeric substance.The example of this base polymer comprises the polyvinylpyrrolidone with 12,000 to 700,000 molecular-weight average and has the polyoxyethylene glycol (PEG) of 600 to 10,000 molecular-weight average.Other examples of polymer that can be used as tackiness agent also has the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and wherein maleic anhydride accounts for 20% (mole) at least in the polymkeric substance.These polymkeric substance can directly use or with solvent such as water, propylene glycol and above-mentioned every mole of C that contains the 5-100 moles of ethylene oxide ₁₀-C ₂₀Alcohol ethoxylate is used in combination.Other examples of adhesives comprises C ₁₀-C ₂₀Single-and two-glycerine alcohol ether and C ₁₀-C ₂₀Lipid acid.

Derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose and Natvosol, and all-or altogether-poly-poly carboxylic acid or their salt is suitable for the examples of adhesives of the present invention's use for other.

A kind of method of coating coating thing comprises agglomeration technique.Preferred agglomeration technique comprises above-mentioned any organic binder bond material of use.Any cyclone agglomerator commonly used (agglomerator)/mixing tank be can use, pot, rotary drum and vertical blending machine etc. included, but is not limited to.Fusion coating thing can be by toppling over, or the mode that the spray quinoline is atomised on the enzyme granulate moving-bed coats.

The alternate manner that the delay that providing needs discharges comprises the physical properties that changes any enzyme containing granule, to control the mechanical system of its solubleness and rate of release.Suitable scheme comprises compacting, mechanical injection, hand spray, and the solvability of regulating the SYNTHETIC OPTICAL WHITNER compound by the granular size of selecting grain fraction.

Although the selection of granular size is depended on the composition of grain fraction and satisfies the hope that ideal postpones release dynamics that granular size preferably should preferably have 800 to 1200 microns median sizes greater than 500 microns.

Any other component that provides the other scheme that postpones delivery mode to comprise suitable selection detergent composition matrix, when being added in the washing soln with convenient composition, the ionic strength environment that wherein provides can provide the delay release dynamics that needs. Increase the mode of rate of release

It is contemplated that all suitable methods that can increase water soluble detergency promoter rate of release in solution.

Increase the mode that discharges and to comprise that the coating thing that is used to provide increase to discharge coats any suitable component.Therefore, the coating thing can comprise for example high water soluble or effervescive water-soluble substances.

The alternate manner that the delay that providing needs discharges comprises the physical properties that changes water soluble detergency promoter, to increase the mechanical system of its solubleness and release rate.

Suitable scheme can comprise any granular size that contains water-soluble builder component of careful selection.The composition of grain fraction is not only depended in the selection of granular size, also depends on to satisfy the hope that ideal increases release dynamics.Granular size preferably should preferably have 1100 to 500 microns median sizes less than 1200 microns.

Provide the other scheme that postpones to discharge to comprise any other component of suitable selection detergent composition matrix.Or suitably select any grain fraction that contains water-soluble washing assistant, when being added in the washing soln with convenient composition, the ionic strength environment that wherein provides can provide the increase release dynamics that needs. The kinetic parameter of relative release rate

With respect to water soluble detergency promoter, the release of enzyme should so be carried out, so that in T50 test method as herein described, the time that reaches 50% water soluble detergency promoter ultimate density is less than 60 seconds, preferably be less than 50 seconds, more preferably less than 40 seconds, and the time that reaches 50% enzyme ultimate density was greater than 90 seconds, be preferably greater than 120 seconds, more preferably greater than 150 seconds.

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

The final wash concentration of enzyme is generally 0.000001% to 0.01% weight organized enzyme, but is preferably 0.00001% to 0.001%, and more preferably 0.00005% to 0.0005%. The testing method that postpones release

Delay release dynamics of the present invention determines that according to " TA test method " this method is when the composition that contains a certain component is dissolved by the standard conditions of the application's proposition, is used to measure this component A% required time of ultimate density/level that reaches.

Standard conditions are to add the 10g composition at 20 ℃ in the 1 liter of glass beaker that fills 1000ml distilled water.Adopt magnetic stirring apparatus with the content in the 100rpm stirring velocity stirring beaker.Ultimate density/level is considered to composition and joins the concentration/level that was reached in 10 minutes afterwards in the beaker that is filled with water.

Select suitable analytical procedure so that after in the water of beaker, adding composition, can accurately measure relevant component at any time and final solution concentration.

This analytical procedure can comprise that those relate to the method for energy continuous monitoring concentration of component level, for example, comprise light-intensity method and conductometric titration.

On the other hand, can use following method, this method comprises with Fixed Time Interval shift out reference liquid from solution, by suitable mode,, dissolution process is stopped for example by the temperature of the liquid that debases the standard rapidly, then by any way, as component concentrations in the chemical titration reference liquid.

If suitable, can use suitable graphics, comprise curve fitting method, analyse the result according to rough segmentation, calculate the TA value.

Measure the selected particular analysis method of concentration of component and depend on the character of component, and the material that contains the composition of described component. Additional detergent components

Detergent component of the present invention also can contain additional detergent components.The definite character of these annexing ingredients with and incorporation depend on the physical form of composition, and the washing operation kind that is adopted.

For example, the present composition can be mixed with hand and use and the machine laundry detergent composition, comprising the composition that laundry is used with addition composite and the pre-treatment of suitable pollution fabric, and the machine dishwashing compositions.

Be suitable for the machine-washing method when being mixed with, as machine laundry and machine wash up method, during the composition that uses, the present composition preferably contains one or more and is selected from following additional detergent components: tensio-active agent, washing assistant, organic polymer, SYNTHETIC OPTICAL WHITNER, suds suppressor, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and inhibiter.Laundry composition can also comprise the softening agent as additional detergent components. Tensio-active agent

Detergent composition of the present invention contains the mixture that is selected from negatively charged ion, positively charged ion, nonionic, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics and they tensio-active agent as the washing composition main ingredient.

Tensio-active agent generally exists with the amount of about 0.1% to 60% (weight), and the add-on of preferred tensio-active agent is 1% to 35% (weight), most preferably is 1% to 20% (weight).

Any enzyme component that exists in the tensio-active agent of screening formulation and the composition is compatible.In liquid state or gel state composition, most preferably Pei Fang tensio-active agent can promote, the stability of any enzyme in these compositions of perhaps not degrading at least.

Listed the concrete kind of negatively charged ion, nonionic, both sexes class tensio-active agent and zwitterionic classes tensio-active agent and these tensio-active agents commonly used among the USP3929678 (authorized on December 10th, 1975 and give Laughlin and Heuring).Other example is seen described in " Surface ActiveAgents and Detergents " (Vol.I and II, Schwartz, Perry and Berch).Suitable cationic surfactants is seen listed among the USP4259217 (this patent is authorized on March 31st, 1981 and given Murphy).

If exist, both sexes and zwitterionics generally are used in combination with one or more negatively charged ion and/or nonionogenic tenside. Anion surfactant

In fact, any anion surfactant that is applicable to the decontamination purpose all can be included in the composition of the present invention basically.They can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant salt (comprise, for example, the ammonium salt of sodium, potassium, ammonium and replacement as single-, two-and three-ethanolamine salt).

Other anion surfactant comprises fatty acid amide, alkyl succinate and the sulfosuccinate of isethionate such as acyl isethinate, N-acyl taurine salt, methyl taurate.The monoesters of sulfosuccinate (particularly saturated and undersaturated C ₁₂-C ₁₈Monoesters), the diester of sulfosuccinate (especially saturated and undersaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are fit to, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in or are derived from fatty oil. The anion sulfate acid salt surfactant

Be fit to primary alkyl sulphates, alkyl ethoxy sulfate, fatty oil base glycerol sulfuric acid, alkyl phenol epoxy ethane ether salt, C that anion sulfate tensio-active agent used in this application comprises straight or branched ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl)-and-N-(C ₁-C ₁₂Hydroxyalkyl) vitriol of the vitriol of glucosamine sulfate and alkyl polysaccharide thing such as alkyl polyglucoside (compound of the nonionic non-sulfuric acidization of the following stated).

Alkyl ethoxy sulfate surfactant is preferably selected from C ₆-C ₁₈Alkyl-sulphate, wherein the above-mentioned vitriol of per molecule by about 0.5 to about 20 moles of ethylene oxide ethoxyquins.Preferred alkyl ethoxy sulfate surfactant is per molecule C ₆-C ₁₈Alkyl-sulphate is by about 0.5 to about 20, preferred about 0.5 C to about 5 moles of ethylene oxide ethoxyquins ₆-C ₁₈Alkyl-sulphate. The anion sulfoacid salt surfactant

The anionic sulphonate tensio-active agent that is fit to the present invention's use comprises C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oil base glycerol sulfonate, and their any mixture. The anionic carboxylic acid salt surfactant

The anionic carboxylate tensio-active agent that is fit to the present invention's use comprises alkyl ethoxy carboxylate, alkyl polyethoxye polycarboxylate tensio-active agent and soap (' alkyl carboxylate '), especially some secondary as described herein soap (secondary soaps).

Preferably the alkyl ethoxy carboxylate that uses for the present invention comprises that those have formula RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Carboxylate salt, wherein R is C ₆To C ₁₈Alkyl, the value of x is between 0 to 10, ethoxylate so distributes, by weight, when x was 0, it is about 20% that the amount of material is lower than, and when x amount of material greater than 7 time be lower than about 25%, when average R is C ₁₃Or when lower, average x is about 2 to 4, and when average R greater than C ₁₃The time, average x is about 3 to 10, and M represents positively charged ion, be preferably selected from basic metal, alkaline-earth metal, ammonium, list-, two-and three-ethanol ammonium, the most preferably mixture of sodium, potassium, ammonium and they and magnesium ion.Preferred alkyl ethoxy carboxylate is represented C for R wherein ₁₂To C ₁₈Those carboxylate salts of alkyl.

The alkyl polyethoxye polycarboxylate tensio-active agent that is fit to the present invention's use comprises that those have RO-(CHR ₁-CHR ₂-O)-R ₃The chemical formula person, wherein R represents C ₆To C ₁₈Alkyl, x are 1 to 25, R ₁And R ₂Be selected from hydrogen, methyl acid group, amber acid radical, hydroxy succinic acid root, and their mixture, wherein at least one R ₁Or R ₂Represent amber acid radical or hydroxy succinic acid root, and R ₃Be selected from hydrogen, replace or unsubstituted alkyl with 1 to 8 carbon atom, and their mixture. The secondary soap surfactant of negatively charged ion

Preferred soap surfactant is to contain the unitary secondary soap surfactant of the carboxyl that is connected with secondary carbon.Secondary carbon can be arranged in ring structure, as is arranged in right-octyl group phenylformic acid, or is arranged in the cyclohexane carboxylic acid salt that alkyl replaces.Secondary soap surfactant should preferably not comprise ehter bond, does not comprise ester bond and does not have hydroxyl.Should preferably there be nitrogen-atoms in the headgroup (amphiphilic moieties).Secondary soap surfactant contains the total carbon atom of 11-15 usually, but the tensio-active agent such as the right-octyl group phenylformic acid that contain more slightly (for example as many as 16) carbon atom also can be allowed.

Following general structure further illustrates the secondary soap of some preferred secondary soap surfactant: A. class very preferably and comprises formula R ³CH (R ⁴) the secondary carboxyl material of COOM, R in the formula ³Represent CH ₃(CH ₂) _xAnd R ⁴Represent CH ₃(CH ₂) _y, wherein y can or be 1 to 4 integer for 0, x be 4 to 10 integer and (x+y) sum be 6-10, preferred 7-9, most preferably 8.B. another kind of preferred secondary soap comprises these carboxylic compounds, and wherein carboxyl substituent is positioned on the cyclic hydrocarbon radical unit, that is, and and formula R ⁵-R ⁶-COOM secondary soap, wherein R ⁵Represent C ⁷-C ¹⁰, preferred C ⁸-C ⁹Alkyl or alkenyl, and R ⁶Be ring structure, as benzene, pentamethylene and hexanaphthene.(annotate: with respect to the carboxyl on the ring, R ⁵Can be positioned at the neighbour, or contraposition on).C. the preferred secondary soap of a class comprises formula CH again ₃(CHR) _k-(CH ₂) _m-(CHR) _n-CH (COOM) (CHR) _o-(CH ₂) _q-(CHR) _q-CH ₃Secondary carboxylic compound, wherein each R represents C ₁-C ₄Alkyl, wherein k, n, o, q are the integer in the 0-8 scope, its condition is that the sum of carbon atom (comprising the carbon atom in the carboxylate salt) is in 10 to 18 scopes.

In above-mentioned formula A, B and C various, M can be any suitable, particularly water-soluble counter ion.

The secondary soap surfactant that particularly preferred suitable the present invention uses is to be selected from following water soluble component: 2-methyl isophthalic acid-undeeanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid. The basic metal sarcosinate surfactant

Other suitable anion surfactant is formula R-CON-(R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R represents C ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Represent C ₁-C ₄Alkyl and M represent alkalimetal ion.Preferred example has the tetradecyl and the oil base methyl sarcosinate of sodium-salt form. Nonionogenic tenside

In fact, any nonionogenic tenside that is applicable to the decontamination purpose all can be included in the composition of the present invention.Typically, the suitable nonionogenic tenside of non-limiting kind is listed as follows. The nonionic polyhydroxy fatty acid amide surfactant

The polyhydroxy fatty acid amide surfactant that is fit to the present invention's use is for having R ²CONR ¹Those acid amides of Z structural formula, wherein R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or their mixture; And Z is the polyhydroxy alkyl with straight-chain alkyl chain of at least 3 hydroxyls that directly link to each other with chain, or its oxidation alkyl derivative (the preferably ethoxyquin or third oxidation).Z preferably is derived from the reducing sugar in the reductive amination reaction; More preferably Z is triose alcohol radical (glycityl). The condenses of nonionic alkylphenol

The condenses of the polyethylene oxide of alkylphenol, poly(propylene oxide), polybutylene oxide is suitable for the present invention to be used.In general, preferred polyethylene oxide condensation compound.These compounds comprise having the straight or branched configuration and containing has an appointment 6 to the alkylphenol of about 18 carbon atom alkyls and the condensation product of alkylene oxide. Nonionic ethoxylated alcohol tensio-active agent

Fatty alcohol and the about 1 alkylethoxylate condensation product that forms to about 25 moles of ethylene oxide are fit to the present invention's use.The alkyl chain of fatty alcohol can be a straight or branched, uncle or secondary structure, and generally contain 6 to 22 carbon atoms.Preferred especially every mole of alcohol and about 2 condensation products to about 10 moles of ethylene oxide with 8 to 22 carbon atom alkyls. Nonionic ethoxylated/third oxidation of fat alcohol tensio-active agent

Ethoxyquin C ₆-C ₁₈Fatty alcohol and C ₆-C ₁₈Mix ethoxyquin/third oxidation fatty alcohol for being fit to the suitable surfactant that the present invention uses, particularly more suitable when being water-soluble when it.Preferred ethoxyquin fatty alcohol is the C with 3 to 50 ethoxylation degrees ₁₀-C ₁₈B oxidation fat alcohol most preferably has the C of 3 to 40 ethoxylation degrees ₁₂-C ₁₈B oxidation fat alcohol.Preferably have 10 to 18 carbon atom alkyl chain lengths, the mixing ethoxyquin of 3 to 30 ethoxylation degrees and 1 to the 10 propoxylation degree/third oxidation of fat alcohol. The condenses of nonionic EO/PO and propylene glycol

Oxyethane is fit to the present invention's use with the condensation product that the hydrophobic alkali that is formed by propylene oxide and propylene glycol condensation forms.The hydrophobic part of these compounds preferably has about 1500 to about 1800 molecular weight, and demonstrates water-insoluble.

The example of this compounds comprises some commercially available Pluronic ^TMTensio-active agent (BASF sale). The condensation product of nonionic EO and propylene oxide/ethylenediamine adduct

The condenses of the product that oxyethane and propylene oxide and 1 reaction form is fit to the present invention to be used.The hydrophobic part of these compounds comprises the reaction product of 1 and excessive propylene oxide, and generally has about 2500 to about 3000 molecular weight.The example of this class nonionogenic tenside comprises commercially available Tetronic ^TMCompound (BASF sale). Nonionic alkyl polysaccharide thing tensio-active agent

See USP4 for the suitable alkyl polysaccharide thing that the present invention uses, 565, disclosed alkyl polysaccharide thing in 647 (being issued to Lienado on January 21st, 1986), it has about 6 to about 30 carbon atoms, preferred about 10 hydrophobic groupings to about 16 carbon atoms, and many saccharidess, as the polysaccharide glycosides, hydrophilic radical contains has an appointment 1.3 to about 10, and preferred about 1.3 to about 3, and most preferably from about 1.3 to about 2.7 saccharides unit.Any reduction saccharides that contains 5 to 6 carbon atoms can be used, the glucosyl part can be replaced as glucose, semi-lactosi and galactosyl part.(hydrophobic grouping can at random be connected on 2-, 3-, the 4-equipotential, thereby obtains glucose or the semi-lactosi different with glucoside or galactoside).Key can be positioned at as the unitary arbitrary position of additional saccharides and the unitary 2-of above-mentioned saccharides, 3-, 4-between sugar, and/or between the 6-position.

Preferred alkyl polysaccharide thing has the following formula structure:

R ²O (C _nH _2nO) _t(glycosyl) _xR wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl, and their mixture, wherein said alkyl contains 10 to 18 carbon atoms, preferred 12 to 14 carbon atoms; N is 2 or 3; T is 0 to 10; Preferred 0; X represents 1.3 to 8, and is preferred 1.3 to 3, and most preferably 1.3 to 2.7.Glycosyl preferably is derived from glucose. The nonionic fatty acid amide surfactant

The fatty acid amide surfactant that is fit to the present invention's use is for having formula R ⁶CON (R ⁷) ₂Those compounds of structure, wherein R ⁶Representative contains 7 to 21, the alkyl of preferred 9 to 17 carbon atoms, and each R ⁷Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein the x value is in 1 to 3 scope. Amphoterics

The suitable amphoterics that uses for the present invention comprises amine oxide surfactant and alkyl both sexes carboxylic acid.

The suitable example of the alkyl both sexes dicarboxylic acid that uses for the present invention has Miranol (TM) C2M Conc[Miranol, Inc. produce (Dayton, NJ)]. Amine oxide surfactant

The amine oxide of practicality of the present invention comprises having formula R ³(OR ⁴) _xN ⁰(R ⁵) ₂Those compounds of structure, wherein R ³Be selected from alkyl, hydroxyalkyl, amido propyl group and alkyl phenyl, or their mixture.These groups contain 8 to 26 carbon atoms, preferred 8 to 18 carbon atoms; R ⁴Representative contains 2 to 3 carbon atoms, the alkylidene group of preferred 2 carbon atoms or hydroxy alkylidene, or their mixture; X is 0 to 5, preferred 0 to 3; And each R ⁵Representative contains 1 to 3, the alkyl of preferred 1 to 2 carbon atom or hydroxyalkyl, and perhaps representative contains 1 to 3, the polyethylene oxide group of preferred 1 ethylene oxide group.R ⁵Group links to each other by oxygen or nitrogen-atoms each other and forms ring structure.

These amine oxide surfactants especially comprise C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₈Alkoxyethyl dihydroxy ethyl amine oxide.These material examples comprise 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, dodecyl amido propyl group dimethylamine oxide compound, hexadecyl dimethyl amine oxide compound, stearyl dimethyl amine oxide compound, butter dimethyl amine oxide compound and dimethyl-2-hydroxyl octadecyl amine oxide.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide, and C ₁₀-C ₁₈Amidoalkyl dimethyl amine oxide compound. Zwitterionics

Zwitterionics also can be incorporated in the detergent composition of the present invention.These tensio-active agents can briefly be called secondary and tertiary amines derived thing, the derivative of heterocyclic secondary and tertiary amine, or quaternary ammonium; The derivative of quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine are for being fit to the representative zwitterionics that the present invention uses. Beet alkali surface activator

The trimethyl-glycine of Shi Yonging is for having formula R (R in the present invention ¹) ₂N ⁺R ²COO ^-Those compounds of structure, wherein R represents C ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl or C ₁₀-C ₁₆Amidoalkyl, each R ¹General proxy C ₁-C ₃Alkyl, preferable methyl, and R ²Represent C ₁-C ₅Alkyl, preferred C ₁-C ₃Alkylidene group, more preferably C ₁-C ₂Alkylidene group.Suitable trimethyl-glycine example comprises Oleum Cocois amido propyl-dimethyl trimethyl-glycine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C ₁₂-C ₁₄Amido propyl betaine; C ₈-C ₁₄Amido hexyl diethyl betaines; 4-[C ₁₄-C ₁₆Acyl group methyl amido diethyl ammonium]-1-carboxylic acid butane; C ₁₆-C ₁₈The amido dimethyl betaine; C ₁₂-C ₁₆Amido-pentane diethyl-trimethyl-glycine; C ₁₂-C ₁₆Acyl group methyl amido dimethyl betaine.Preferred trimethyl-glycine is C ₁₂-C ₁₈Dimethylammonio acetate and C ₁₀-C ₁₈Amido propyl group (or ethyl) dimethyl (or diethyl) trimethyl-glycine.The beet alkali surface activator that cooperates also is fit to the present invention to be used. The sultaine tensio-active agent

The spendable sultaine of the present invention has formula R (R for those ¹) ₂N ⁺R ²SO ₃ ^-Compound, wherein R represents C ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl, more preferably C ₁₂-C ₁₃Alkyl, each R ¹General proxy C ₁-C ₃Alkyl, preferable methyl, and R ²Represent C ₁-C ₆Alkyl, preferred C ₁-C ₃Alkylidene group, perhaps preferred hydroxy alkylidene.

Amphoterics can mix in the detergent composition of the present invention.These tensio-active agents can briefly be called the aliphatic derivatives of the second month in a season or tertiary amine, or the aliphatic derivatives of the heterocycle second month in a season or tertiary amine, and wherein said aliphatic group can be a straight or branched. Cats product

Cats product also can use in detergent composition of the present invention.Suitable cats product comprises and is selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀The quaternary ammonium surfactant of N-alkyl or alkenyl ammonium surfactant wherein remains the N-position by methyl, and methylol or hydroxypropyl replace. Be partly dissolved or insoluble washing-aid compound

Detergent composition of the present invention can contain and is partly dissolved or insoluble washing-aid compound, and its amount is generally 1% to 80% of composition weight, and is preferred 10% to 70%, most preferably 20% to 60% (weight).

Part water soluble detergency promoter example comprises stratiform crystalline form (crystalline layered) silicate.The washing assistant example that the utmost point is insoluble in water comprises sodium silicoaluminate.

Stratiform crystalline form sodium silicoaluminate has following general formula:

NaMSi _xO _2x+1YH ₂O wherein M is sodium or hydrogen, and x is 1.9 to 4 numerical value, and y is 0 to 20 numerical value.This class stratiform crystalline form sodium silicoaluminate sees described in the EP-A-0164514 that its preparation method is seen described in DE-A-3417649 and the DE-A-3742043.For the present invention, the value of x is 2,3 or 4 in the above-mentioned general formula, and preferred 2.Most preferred material is δ-Na ₂Si ₂O ₅(buying with the NaSKS-6 trade(brand)name) from Hoechst AG.

Stratiform crystalline form water glass in granular detergent composition preferably to exist with the fine and close blended particle form of solid-state, water-soluble ionizable material.Solid-state, water-soluble ionizable species is selected from organic acid, organic and inorganic acid salt and composition thereof.

Suitable aluminosilicate zeolite has formula Na _z[(AlO ₂) _z(SiO ₂) _y] XH ₂The O structure cell, wherein z and y are at least 6; The mol ratio of z and y is between 1.0 to 0.5, and x is at least 5, and is preferred 7.5 to 276, and more preferably 10 to 264.The silico-aluminate thing is hydrated form and is preferably xln that they contain 10% to 28%, more preferably the water of 18% to 22% combining form.

The silico-aluminate ion exchange material can be naturally occurring material, but preferred through the synthetic material that obtains.Synthetic crystalline silico-aluminate ion-exchange thing can trade names ZeoliteA, ZeoliteB, ZeoliteP, ZeoliteX, ZeoliteMAP, ZeoliteHS and composition thereof buy.ZeoliteA has following chemical formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] XH ₂O wherein X is 20 to 30, particularly 27.ZeoliteX has chemical formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂O. SYNTHETIC OPTICAL WHITNER

Detergent composition of the present invention contains the organic peroxide acid bleach source as basal component.The organic peroxide acid bleach source can be an organic peroxide acid itself, perhaps can be the peroxyacid bleach precursor compound.

When above-mentioned source was the peroxyacid bleach precursor compound, the generation of peroxy acid was undertaken by this precursor and hydrogen peroxide cource situ reaction.Suitable hydrogen peroxide cource comprises inorganic perhydrate (perhydrate) SYNTHETIC OPTICAL WHITNER.

The organic peroxide acid bleach source also provides the mode that itself discharges of postponing in washing soln, so that in the T50 test, the time that reaches 50% peroxyacid bleach ultimate density was preferably greater than 240 seconds greater than 180 seconds.Can use the described acquisition of the application to postpone any way that discharges. Peroxyacid bleach precursor

Peroxyacid bleach precursor (bleach-activating agent) is the preferred peroxide acid source of the present invention.Peroxyacid bleach precursor is usually to account for 1% to 20% of composition weight, and more preferably 2% to 10%, most preferably the amount of 3% to 5% (weight) adds.

Suitable peroxyacid bleach precursor generally contains one or more N-or O-carboxyl groups, and this precursor can be selected from classes of compounds.Suitable kind comprises the acylated derivatives of acid anhydride, ester, imide and imidazoles and oxime, and the suitable examples of compounds of these kinds is seen described in the GB-A-1586789.

Suitable ester see GB-A-836988,864798,1147871,2143231 and EP-A-0170386 described in.The acylate of Sorbitol Powder, glucose and all saccharidess and benzozlating agent and acetylizing agent also is suitable.

Concrete O-acidylate precursor compound comprises 2; 3; the cationic derivative of 3-trimethyl acetyl base oxygen base benzene sulfonate, benzoyl oxygen base benzene sulfonate, the amino hexylyloxy benzene sulfonate of nonanoyl-6-, the tetra-acetylated glucose benzoyl peroxide of single benzoyl and above-mentioned any compound comprises alkylammonium derivative and penta-acetyl glucose.Tetra hydro Phthalic anhydride is suitable acid anhydride class precursor.

The cationic derivative of concrete O-acyl group precursor compound comprises 2-(N, N, N-trimethyl ammonium) ethyl 4-sulfo group benzol carbonate na chloride, and the alkylammonium derivative that comprises any benzoyloxy benzene sulfonate of 4-(trimethyl ammonium) methyl-derivatives.

GB-A-855735,907356 and GB-A-1246338 in useful N-acyl compounds is disclosed.

Preferred acid imide precursor compound comprises N-benzoyl succinimide, four benzoyl 1, and the N-benzoyl replaces urea and N-, N, N ¹, N ¹-tetrem acidylate Alkylenediamine, wherein alkylidene group contains 1 to 6 carbon atom, and particularly wherein alkylidene group contains those compounds of 1,2 and 6 carbon atom.Preferred especially tetra-acetylated 1 (TAED).

Lactams N-acidylate precursor compound is disclosed among the GB-A-955735 widely.Though in a broad sense, the present invention can use any lactan that can be used as peroxyacid precursor, and preferred compound comprises hexanolactam and Valerolactim.

Suitable N-acylated lactams precursor has the following formula structure, Wherein n is 0 to about 8, and is preferred 0 to 2, and R ⁶Represent H, contain alkyl, aryl, alkoxy aryl or the alkaryl of 1 to 12 carbon atom, or contain the substituted-phenyl of 6 to 18 carbon atoms.

Suitable caprolactam bleach agent precursor has the following formula structure:

R wherein ¹Represent H or contain 1 to 12 carbon atom, alkyl, aryl, alkoxy aromatic yl or the alkaryl of preferred 6 to 12 carbon atoms, most preferably R ¹Be phenyl.

Suitable Valerolactim has the following formula structure: R wherein ¹For H or contain 1 to 12 carbon atom, alkyl, aryl, alkoxy aromatic yl or the alkaryl of preferred 6 to 12 carbon atoms.In most preferred scheme, R ¹Be selected from phenyl, heptyl, octyl group, nonyl, 2,4,4-tri-methyl-amyl, decyl and their mixture.

Most preferred is generally to be those solid-state compounds at＜30 ℃; phenyl derivatives particularly; be benzoyl Valerolactim, benzoyl caprolactam and their substituted benzoyl analogue, as chlorine, aminoalkyl group, alkyl, aryl and alkoxy derivative.

R wherein ¹Part contains at least 6, and the hexanolactam of preferred 6 to 12 carbon atoms and Valerolactim precursor compound obtain peroxy acid by the peroxidation hydrogenolysis reaction of hydrophobic property, and they provide nucleophilic and body dirt cleansing power.R wherein ¹The precursor compound that comprises 1 to 6 carbon atom provides hydrophilic SYNTHETIC OPTICAL WHITNER kind material, and they are effective especially to the bleaching of beverage spot.For the removal of mixed dirt, it is 1: 5 to 5: 1 that the present invention can use general weight ratio, preferred 1: 1 " hydrophobic " and the mixture of " hydrophilic " hexanolactam and Valerolactim.

Highly preferred hexanolactam and Valerolactim precursor comprise benzoyl caprolactam; the nonanoyl hexanolactam; the benzoyl Valerolactim; the nonanoyl Valerolactim; 3; 5; 5-trimethyl acetyl hexanolactam; 3; 5; 5-trimethyl acetyl Valerolactim; the capryloyl hexanolactam; capryloyl penta lactim; the decanoyl hexanolactam; the decanoyl Valerolactim; the undecanoyl hexanolactam; the undecanoyl Valerolactim; (the amino caproyl of 6-decoyl) oxygen base benzene-sulfonate; (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate; (the amino caproyl of 6-decyl) oxygen base benzene sulfonate, and their mixture.The example of highly preferred substituted benzene formyl lactan comprises the toluyl hexanolactam; the toluyl Valerolactim; the ethylbenzoyl hexanolactam; the ethylbenzoyl Valerolactim; the propyl group benzoyl caprolactam; propylbenzene carbamoyl pentyl lactan; the sec.-propyl benzoyl caprolactam; isopropyl benzene carbamoyl pentyl lactan; the butyl benzoyl caprolactam; butylbenzene carbamoyl pentyl lactan; tertiary butyl benzoyl caprolactam; tert.-butylbenzene carbamoyl pentyl lactan; the amyl group benzoyl caprolactam; amylbenzene carbamoyl pentyl lactan; the hexyl benzoyl caprolactam; hexyl benzene carbamoyl pentyl lactan; phenetole formyl hexanolactam; phenetole formyl Valerolactim; the propoxy-benzoyl caprolactam; propoxy-benzoyl Valerolactim; isopropoxy benzoyl hexanolactam; isopropoxy benzene carbamoyl pentyl lactan; the butoxy benzoyl caprolactam; butyl phenyl ether carbamoyl pentyl lactan; the tert.-butoxy benzoyl caprolactam; tert.-butoxy benzoyl Valerolactim; the pentyloxy benzoyl caprolactam; amyl phenyl ether carbamoyl pentyl lactan; the hexyloxy benzoyl caprolactam; hexyloxy benzoyl Valerolactim; 2; 4; 6-trichlorine benzoyl caprolactam; 2; 4; 6-trichlorobenzene carbamoyl pentyl lactan; penta fluoro benzene formyl hexanolactam; penta fluoro benzene carbamoyl pentyl lactan; the dichloro-benzoyl hexanolactam; dimethoxy benzoyl hexanolactam; 4-chlorobenzoyl hexanolactam; 2; 4-dichloro-benzoyl hexanolactam; the terephthaloyl dicaprolactam; penta fluoro benzene formyl hexanolactam; penta fluoro benzene carbamoyl pentyl lactan; the dichloro-benzoyl Valerolactim; dimethoxy benzene carbamoyl pentyl lactan; 4-chlorobenzene formacyl Valerolactim; 2; 4-dichloro-benzoyl Valerolactim; terephthaloyl two Valerolactims; 4-oil of mirbane formyl hexanolactam; 4-oil of mirbane formyl Valerolactim, and their mixture.

Suitable imidazoles comprises N-benzoyl imidazoles and N-benzoyl benzoglyoxaline, and other peroxyacid precursor that contains the N-carboxyl groups that is suitable for comprises N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

The acid amides substitution compound that another kind of preferred peroxy acid bleach activator compound is following general formula:

Or R wherein ¹For having alkyl, aryl or the alkaryl of 1 to 14 carbon atom, R ²For containing alkylidene group, arylidene or the alkarylene of 1 to 14 carbon atom, and R ⁵For H or contain alkyl, aryl or the alkaryl of 1 to 10 carbon atom, L can be any leavings group basically.R ¹Preferably contain 6 to 12 carbon atoms, R ²Preferably contain 4 to 8 carbon atoms.R ¹Can be the straight or branched alkyl, substituted aryl or contain the alkaryl of side chain, substituting group or both of these case, and can come from synthetic source or comprise natural source as shea butter, similar structures changes R ²Also tolerable.Substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur or other typical substituting group or organic compound.R ⁵Be preferably H or methyl.R ¹And R ⁵Ying Buhan amounts to greater than 18 carbon atoms.This type of substituted amide bleach activating immunomodulator compounds is seen described in the EP-A-0170386.

Reaction takes place for must have enough activity in Best Times scope (as the washing phase) in the L group.Yet if the activity of L is strong excessively, this activator is used for bleaching composition and will be difficult to be stabilized.These character are generally corresponding with the PKa of the conjugate acid of leavings group, but the exception of this routine is known.The leavings group that shows this character is generally its conjugate acid and has 4 to 13, and preferred 6 to 11 and those groups of most preferably 8 to 11PKa values.

Preferred bleach precursor is R wherein ¹, R ²And R ⁵Definition with the definition in the substituted amide compound, and L is selected from those compounds of following radicals and composition thereof: With

With

R wherein ¹Representative contains alkyl, aryl or the alkaryl of 1 to 14 carbon atom, R ³Representative contains the alkyl chain of 1 to 8 carbon atom, R ⁴Represent H or R ³, and Y represents H or solubilizing group (solubilizing group).

Preferred solubilizing group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-With-O＜---N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³For containing the alkyl chain of 1 to 4 carbon atom, M represents deliquescent positively charged ion to bleach-activating agent is provided, and the X representative provides deliquescent negatively charged ion to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, wherein most preferably sodium and potassium, and X is halogenide, oxyhydroxide, methylsulfate or acetic acid anion.Should be noted that in order to help their dissolving the bleach-activating agent that has leavings group (not containing solubilizing group) should be dispersed in the liquid lime chloride well.

The example of preferred above-mentioned general formula bleach-activating agent comprises (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate, and their mixture.

Other preferred precursor compound comprises the benzo oxazinyl compound with following formula structure:

Above-claimed cpd comprises that also lower class replaces benzoxazine compound: R wherein ₁Be H, alkyl, alkaryl, aryl, aralkyl, and R wherein ₂, R ₃, R ₄And R ₅Identical or different substituting group be can be, and H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, COOR are selected from ₆(R wherein ₆Be H or alkyl) and the carbonyl functional group.

Particularly preferred benzo oxazinyl precursor is: Organic peroxide acid

Detergent composition also can contain and accounts for composition weight 1% to 15%, the more preferably organic peroxide acid of 1% to 10% (weight).

A preferred class organic peroxy acid compound is the substituted amide compound with following formula: Or

R wherein ¹For containing the aryl or the alkaryl of 1 to 14 carbon atom, R ²For containing alkylidene group, arylidene or the alkarylene of 1 to 14 carbon atom.R ⁵For H or contain alkyl, aryl or the alkaryl of 1 to 10 carbon atom, R ¹Preferably contain 6 to 12 carbon atoms, R ²Preferably contain 4 to 8 carbon atoms.R ¹Can be the straight or branched alkyl, substituted aryl or contain the alkaryl of side chain, substituting group or both of these case, and can come from synthetic source or comprise for example natural source of shea butter, similarly structural changes is to R ²Also allow.Substituting group comprises alkyl, aryl, halogen, nitrogen, sulphur or other typical substituting group or organic compound.R ⁵Be preferably H or methyl.R ¹And R ⁵Should not contain and total over 18 carbon atoms.The organic peroxy acid compound that this class acid amides replaces is seen described in the EP-A-0170386.

Other organic peroxide acid for example comprises disclosed diperoxy sebacic acid among the EP-A-0341947, diperoxy tetradecane diacid, diperoxy Thapsic acid, list-and two-cross nonane diacids, list-and two mistake undecane dicarboxylic acids, single peroxide phthalic acid, peroxybenzoic acid, and their salt. Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

The present composition preferably comprises the inorganic perhydrate salt as hydrogen peroxide cource, and is particularly the most all the more so when organic peroxy acid source is the peroxyacid bleach precursor compound.

Inorganic perhydrate salt is usually with its sodium-salt form and to account for 1% to 40% of composition weight, more preferably 2% to 30% and most preferably the amount of 5% to 25% (weight) mix.

The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is generally an alkali metal salt.Inorganic perhydrate salt is can crystalline solid forms involved, need not to add in addition protection.Yet for some perhydrate salt, this granular composition preferably adopts the coating form material to realize, this coating form material provides better storage stability for the perhydrate salt in the partical.

Sodium peroxoborate can be standard type NaBO ₂H ₂O ₂The monohydrate of form or tetrahydrate NaBO ₂H ₂O ₂3H ₂O.

SPC-D (the preferred perhydrate that detergent composition of the present invention comprised) is for having corresponding to 2Na ₂CO ₃3H ₂The addition compound of O chemical formula, and can obtain from the market by crystalline solid forms.Percarbonate most preferably is admixed in this composition with the coating form that product stability is provided.

Can provide the suitable thing of filming of product stability to comprise the mixed salt of water-soluble alkali vitriol and carbonate.Yet this coating allows percarbonate bleach to be discharged into rapidly in the washing soln, does not therefore provide percarbonate bleach and postpones to be discharged into the interior suitable means of washing soln.This coating and coating process are described in GB-1466799 (being issued to Interox on March 9th, 1977).Mixed salt is filmed the weight ratio of thing and percarbonate at 1: 200 to 1: 4, and more preferably 1: 99 to 1: 9, most preferably in 1: 49 to 1: 19 the scope.Preferred mixed salt is for having general formula Na ₂SO ₄.n..Na ₂CO ₃Sodium sulfate and yellow soda ash, wherein n is 0.1 to 3, preferred n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5.

Permonosulphuric acid potassium is the another kind of inorganic perhydrate salt that uses in detergent composition of the present invention. Bleaching catalyst

The present invention also comprises the composition that contains catalytically effective amount bleaching catalyst and water-soluble magnesium salt.

Bleaching catalyst uses with catalytically effective amount in the compositions and methods of the invention." catalytically effective amount " is meant and adopting under any simultaneous test condition, the amount that is enough to improve whitening capacity and removes the dirt of desiring to remove from target base thing.Therefore, in the fabric washing operation, target base thing is generally the fabric that is polluted by for example various food soil.For the automatic tableware washing, target base thing can be the polyethylene pan that for example has the porcelain cup or the dish of tea stain or have tomato soup.Test conditions changes with used washing plant and user's custom.For example, compare with the washing machine of top feeding formula american-style, the used front-loading washing machine in Europe makes water consumption less and detergent concentration is higher.Some washing machine has the quite long washing phase than other type washing machine.In the fabric washing operation, some users select very hot water, and other people then use warm water, even cold water.Certainly, the catalytic performance of bleaching catalyst is influenced by this selection, and the amount of the bleaching catalyst that uses in the washing composition of full formula and the whitener composition can suitably be adjusted.As a kind of practical situation (and non-limiting), regulate the compositions and methods of the invention, so that in water washing liquor, obtain the active bleaching catalyst thing of per approximately at least 10,000,000/concentration, and preferably in washing liquid, provide about 1ppm to about 200ppm concentration catalyzer thing.For further specifying this point, adopt perborate and bleach precursor (as benzoyl caprolactam), under European wash conditions, about 3 micromole's manganese salt are at 40 ℃, and are very effective under the pH10.Under the U.S. condition, concentration is increased 3-5 doubly can obtain identical result.On the contrary, compare, use bleach precursor and Mn catalyst and perborate, make the prescription teacher under low peroxyboric acid consumption situation, obtain the whitening capacity that is equal to no Mn catalyst.

Bleaching catalyst thing of the present invention comprises free acid or is any suitable salt form.

One class bleaching catalyst is the catalyst system that comprises following component: the active heavy metal cation of bleach catalyst with regulation, as copper, iron or manganese positively charged ion, have a little or do not have the active assistant metal positively charged ion of bleach catalyst, as zinc or aluminium cations, and the sequestrant that catalysis and assistant metal positively charged ion are had the stability constant of regulation, as ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and water-soluble salt thereof.This class catalyzer is seen USP4, described in 430,243.

The bleaching catalyst of other kind comprises U.S.P.5, disclosed manganese basigamy compound in 246,621 and USP5,244,594.The preferred example of these catalyzer comprises Mn ₂ ^IV(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ₂ ^III(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ₄ ^IV(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂, Mn ^IIIMn ₄ ^IV(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃, and their mixture.Other catalyzer is seen described in No. 549,272, the european patent application.The ligand that other suitable the present invention uses comprises 1,5,9-trimethylammonium-1,5,9-three nitrogen heterocyclic decane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane, and their mixture.

Used bleaching catalyst can be chosen as suitable suitable catalyst of the present invention in the composition herein.Suitable bleaching catalyst example is referring to U.S.P.4, and 246,612 and USP5,227,084.

Also can be referring to USP5,194,416, this patent disclosure monokaryon manganese (IV) title complex, as Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃-(PF ₆).

A class bleaching catalyst (as USP5,114,606 in disclosed) is for manganese (II), (III) and/or (IV) and at least have the water-soluble complexes of the non-carboxylated polyol ligand formation of three consecutive C-OH again.Preferred ligand comprises Sorbitol Powder, iditol, melampyrum (dulsitol), mannitol, Xylitol, arabitol, adonitol, meso tetrahydroxybutane, meso-inositol, lactose, and their mixture.

USP5,114,611 disclose a class bleaching catalyst, and it comprises transition metal, comprises Mn, Co, Fe or Cu, with the title complex of non--(greatly)-ring ligand formation.Described ligand has the following formula structure:

R wherein ¹, R ², R ³And R ⁴Can be selected from H separately, substituted alkyl and aryl, its result makes each R ³-C=N-R ⁴Formation five or six-ring.Described ring can further be substituted.B is for being selected from O, S, CR ⁵R ⁶, NR ⁷With the abutment of C=O, wherein R ⁵, R ⁶And R ⁷The H that can respectively do for oneself, alkyl or aryl, they comprise and replacing or unsubstituted group.Preferred ligand comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles, and triazole ring, and described ring can randomly be replaced by the substituting group as alkyl, aryl, alkoxyl group, halogen and nitro.Particularly preferred ligand is 2,2 '-two pyridyl amine.Preferred bleaching catalyst comprise Co, Cu, Mn, Fe ,-bipyridyl methane and-the bipyridyl amine complex.Highly preferred catalyzer comprises dichloride (2,2 '-bipyridyl amine) close cobalt, two (isosulfocyanate radical) bipyridyl amine closes cobalt (II), perchloric acid three (bipyridyl amine) closes cobalt (II), perchloric acid dioxy two (2,2-bipyridyl amine) close cobalt, perchloric acid two (2,2 '-bipyridyl amine) close copper (II), perchloric acid three (two-2-pyridyl amine) closes iron (II), and their mixture.

Other example comprises managanese gluconate, Mn (CF ₃SO ₃) ₂, Co (NH ₃) ₅Cl and by four-N-dentate and two-N-dentate ligand coordinate double-core manganese comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺(Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Bleaching catalyst of the present invention also can make by the formed mixture of chemical combination water soluble ligand and water-soluble manganese salt and evaporation concentration in water medium.Any suitable water-soluble manganese salt all can here use.Manganese (II), (III), (IV) and/or (V) be easy to obtain with commercial size.In some cases, may exist enough manganese in the washings, but generally also preferably in composition, add the Mn positively charged ion, can exist with catalytically effective amount to guarantee it.For example, with the sodium salt of ligand be selected from MnSO ₄, Mn (ClO ₄) ₂Or MnCl ₂The manganese salt of (least preferred) is with ligand: the amount ratio of the mol ratio of Mn salt in about 1: 4 to 4: 1 scope is dissolved in neutrality or slightly in the water of alkaline pH.Water cools off by the boiling deoxidation and by nitrogen-burst agitation earlier.Evaporate formed solution (if desired, at N ₂Carry out under existing), formed solid need not to be further purified and uses in bleaching of the present invention and detergent composition.

In another program, with water-soluble manganese source, as MnSO ₄, be added in the bleaching/cleaning composition that comprises ligand, or be added in the aqueous bleaching/washing bath that comprises ligand.The title complex of some kind obviously forms on the spot, and obtains improved bleachability.In this in situ method, suitable is to use than the ligand of manganese than big molar excess, and the mol ratio of typical ligand: Mn is 3: 1 to 15: 1.Additional ligand also plays a part to catch the metal ion of drifting, as catches iron and cupric ion, thereby the protection SYNTHETIC OPTICAL WHITNER exempts from decomposition.This system of a kind of acceptable sees that european patent application discloses described in No. 549271.

Though the structure of the manganese complex of catalytically bleaching of the present invention is not illustrated yet, can infer that they comprise inner complex or other is by the carboxyl of part and the hydration coordination compound of nitrogen-atoms and mn ion interaction formation.Equally, in the catalytic process the cationic, oxidized attitude of manganese also non-definite known to, can for (+II), (+III), (+IV) or (+V) valence state.Because six kinds of possible positions existing ligand to be connected with the manganese positively charged ion, thus can legitimate inference, bleach in the medium at water and may have multinuclear class and/or " cage shape " structure.No matter in fact active Mn-ligand kind with which kind of form exists, and they all obviously play katalysis, dirts such as reluctant dirt such as tea, tomato-sauce, coffee, blood is had the bleachability of improvement.

Other bleaching catalyst is for example stated described in the document as follows: european patent application discloses No. 408131 (cobalt complex catalyzer), european patent applications and discloses No. 384503 and 306, No. 089 (catalysis of metalloporphyrin agent), USP4728455 (manganese/multidentate ligand catalyzer).US4,711,748 and european patent application disclose 224, No. 952 (being absorbed in the Mn catalyst on the silico-aluminate), USP4,601,845 (being loaded with the silico-aluminate of manganese and zinc or magnesium salts), USP4,626,373 (manganese/ligand catalyzer), U.S.P4,119,557 (positive iron complex catalyzer), DE2054019 (cobalt sequestrant catalyzer), CA866,191 (salt that contain transition metal), US4430243 (with manganese positively charged ion and on-catalytic metallic cation bonded sequestrant), and U.S.4728455 (gluconic acid Mn catalyst). Heavy metal ion chelating agent

Detergent composition of the present invention can comprise the heavy metal ion chelating agent as the preferred optional component.Heavy metal ion chelating agent herein has been meant the component of sequester heavy metal ion effect.These components also have chelating calcium and magnesium ability, but preferably, they demonstrate the selectivity of bonding heavy metal ion such as iron, manganese and copper.

The consumption of heavy metal ion chelating agent is preferably 0.005% to 20% of composition weight, and more preferably 0.1% to 10%, most preferably 0.5% to 5%.

The heavy metal ion chelating agent (its character is for acid) that has as phosphonic acids or carboxylic functionality can exist with its acid form, or with suitable counter cation such as basic metal or alkaline-earth metal ions, ammonium, or substituted ammonium ion, or the title complex/salt of its any mixture formation.Any salt/title complex all is preferably water miscible.The mol ratio of described counter cation and heavy metal ion chelating agent is preferably at least 1: 1.

The suitable heavy metal ion chelating agent that is fit to the present invention's use includes organic phosphonates, as amino alkylidenyl poly-(alkylene phosphonic acids salt), ethane 1-hydroxyl di 2 ethylhexyl phosphonic acid an alkali metal salt and nitrilo trimethylene phosphonic salt.

In the above-mentioned various sequestrant, preferred diethylenetriamine five (methylene phosphonic acid salt), ethylene diamine three (methylene phosphonic acid salt) hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene-1,1-diphosphonate.

Other suitable heavy metal ion chelating agent that the present invention uses comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid such as ethylenediamine tetraacetic acid (EDTA), second pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or their any salt.

Preferred especially quadrol-N, N '-disuccinic acid (EDDS) or its an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, perhaps their mixture.Preferred EDDS compound is free acid form and its sodium or magnesium salts or title complex.The sodium salt example of the preferred EDDS of this class comprises Na ₂EDDS and Na ₃EDDS.The magnesium complex example of the preferred EDDS of this class comprises MgEDDS and Mg ₂EDDS.

Other suitable heavy metal ion chelating agent that suitable the present invention uses is iminodiacetic acid derivatives such as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid, and they see EP-A-317542 and EP-A-399, described in 133.

Iminodiethanoic acid described in the EP-A-516102, N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are fit to the present invention.β-An Jibingsuan-N described in the EP-A-509382, N '-oxalic acid, aspartic acid-N, N '-oxalic acid, single acetate of aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are fit to.

EP-A-476 has described suitable aminoacetic chelating agent in 257.EP-A-510331 has described and has been derived from collagen, Keratin sulfate or caseic suitable sequestrant.EP-A-528859 has described suitable alkyl imino oxalic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2,4-tricarboxylic acid also are suitable.G-NH2-N, N '-disuccinic acid (GADS) is also more suitable. Organic polymer

Organic polymer is the particularly preferred component of detergent composition of the present invention.In fact organic polymer is meant and is used as dispersion agent usually in detergent composition, and any organic polymer of antiredeposition and soil-suspending agent.

Organic polymer is generally accounting for composition weight 0.1% to 30%, and is preferred 0.5% to 15%, and most preferably the amount of 1% to 10% (weight) is incorporated in the detergent composition of the present invention.

The example of organic polymer comprises water soluble organic substance homogeneous or copolymerization poly carboxylic acid or its salt, and wherein poly carboxylic acid comprises at least two carboxyls that separated by no more than two carbon atom each other.A kind of type polymer in back is disclosed among the GB-A-1596756.It is the multipolymer of the polyacrylate of 2000-5000 and they and maleic anhydride that the example of this salt has MWt.This multipolymer has 20,000 to 100,000, especially 40,000 to 80,000 molecular weight.

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

The polyamino compound also is suitable in the present invention, and they comprise those compounds that obtained by aspartate-derived, as among EP-A-305282, EP-A-305283 and the EP-A-351629 disclosed those.

Other organic polymer that is suitable for mixing in the detergent composition of the present invention comprises derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose and Natvosol.

The organic polymer of Shi Yonging is that polyoxyethylene glycol, particularly molecular weight are 1000-10000 in addition, more preferably 2000 to 8000, and those polyoxyethylene glycol of 4000 most preferably from about. The lime soap dispersing agent compound

The present composition can contain the lime soap dispersing agent compound, and they have and followingly definedly are no more than 8, preferably are no more than 7, are most preferably not exceeding 6 dispersion of calcium soap (LSDP).The lime soap dispersing agent compound is preferably to account for composition weight 0.1% to 40%, and more preferably 1% to 20%, most preferably 2% to 10% amount exists.

Lime soap dispersing agent is to be used to prevent that calcium or magnesium ion from causing the sedimentary material of an alkali metal salt, ammonium salt or amine salt of lipid acid.The numerical measuring that lime soap dispersing agent is renderd a service provides with dispersion of calcium soap (LSDP), and they pass through to adopt H.C.Borghetty and C.A.Bergman, J.Am.Oil.Chem.Soc., and Volume 27, and the calcium soap distributed test described in the p88-90 (1950) is measured.This calcium soap distributed test method is extensive use of by the professional in related field in the following summary document: W.N.Linfield, and Surfactant Science Series, Volnme 7, p3; W.N.Linfield, Tenside Surf.Det.Volume 27, pages 159-161 (1990); And M.K.Nagatajan, W.F.Masler, Cosmetics and Toiletries, Volume 104, pages71-73 (1989).LSDP is meant needs to disperse the 0.025g sodium oleate at 30ml 333ppmCaCO ₃(Ca: Mg=3: 2) the sedimentary dispersion agent of calcium soap that forms in equivalent hardness (equivalent hardness) water and the % weight ratio of sodium oleate.

Tensio-active agent with good lime soap dispersing power comprises some amine oxides, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylated alcohol.

The typical surface promoting agent that is not more than 8LSDP that has that uses for the present invention comprises C ₁₆-C ₁₈The dimethyl amine oxide compound, the C with 1-5 average degree of ethoxylation ₁₂-C ₁₈Alkyl ethoxy sulfate particularly has the C of about 3 ethoxylation degrees ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant (LSDP=4), and C with 12 (LSDP=6) or 30 average degree of ethoxylation ₁₃-C ₁₅Ethoxylated alcohol, they sell (BASF GmbH) with Lutensol A012 and LutensolA030 trade(brand)name respectively.

The polymerization lime soap dispersing agent that is fit to the present invention's use is seen M.K.Nagarajan and W.F.Masler, Cosmetics and Toilteries, and Volume 104, described in the article of p71-73 (1989).The example of this class polymerization lime soap dispersing agent comprises some vinylformic acid, methacrylic acid or its mixture, and with the water-soluble salt of the multipolymer of acrylamide or substituted acrylamide, wherein this polymkeric substance generally has 5,000 to 20,000 molecular weight. Press down foam system

When being mixed with the machine washing composition when using, detergent composition of the present invention preferably contains and presses down foam system, and its amount is 0.01% to 15% of a composition weight, and is preferred 0.05% to 10%, and most preferably 0.1% to 5%.

In fact the suitable foam system that presses down that uses for the present invention can comprise any known anti-foam compound, comprises for example anti-foam compound of siloxanes, and 2-alkyl-alkane alcohols is prevented the foam compound.

Anti-foam compound has been meant that in this application suppressing detergent composition solution (particularly under this solution situation of stirring) produces any compound of foamy effect or the mixture of these compounds.

The particularly preferred anti-foam compound that uses for the present invention is the anti-foam compound of siloxanes, and it is defined as any anti-foam compound that comprises silicone components.The anti-foam compound of this class siloxanes generally also contains silica component.The used term " siloxanes " (generally also being applicable to industry) of the application comprises the various relative high-molecular weight polymers that contain siloxane unit and various alkyl.The anti-foam compound of preferred polysiloxane is a siloxanes, particularly has the unitary polydimethylsiloxane of TMS end-block.

Other suitable anti-foam compound comprises monobasic aliphatic carboxylic acid and water-soluble salt thereof.These materials are seen described in the USP2954347 (being issued to Wayne St.John September 27 nineteen sixty).Monobasic aliphatic carboxylic acid and salt thereof as suds suppressor generally have 10 to about 24 carbon atoms, the hydrocarbyl chain of preferred 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt such as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salts.

Other suitable anti-foam compound comprises, for example, and the fatty acid ester of high molecular fatty ester (as fatty acid triglycercide), monovalent alcohol, aliphatic C ₁₈-C ₄₀Ketone (as stearone), N-alkylation aminotriazine, as three-to six-alkyl melamine or two-to four-alkyl diamine chlorotriazine (cyanuryl chloride and two or three moles contain the uncle of 1 to 24 carbon atom or the product that secondary amine forms), propylene oxide, two stearic amide and single stearyl di(2-ethylhexyl)phosphate-an alkali metal salt (as sodium, potassium, lithium) and phosphoric acid ester.

The multipolymer of oxyethane and propylene oxide particularly has the mixing ethoxyquin/third oxidation of fat alcohol (having 10 to 16 carbon atom alkyl chain lengths) of 3 to 30 ethoxylation degrees and 1 to 10 propoxylation degree, also for being fit to the suitable anti-foam compound that the present invention uses.

The anti-foam compound of suitable 2-alkyl-alkane alcohols that is fit to the present invention's use is seen described in the DE4021265.2-alkyl-the alkanol that is fit to the present invention's use is by the C that is loaded with terminal hydroxy group ₆To C ₁₆Alkyl chain constitutes, described alkyl chain in described position by C ₁To C ₁₀Alkyl chain replaces.2-alkyl-chain triacontanol mixture also can use in the present composition.

The preferred foam system that presses down comprises:

(a) anti-foam compound, the anti-foam compound of preferred siloxanes, most preferably in conjunction with the anti-foam compound of the siloxanes that comprises following component:

(i) polydimethylsiloxane accounts for 50% to 99% of silicone compounds weight, and preferred 75% to 95%; With

(ii) silica comprises siloxanes/silicon-dioxide is prevented 1% to 50%, preferred 5% to 25% of foam compound weight;

The anti-foam compound of wherein said silica/silicon oxygen alkane is with 5% to 50%, and the amount of preferred 10% to 40% (weight) is mixed;

(b) compound dispersing agent most preferably comprises siloxanes ethylene glycol coarse grain (rake) multipolymer with 72-78% polyoxyalkylene content and 1: 0.9 to 1: 1.1 oxyethane and ratio of propylene oxide, and its amount is 0.5% to 10%, preferred 1% to 10% (weight); Particularly preferred this siloxanes ethylene glycol coarse grain multipolymer is DCO544, buys with the DCO544 trade(brand)name from DOWCorning;

(c) inert support fluid compound most preferably comprises having 5 to 50, the C of preferred 8 to 15 ethoxylation degrees ₁₆-C ₁₈Ethoxylated alcohol, its amount are 5% to 80%, preferred 10% to 70% (weight);

The granular suds suppressing agent system that preferred the present invention is suitable for comprises the mixture of the above-mentioned type alkylation siloxanes and solid-state silicon-dioxide.

Solid-state silicon-dioxide can be fumed silica, precipitated silica or the silicon-dioxide that is prepared by the gel formation technology.These suitable silica dioxide granules have 0.1 to 50 micron, preferred 1 to 20 micron average particulate size and 50m at least ²/ g surface-area.By with Direct Bonding on silicon-dioxide or handle these silica dioxide granules by means of the dialkyl group silyl and/or the trialkylsilkl of silicone resin, give their hydrophobicitys.Preferred its particle that uses is by the silicon-dioxide of dimethyl and/or trimethyl silyl hydrophobic property.The anti-foam compound of particle that preferably is included in the detergent composition of the present invention comprises a certain amount of silicon-dioxide, so that the weight ratio of silicon-dioxide and siloxanes is positioned at 1: 100 to 3: 10, in preferred 1: 50 to 1: 7 scope.

Another kind of suitable granular suds suppressing system is used and is had about 500 to about 200, the well-mixed hydrophobic silanization of the dimethyl-silicone-polymer fluid of 000 molecular weight (most preferably trimethylammonium-silanization) silicon-dioxide represents, described silanized silica has 10 nanometer to 20 nano-particles size and greater than 50m ²/ g specific surface area, wherein the weight ratio of polysiloxane and silanized silica is about 1: 1 to about 1: 2.

Particularly preferred granular suds suppressing system is seen described in the EP-A-0210731, and comprise anti-foam compound of siloxanes and the organic carrier material of fusing point in 50 ℃ to 85 ℃ scopes, wherein the organic carrier material comprises the monoesters of glycerine and the lipid acid with 12 to 20 carbon atom carbochains.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein the organic carrier material is lipid acid or the alcohol with 12 to 20 carbon atom carbochains, or their mixture, and has 45 ℃ to 80 ℃ fusing points.

Other particularly preferred granular suds suppressing system is seen described in the co-pending European application 91870007.1 of Procter and Gamble Company, this system comprises that siloxanes prevents the foam compound, carrier substance, organic coating and glycerine, wherein glycerine: the anti-foam compound of siloxanes is 1: 2 to 3: 1 (weight ratio).Common unsettled european patent application 91201342.0 also discloses granular suds suppressing system very preferably, this system comprises the anti-foam compound of siloxanes, carrier substance, organic coating and crystallization or amorphous aluminosilicate, wherein silico-aluminate: the anti-foam compound of siloxanes is 1: 3 to 3: 1 (weight ratio).In above-mentioned two pieces of documents, the carrier substance that uses in the particularly preferred granular foam control agent is starch.

The particle agglomerates component that the typical granular suds suppressing system of using for the present invention is produced as agglomeration technique, their are in conjunction with comprising following component:

(i) account for this component 5% to 30%, preferred 8% to 15% (weight) siloxanes is prevented the foam compound, and this compound preferred combination comprises polydimethylsiloxane and silicon-dioxide;

(ii) account for this component 50% to 90%, preferred 60% to 80% weight carrier substance, preferred starch;

(iii) account for this component 5% to 30%, preferred 10% to 20% weight agglomerate binder compound, here, this compound can be any compound that generally is used as the agglomerate tackiness agent, or its mixture, most preferred above-mentioned agglomerate binder compound comprises the C with 50 to 100 ethoxylation degrees ₁₆-C ₁₈Ethoxylated alcohol; With

(iv) 2% to 15%, preferred 3% to 10% weight C ₁₂-C ₂₂Hydrogenated fatty acid. The polymeric dye transfer inhibitor

Detergent composition of the present invention also can comprise 0.01% to 10%, preferred 0.05% to 0.5% (weight) polymeric dye transfer inhibitor.

The polymeric dye transfer inhibitor preferably is selected from the multipolymer of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, polyvinyl pyrrolidone polymers or their binding substances. A) polyamine N-oxide pllymers

The polyamine N-oxide pllymers that is fit to the present invention's use comprises the unit with following structural formula:

Wherein P is for can gather the unit, and it can be connected with the R-N-O group, or wherein the R-N-O group forms the combination that can gather a unitary part or both of these case.A is

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

R is aliphatic series, aliphatic, the aromatics of ethoxyquin, heterocycle or alicyclic group, or their any combination, and they can be connected with the nitrogen of N-O group, and perhaps wherein the nitrogen of N-O group is the part of these groups.

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

Or R wherein ₁, R ₂And R ₃Be aliphatic group, aromatics, heterocycle or alicyclic group or its binding substances, x or/and y or/and z is 0 or 1, the part that the nitrogen of N-O group can be connected or wherein the nitrogen of N-O group forms these groups wherein.The N-O group can be can gather the part of unit (P) or can be connected with polymer backbone, perhaps is the combination of both of these case.

Wherein the N-O group forms the suitable polyamine N-oxide can gather a unit part and comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatics, alicyclic and heterocyclic group.The described polyamine N-oxide of one class comprises one group of wherein polyamine N-oxide of the nitrogen formation R-group part of N-O group.Preferred polyamine N-oxide compound is that wherein R represents those compounds of heterocyclic radical such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.

Another kind of described polyamine N-oxide comprises one group of wherein nitrogen and the basic polyamine N-oxide that links to each other of R-of N-O group.

Other suitable polyamine N-oxide is the N-O group and can gather the polyamine oxide compound that the unit is connected.

The preferred kind of these polyamine N-oxide is for to have the polyamine N-oxide of general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of described R group.The example of this class polyamine N-oxide comprises that wherein R is the polyamine oxide compound of heterogeneous ring compound such as pyridine, pyrroles, imidazoles and derivative thereof.

The polyamine N-oxide of other preferred kind is for having the polyamine oxide compound of general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group links to each other with described R group.The example of these kind polyamine oxide compounds is that wherein the R group can be the polyamine oxide compound of aromatic group such as phenyl.

Can use any polymer backbone, as long as the amine oxide polymers that forms is water-soluble and has the dye transfer inhibition activity.The example of suitable polymer blend skeleton comprises polyethylene kind, polyalkylene class, polyester, polyethers, polymeric amide, pi, polypropylene ester and their mixture.

Amine n-oxide polymkeric substance of the present invention generally has 10: 1 to 1: 1000000 the amine and the ratio of amine n-oxide.Yet the amount of existing amine oxide class can change by suitable interpolymerization or by suitable N-oxidisability in the polyamine oxide polymer.Preferred amines is 2: 3 to 1: 1000000 with the ratio of amine oxide, more preferably 1: 4 to 1: 1000000, and most preferably 1: 7 to 1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and wherein a kind of monomer type is an amine n-oxide, another kind of monomer type or be amine n-oxide or non-amine n-oxide.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.

The polyamine oxide compound is gone up substantially and can any polymerization degree be obtained.The polymerization degree is unimportant, as long as the gained material has water-soluble and the dye suspension ability that needs.Molecular-weight average is generally in 500 to 1000,000 scopes, and is preferred 1,000 to 50,000, and more preferably 2,000 to 30,000, most preferably 3,000 to 20,000. B) multipolymer of N-vinyl pyrrole ketone and N-vinyl imidazole

The polymkeric substance that the preferred the present invention of being fit to uses can comprise the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, and wherein said polymkeric substance has 5,000 to 50,000, more preferably 8,000 to 30,000,10,000 to 20,000 molecular-weight average most preferably.The mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1 to 0.2 in the preferred N-vinyl imidazole N-vinylpyrrolidone copolymer, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4. C) polyvinylpyrrolidone

Detergent composition of the present invention also can use polyvinylpyrrolidone (" PVP "), and its molecular-weight average is 2,500 to 400,000, and is preferred 5,000 to 200,000, and more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.Suitable polyvinylpyrrolidone can be from ISPCorporation, New York, NY and Montreal, Canada is with PVP K-15 (viscosity-average molecular weight 10,000), PVP K-30 (molecular-weight average 40,000), PVP K-60 (molecular-weight average 160,000), buy with PVP K-90 (molecular-weight average 360,000) trade(brand)name, PVP K-15 also can obtain from ISP Corporation.What other was suitable also can comprise Sokalan HP165 and Sokalan HP12 from the polyvinylpyrrolidone that BASF Co rperation buys.

Polyvinylpyrrolidone can account for 0.01% to 5% of washing composition weight, and is preferred 0.05% to 3%, and more preferably 0.1% to 2% amount is admixed in the detergent composition of the present invention.The amount of the polyvinylpyrrolidone that disengages in washings is preferably 0.5ppm to 250ppm, more preferably 25ppm to 150ppm, more preferably 5ppm to 100ppm. D) Ju Yi Xi oxazolidone

Detergent composition of the present invention also can use Ju Yi Xi oxazolidone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidone is 2500 to 400,000, and is preferred 5,000 to 200,000, more preferably 5,000 to 50,000, most preferably 5,000 to 15,000.

The amount that is incorporated into the poly-second alkene oxazolidone in the detergent composition can be 0.01% to 5% by weight, and is preferred 0.05% to 3%, more preferably 0.1% to 2%.The amount of Ju Yi Xi oxazolidone in washing soln is generally 0.5ppm to 250ppm, preferred 2.5ppm to 150ppm, more preferably 5ppm to 100ppm. E) polyvinyl imidazole

Detergent composition of the present invention also can use polyvinyl imidazole as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazole is preferably 2,500 to 400,000, and more preferably 5,000 to 50,000, most preferably 5,000 to 15,000.

The amount that is incorporated into the polyvinyl imidazole in the detergent composition can be 0.01% to 5% by weight, and is preferred 0.05% to 3%, more preferably 0.1% to 2%.The amount of the polyvinyl imidazole that disengages in washings is 0.5ppm to 250ppm, preferred 2.5ppm to 150ppm, more preferably 5ppm to 100ppm. White dyes

Detergent composition of the present invention can randomly contain the hydrophilic white dyes of some kind of 0.005% to 5% weight of having an appointment, and they also play the dye transfer restraining effect.If use, the present composition will preferably comprise this white dyes of about 0.01% to 1% weight.

The hydrophilic white dyes of Shi Yonging is the compound with following structural formula in the present invention: R wherein ₁Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; And M is salt-forming cation such as sodium or potassium.

R in following formula ₁Represent anilino, R ₂Represent N-2-two-when hydroxyethyl and M were positively charged ion such as sodium, described whitening agent was 4,4 '-two [(4-anilino-6-(the two hydroxyethyls of N-2-)-sym-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.The whitening agent of this particular variety can be buied with Tinopal-UNPA-GX trade(brand)name (Ciba-Geigy Corporation) from the market.The wetting ability white dyes of Tinopal-UNPA-GX for using in the preferred suitable detergent composition of the present invention.

R in following formula ₁Be anilino, R ₂When being positively charged ion such as sodium for N-2-hydroxyethyl-N-2-methylamino and M, described whitening agent be 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-sym-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.The whitening agent of this particular variety can be buied with Tinopal5BM-GX trade(brand)name (Ciba-Geigy Corporation) from the market.

R in following formula ₁Be anilino, R ₂When being positively charged ion such as sodium for morpholino and M, described whitening agent is 4,4 '-two [(4-anilino-6-morpholino-sym-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid, sodium salt.The whitening agent material of this particular variety can be buied with Tinopal AMS-GX trade(brand)name from CibaGeigy Corporation.

When being used in combination with foregoing specific aggregation dye transfer inhibitor, the selected special white dyes material that uses for the present invention can provide especially effectively dye transfer rejection characteristic effect.Compare with any of these two kinds of detergent composition components of independent use, being combined in of white dyes (as TinopalUNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) that the polymkeric substance (as PVNO and/or PVPVI) that this class is specific and this class are selected can provide better dye transfer restraining effect in the aqueous solution.Needn't be bound by theory, it is believed that this whitening agent has high affinity to fabric in washing soln, so adhere on these fabrics than comparatively fast, old friends can think that this whitening agent works in such a way.In washing soln, the adhesion amount of whitening agent on fabric can be with the parameter-definition that is called " consumption coefficient " (" exhaustioncoefficient ").The consumption coefficient General Definition is made the whitening agent material and the b that adhere on a) fabric) ratio of the initial concentration of whitening agent in the washings.Whitening agent with comparison high flow rate coefficient is adapted at being used in the present composition suppress dye transfer most.

Of course it is to be understood that other conventional white dyes species compound also can randomly use in the present composition, " brighten " effect so that conventional fabric to be provided, rather than real dye transfer suppresses effect.This use is conventional, and for washing composition preparation known. Softening agent

Fabric softener also can be incorporated in the laundry detergent composition of the present invention.These softening agents divide from type can comprise inorganic or organic two classes.Inorganic softening agent can illustrate with disclosed smectic clays among the GB-A-1400898 (Smectite Clays).The organic fabric softening agent comprises as disclosed water-insoluble tertiary amine among GB-A-1514276 and the EP-B-0011340.

The amount of smectic clays is generally 5% to 15%, more preferably in 8% to 12% weight range, and is added in the remainder of prescription with dry mixed component form.Organic fabric softening agent such as water-insoluble tertiary amine or dilong chain acid amides material are with 0.5% to 5% (weight), the amount that is generally 1% to 3% (weight) is mixed, but high molecular weight polyethylene oxide material and water-insoluble cationic substance are by weight with 0.1% to 2%, and 0.15% to 1.5% amount that is generally adds. Other optional member

Be fit to other optional member of the present invention and also can be included in the present composition, they comprise spices, colorant and filling salt, and wherein preferably sulfuric acid sodium is as filling salt. Composition forms

Detergent composition of the present invention can be mixed with any form that needs, as powdery, particle, pasty state, liquid, tablet and gel. Fluid composition

Detergent composition of the present invention can be mixed with liquid detergent compositions.This liquid detergent compositions generally comprises 94% to 35%, and is preferred 90% to 40%, 80% to 50% weight liquid carrier most preferably, and as water, preferably water and ORGANIC SOLVENT MIXTURES. Gelatinous composition

Detergent composition of the present invention can also be gel form.The general apparatus of this composition has an appointment 750,000 to the preparation of the polyalkenyl polyether of about 4,000,000 molecular weight. Solid-state composition

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

The granular size of granular composition component of the present invention should be preferably so, has the diameter greater than 1.4mm so that be no more than 5% particle, and is no more than 5% particle and has diameter less than 0.15mm.

The tap density of granular detergent composition of the present invention generally is at least the 450g/ liter, more common is 600g/ liter at least, and more preferably 650g/ rises to the 1200g/ liter.

Utilizing firmly is embossed on the pedestal, and its lower end is furnished with the simple funnel-beaker device of the conical hopper composition of plate valve, measure tap density, can make by the clack valve on the funnel in the round beaker of the content streamer axial array below placing funnel in the funnel.The top and bottom of funnel are respectively 130mm and 40mm, and fixed funnel makes its lower end from base upper surface 140mm, and the beaker total height is 90mm, and interior height is 87mm, and internal diameter 84mm, nominal volume are 500ml.

When measuring, hand is poured powder into and is filled up funnel, opens clack valve, makes powder overfill beaker.The filler beaker shifts out from frame, removes excess powder by crossing upper surface with straight flange instrument such as cutter.The filler beaker of weighing then doubles the powder weight value, obtains rising with g/ the tap density of expression.Carry out replicate measurement on request. The preparation method of granular composition

In general, granular composition of the present invention can pass through prepared in various methods, and these methods comprise dry mixed, spraying drying, agglomeration and granulating. Washing methods

The present composition can use in any washing or cleaning method basically, and these methods comprise machine laundry and wash up method. Machine wash up method

Preferred machine wash up method comprises with the water liquid of the machine dishwashing compositions of the present invention that is dissolved with or wherein is dispersed with significant quantity handles contaminated articles, and these article are selected from pottery, glasswork, holloware and cutlery and their mixture.The significant quantity of machine dishwashing compositions is meant dissolving or dispersion 8g to 60g product in 3 to 10 liters of washing solns.This also is normally used typical product dosage and a washing soln volume in the conventional machine wash up method. The machine clothes washing method

Machine clothes washing method of the present invention is included in the clothing of handling pollution in the washing machine with the water washing liquor of the machine laundry detergent composition of the present invention that wherein is dissolved with or is dispersed with significant quantity.Utilize the material feeder drawer or the dosing unit of washing machine, washing composition is added in the washings.The significant quantity of detergent composition is meant in 5 to 65 liters of volume washingss and is dissolved with or is dispersed with 40g to 300g washing composition product.This also is typical product dosage and the washings volume that adopts usually in the conventional machine clothes washing method.

In the preferred washing methods of the present invention, the dosing unit that contains the significant quantity detergent composition inserted in the cylinder of front-loading washing machine before the washing phase begins.

Dosing unit is the container that holds Betengent product, and it can be used for product is directly delivered in the cylinder of washing machine.Its volume capacity should be so big, so that it can comprise normally used capacity Betengent product in the washing methods.

The clothes that will wash in case pack in the washing machine and the dosing unit that contains Betengent product place cylinder, feed water in the cylinder when the washing machine washing phase begins and make the cylinder periodic rotation.Dosing unit should so design, and holds dry Betengent product so that it is allowed, and during washing subsequently, along with cylinder rotates the stirring that causes, and is immersed in the washing water by it, should allow to disengage this washing composition product.

During the washing, disengage for making Betengent product, dosing unit should have the eyelet that a large amount of permission products pass through.Perhaps, this device can be by liquid permeable but the material preparation of impermeable solid phase prod, and this sampling device will allow lysate to disengage.Preferably the washing phase at the beginning, Betengent product can disengage rapidly, thereby in the initial stage of washing phase, forms local high product concentration of moment in the cylinder of washing machine.

Preferred dosing unit is reusable, and is designed in dry state and can both keeps the integrity of container between the washing phase.The dosing unit that particularly preferred suitable the present invention uses is stated described in the patent documentation as follows: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.J.Bland is published in Manufacturing Chemist, and November 1989, also describes in the article of p41-46 to be fit to the particularly preferred dosing unit that the granular laundry product uses, and the granular laundry product is a series products of so-called " granulette ".

Particularly preferred dosing unit is disclosed in european patent application and discloses 0343069 ﹠amp; In No. 0343070.Back one application discloses a kind of dosing unit, and there is a flexible bag shape cover front portion that this device is included in bag, and described bag stretches out from stipulate foraminate supporting ring, regulates little ring to allow to have in the bag capacity Betengent product of using for washing phase in the washing process.The part washing medium flows in the bag by aperture, lysate, and solution flow in the washing medium from the outside by aperture then.Supporting ring has and prevents moistening and the shielding structure outflow of not molten product, this structure generally comprises radially wall extension (radially extending walls), this wall extends out from the central hub of width of cloth bar wheel construction, and perhaps wherein said wall has the similar structures of spiral form. The pre-treatment washing methods

In pre-treatment washing methods scheme of the present invention, pollution/spot base thing is handled with the preprocessing solution (not containing the enzyme component) that significant quantity contains water-soluble washing assistant.This solution can be chosen wantonly and contain other non-enzyme detergent component, as tensio-active agent, washing assistant and washing composition polymkeric substance, also contains water soluble detergency promoter in the preferred solution.

The amount of water soluble detergency promoter is generally 0.05% to 80% in the described preprocessing solution, and is preferably greater than 1%.

Make preprocessing solution and the basic thing of pollution keep in touch one period working lipe.The described timed interval was generally 10 seconds to 1800 seconds, more preferably 60 seconds to 600 seconds.

Pollute basic thing then with suitable washing methods washing, wherein use the Betengent product that contains enzyme.Washing methods can be any as described in the present invention machine wash up method or machine clothes washing method.

In detergent composition of the present invention, abbreviation component symbol has following implication: XYAS: C _1x-C _1ySodium alkyl sulfate 25EY: with the linear C that is mainly of average Y moles of ethylene oxide condensation _12-15

Primary alconol XYEZ: with the linear C that is mainly of average Z moles of ethylene oxide condensation _1x-

C _1yPrimary alconol XYEZS: every mole with average Z moles of ethylene oxide condensation C _1x-C _1y

Sodium alkyl sulfate TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide Silicate: amorphous silicic acid sodium (SiO ₂: Na ₂O=2.0) NaSKS-6: the formula δ of crystallization stratification-Na ₂Si ₂O ₅Silicate Carbonate: anhydrous sodium carbonate Polycarboxylate:1: 4 toxilic acids/acrylic copolymer, molecular-weight average 80,000Zeolite A: formula with 1 to 10 micron main granular size

Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydrated sodium aluminosilicate Citrate of O: citrate trisodium dihydrate Percarbonate is (fast: as to be tested formula Na ₂SO ₄.n.Na ₂CO ₃Mixed salt (wherein n is 0.29) mixes release particles) salt coat have an empirical formula 2Na ₂CO ₃3H ₂O ₂The anhydrous carbon of crossing

Acid sodium SYNTHETIC OPTICAL WHITNER, wherein the weight ratio of percarbonate and mixed salt is 39: 1Percarbonate is (slow: by water glass (SiO ₂: Na ₂O=2: yellow soda ash SYNTHETIC OPTICAL WHITNER 1) the anhydrous release particles of crossing that thing coats of filming); the weight ratio of percarbonate and water glass is 39: 1TAED: tetra-acetylated-1; 2-quadrol TAED (slow release is put: use citric acid and polyoxyethylene glycol (PEG) (Mw=4,000) with particle) component TAED: citric acid: PEG=75: 10: 5 weight is made a farfetched comparison

Poly-TAED forms, and is filmed thing with agglomerate by the citric acid external application:

The film weight ratio coated pellet Benzoyl of thing=95: 5 of citric acid: with citric acid and Mw=4,000 polyoxyethylene glycol (PEG) forms with Caprolactam (slow release B component zCl: citric acid: PEG=63: 21: 16 weight ratio is put particle) agglomeration benzoyl caprolactam (BzCl), and uses lemon

The acid external application is filmed thing with agglomerate: film thing=95: 5 of citric acid

Weight ratio coated pellet TAED (fast release: with part neutral multi-carboxylate with TAED: forming multi-carboxylate=93: 7 particles) than agglomeration TAED, and with multi-carboxylate's external application thing of filming

With agglomerate: weight ratio coated pellet EDDS (fast release: use MgSO of the thing of filming=96: 4 ₄Particle with weight ratio spraying drying EDDS formation in 26: 74) particle Protease: the egg that Novo Industries A/S sells with the Savinase trade(brand)name

White enzyme, activity is sold for 13KNPU/gProtease (slow release is put: contain Novo Industries A/S and go out particle with the Savinase trade(brand)name) and activity is the proteolytic enzyme of 13KNPU/g, and by water glass

(SiO ₂: Na ₂O=2: the 1) enzyme granulate that thing coats of filming, wherein

The thing amount of filming is 5%Amylase: Novo Industries A/S is with Termamyl 60T trade(brand)name

The amylase of selling, activity are the cellulase that 300KNU/gCellulase:Novo Industries A/S sells, and activity is

2000CEVU/gLipase: the fat that Novo Industries A/S sells with the Lipolase trade(brand)name

Separate enzyme, activity is 165KLU/gCMC: Xylo-Mucine HEDP: 1,1 hydroxyl ethane di 2 ethylhexyl phosphonic acid EDDS: the quadrol-N of sodium-salt form, N '-disuccinic acid, [S, S] isomery

Body PVNO: poly-(the 4-vinylpyridine of vinyl imidazole and vinyl pyrrolidone

Pyridine)-and N-oxide block copolymer Granular Suds: particle form 12% siloxanes/silicon-dioxide, 18% stearyl alcohol, Suppressor 70% starch

Embodiment 1

Prepare following laundry detergent composition, wherein the percentage amounts of each composition weight in each numeric representation composition: composition A is the prior art composition, and composition B to D is the present composition.

	A	B	C	D
	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	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	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	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 (fast release particles)	6.3	-	-	-	Carbonate	7.6	7.6	7.6	7.6
TAED (fast release particles)	6.3	-	-	-	TAED (slow release is put particle)	-	5.0	-	2.3
Benzoyl Caprolactam (slow release is put particle)	-	-	5.0	2.7	TAED (slow release is put particle)	-	5.0	-	2.3
Benzoyl Caprolactam (slow release is put particle)	-	-	5.0	2.7	Percabonate (fast release particles)	22.5	-	-	22.5
Percabonate (slow release is put particle)	-	22.5	22.5	-	Percabonate (fast release particles)	22.5	-	-	22.5
Percabonate (slow release is put particle)	-	22.5	22.5	-	DETPMP	0.5	0.8	-	-
EDDS (fast release particles)	-	-	0.3	0.75	DETPMP	0.5	0.8	-	-
EDDS (fast release particles)	-	-	0.3	0.75	Protease	0.55	-	-	-
Protease (slow release is put particle)	-	1.27	0.55	1.27	Protease	0.55	-	-	-
Protease (slow release is put particle)	-	1.27	0.55	1.27	Lipase	0.15	0.15	0.15	0.15
Cellulase	0.28	0.28	0.28	0.28	Lipase	0.15	0.15	0.15	0.15
Cellulase	0.28	0.28	0.28	0.28	Amylase	O.27	0.27	0.27	0.27
PolycarbOxylate	5.1	5.1	5.1	5.1	Amylase	O.27	0.27	0.27	0.27
PolycarbOxylate	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	CMC	0.4	0.4	0.4	0.4
PVNO	0.03	0.03	0.03	0.03	Granular suds suppressor	1.5	1.5	1.5	1.5
Accessory constituent/other component adds to 100%					Granular suds suppressor	1.5	1.5	1.5	1.5

Claims

1. detergent composition, said composition comprises:

(a) water soluble detergency promoter; With

(b) enzyme wherein provides the mode that discharges with respect to described enzyme of the hang-over n. of described water soluble detergency promoter in washing soln, so that in described T50 test method, the 50% described required time of water soluble detergency promoter ultimate density that reached is lower than 60 seconds, and reaches the required time of 50% described enzyme ultimate density greater than 150 seconds.

2. according to the detergent composition of claim 1, wherein said enzyme comprises amylase.

3. according to the detergent composition of claim 1 or 2, described composition comprises organic peroxyacid bleach source, the mode that discharges in washing soln with respect to described peroxyacid bleach of the hang-over n. of described tensio-active agent wherein is provided, so that in the T50 test, the time that reaches 50% peroxyacid bleach ultimate density was greater than 180 seconds.

4. according to the detergent composition of claim 3, wherein said peroxyacid bleach source is the peroxybenzoic acid source.

5. according to the detergent composition of claim 3 or 4, wherein said peroxyacid bleach source is in conjunction with comprising following component:

(i) hydrogen peroxide cource; With

(ii) peroxyacid bleach precursor compound.

6. according to the detergent composition of claim 5, wherein said peroxyacid bleach precursor compound has cationic charge.

7. according to the detergent composition of claim 6, wherein said peroxyacid bleach precursor is 2-(N, N, N-trimethyl ammonium) ethyl 4-sulfo group benzol carbonate na chloride or 4 (trimethyl ammonium) toluyl oxygen base benzene sulfonate.

8. according to the detergent composition of claim 4, wherein said peroxyacid bleach precursor compound is selected from:

A) the substituted amide bleach precursor of following general formula or its mixture: R wherein ¹For containing alkyl, aryl or the alkaryl of 1 to 14 carbon atom, R ²For containing alkylidene group, arylidene or the alkarylene of 1 to 14 carbon atom, R ⁵For H or contain alkyl, aryl or the alkaryl of 1 to 10 carbon atom, and L is a leavings group;

B) following formula benzo oxazinyl bleach precursor: R wherein ₁Be H, alkyl, alkaryl, aryl, aralkyl, and R ₂, R ₃, R ₄And R ₅Can be identical or different substituting group, they be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino ,-COOR ₆, R wherein ₆Be H or alkyl and carbonyl functional group;

C) following formula N-acylated lactams bleach precursor: Wherein n is 0 to 8, and is preferred 0 to 2, and R ⁶For H, contain alkyl, aryl, alkoxy aromatic yl or the alkaryl of 1 to 12 carbon atom, perhaps for containing the substituted-phenyl of 6 to 18 carbon atoms; And a), b) and any mixture c).

9. according to the detergent composition of claim 3, described composition also comprises bleaching catalyst in addition.

10. according to the detergent composition of claim 9, wherein said bleaching catalyst is selected from: Mn ₂ ^IV(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂Mn ₂ ^III(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂Mn ₄ ^IV(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂Mn ^IIIMn ₄ ^IV(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃, Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH ₃) ₃-(PF ₆); Co (2,2 '-bipyridyl amine) Cl ₂Two-(isosulfocyanate radical) bipyridyl amine close cobalt (II); Perchloric acid three (bipyridyl amine) closes cobalt (II); Co (2,2-bipyridyl amine) ₂-O ₂ClO ₄Perchloric acid is two-and (2,2 '-bipyridyl amine) close copper (II); Perchloric acid-three (two-2-pyridine amine) closes iron (II); Managanese gluconate; Mn (CF ₃SO ₃) ₂CO (NH ₃) ₅Cl; Double-core manganese with four-N-dentate and two-N-dentate ligand cooperate comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃And their mixture.

11. the application of the composition of one of claim 1-10 in contamination with wash base thing.