CN1352678A - Detergent compositions - Google Patents

Abstract

The present invention relates to detergent compositions which comprise low levels of inorganic sulphate filler salts, but instead high levels of carbonate salts and a system to counter balance the carbonate. This system comprises a floculating agent and a clay. Preferably only very low levels of an inorganic sulphate salt are present. Preferably, also other salts or silicates are present, including phosphates and/or zeolites.

Description

Detergent composition

Technical field

It is low to the present invention relates to mineral sulfates content, but the carbonate content height, and contains the detergent composition of the system of the carbonate effect that can contend with.

Background technology

Many detergent composition comprise filling salt, as sodium sulfate.Some prescription even this type of sulphate content are very high, and particularly low density product contains the vitriol above 30wt% sometimes.

Yet people wish to reduce the content of alkyl-sulphate in product, particularly consider from environmental angle.For substituting this mineral sulfates, can use other inorganic materials.In the middle of these materials some may be the washing assistant that comprises zeolite, phosphoric acid salt or silicate etc.Yet these become branch to increase the cost of preparation greatly.Having, in view of the reason of environment, is not all to accept at All Countries with the high-content phosphorus hydrochlorate as filler again.Other cheaper inorganic materials comprise for example inorganic carbonate etc., and it can be incorporated in the detergent formulation easily.Another advantage that they possess provides high alkalinity, and this is favourable for decontamination.

Yet the inventor finds that the preparation with high-content inorganic carbonate salt can cause hardening or a deadlock with the fabric of this series products washing.So the inventor finds that such product needed contains certain system to be offset the hardening of fabric or become stiff tendency.

Technical knownly have various compounds can provide than the softish fabric feeling.But they are not always compatible with high-content carbonate.

The inventor has now found that particularly some mineral clay can help to overcome by the caused problem of high-content carbonate.Also find when having this kind high-content carbonate, only still to be not enough to obtain desired flexibility, but also to need a kind of flocculation agent by clay.

Clay and flocculation agent are known on prior art to be used for increasing to fabric gentle, for example is described among the EP313146-A.But, before this and do not know that clay and flocculation agent can offset the shortcoming that high-content carbonate brings.

Summary of the invention

The present invention relates to a kind of detergent composition, it comprises

A) clay;

B) flocculation agent;

C) 18wt% at least, the preferred basic metal and/or the alkaline earth salt of 20wt% carbonic acid at least.

The invention still further relates to clay and flocculation agent and containing 18wt% or the more application in the composition of high basic metal and/or alkaline earth metal carbonate.

Preferred its sulphate content of said composition is low.

Said composition both can be used for machine washing and also can be used for hand washing, also comprised pre-treatment, immersion and conditioning.Carbonate

The employed carbonate of this paper comprises any carbonate, but particularly basic metal and/or alkaline earth metal carbonate, especially carbonate, supercarbonate and sesquicarbonate.Preferred salt comprises carbonate, sesquicarbonate and the supercarbonate of potassium, lithium, sodium etc., the carbonate of preferred again sodium and potassium in the middle of this.Be fit to supercarbonate used herein and comprise any alkali-metal supercarbonate, as lithium, sodium, potassium and so on, the supercarbonate of preferred sodium and potassium in the middle of this.Yet the selection of carbonate in the dried effervescent granule or supercarbonate or its mixture can be determined according to the desired pH of this particulate water medium of dissolving.For example, (for example be higher than pH9.5) when requiring water medium to have higher pH, then preferably only use the combination of carbonate or use carbonate and supercarbonate, wherein carbonate content should be higher than supercarbonate content.The inorganic base metal of the present composition and/or alkaline earth metal carbonate preferably comprise potassium, or the more preferably carbonate and/or the supercarbonate of sodium.Preferred described carbonate comprises yellow soda ash, optionally also contains sodium bicarbonate.

The inorganic carbonate here preferably exists with the content of the 20wt% at least of composition.Preferably with at least 23% or even 25%, or even 30wt%, preferably the highest about 60wt%, or more preferably the highest by 55%, or even the content of 50wt% exist.

They can be completely or partially add as scattered Powdered or particulate state composition, as with other detergent ingredients, add as the composite particles of other salt or tensio-active agent.In solid detergent composition of the present invention, they also can completely or partially be present in the detergent particles such as agglomerate or spray-dried granules.

In a kind of embodiment of the present invention, there is effervesce (foaming) source, preferred package contains organic acid such as carboxylic acid or amino acid, and carbonate.Under such situation, part or all of preferred carbonate and organic acid pre-mixing, thus exist with independent particulate component.

Carbonate can have any granularity.In one embodiment, especially be present in the particle rather than add fashionable when carbonate as independent compound, the volume median particle of carbonate is preferably between 5～375 μ m, in view of the above, preferably at least 60%, preferably at least 70%, or even at least 80%, or even at least 90% (volume) have granularity between 1～425 μ m.More preferably the volume median particle of carbonate particle is between 10～250, in view of the above, preferably at least 60%, or even at least 70%, or even at least 80%, or even at least 90% (volume) have granularity between 1～375 μ m; Or even preferably between the volume median particle of 10～200 μ m, in view of the above, preferably at least 60%, preferably at least 70%, or even at least 80%, or even at least 90% (volume) have granularity between 1～250 μ m.

Especially add fashionablely as separate constituent when carbonate, for example " do and add " or be blended in other detergent ingredients, then carbonate can have any granularity, comprise the granularity of stipulating above, yet preferred at least 200 μ m, or even 250 μ m, or even the volume average particle sizes of 300 μ m.

Preferably, optionally pursue the proper method again and select to obtain the carbonate of desired particle size by grinding than the volume particle size material.

Though may have percarbonate as SYNTHETIC OPTICAL WHITNER in the present composition, they are not included in the carbonate defined herein.Clay

The present composition comprises clay, and its content is preferably between 0.05%～40wt% of composition weight, more preferably 0.5%～30wt%, most preferably 2%～20wt%.Wanting clarifying is that this term clay is pressed implication herein, do not comprise sodium aluminium silicate zeolite builders compound, yet the latter can be included in the composition of the present invention as optional member but.

Clay: the weight ratio of flocculating polymer is preferably between 1000: 1～1: 1, more preferably 500: 1～1: 1, most preferably 300: 1～1: 1, or even more preferably 80: 1～10: 1, perhaps in some purposes even 60: 1～20: 1.

A kind of preferred clay is a wilkinite.It is highly preferred that terre verte, for example be disclosed in United States Patent (USP) 3,862,058,3,948,790,3,954,632 and 4,062, in 647 and European patent EP-A-299,575 and EP-A-313,146, all with the name application of Procter and Gamble company.

Term " terre verte " comprises that in this article aluminum oxide is present in the clay that constitutes in the lattice silicate, and magnesium oxide is present in the clay that constitutes in the lattice silicate.Typical terre verte compound comprises general formula Al ₂(Si ₂O ₅) ₂(OH) ₂.nH ₂The compound of O, and formula M g ₃(Si ₂O ₅) ₂(OH) ₂.nH ₂The compound of O.Terre verte tends to take extendible three-decker.

Suitable terre verte object lesson comprises those that are selected from following classification: polynite, hectorite, chromium polynite, nontronite, talcum powder (bentonite) and sauconite particularly have those of basic metal and alkaline-earth metal ions in crystalline network.The polynite of sodium or potassium is especially preferred.

Suitable terre verte, especially polynite have how tame manufacturer-supplied, comprise companies such as EnglishChina Clays, Laviosa, Georgia Kaolin and Colin Stewart Minerals.

Here employed clay preferably has 0.01 μ m～800 μ m, more preferably 1mm～400mm, the most preferably maximum particle size of 5mm～200mm.

The particle of clay mineral compound can be used as the agglomerated particle composition that also contains other detergent compounds and adds in the composition.Under situation about existing with this kind composition, " maximum particle size " of term clay mineral compound is meant the overall dimension of original clay mineral composition rather than the whole particle after the agglomeration.

Small cation as proton, sodium ion, potassium ion, magnesium ion and calcium ion, and some organic molecule, includes those of positively charged functional group, can replace in the terre verte crystalline network usually.Can select can 1 type of cationic clay of preferential adsorption, and this kind ability can be assessed by measuring relative ion-exchange capacity (capacity).Here the terre verte of Shi Yonging has the cation exchange capacity (CEC) of 50meq/100g (milligramequivalent/100 grams) at least usually.United States Patent (USP) 3,954,632 have described a kind of method of measuring cation exchange capacity (CEC).

The crystalline network of clay mineral compound by embodiment preferred, can comprise the cationic fabric softener that replaces.The clay of this kind replacement is referred to as " hydrophobic activation " clay usually, is for example sold by trade(brand)name Claytone EM by English China Clays International company.The typical amount of cationic fabric softener, by cationic fabric softener: the weight ratio of clay represents, between 1: 200～1: 10, preferred 1: 100～1: 20.Suitable cationic fabric softener comprises water-fast tertiary amine or two long-chain acid amides material, as is disclosed among GB-A-1 514 276 and the EP-B-0 011 340.

Parent organically clay also can here use.They have carried out hydrophobically modified, have replaced the clay that inorganic metal ion obtains by organic ion with known ion exchange on the prior art.This class clay mixes with organic solvent easily, and has the ability that absorbs organic solvent at interlayer.Suitable example or to can be used for close organic clay of the present invention be Bentone SD-1, SD-2 and SD-3 is supplied by Rheox (Highstown, New Jersey).

In highly preferred embodiment of the present invention, this clay with wetting agent and hydrophobic compound, preferred wax or oil, intimate mixture or the particle form formed as paraffin oil exist.Preferred wetting agent is an organic compound, comprises the dimer or the tripolymer of propylene glycol, ethylene glycol, glycol, most preferably glycerine.This particle is agglomerate preferably.In addition, this particle can be the capsule that is wrapped in clay that is formed by wax or wetting agent oily and that optionally add, is perhaps sealing wax or oil and wetting agent by clay.Preferably this particle comprises organic salt or silicon-dioxide or silicate.

Yet, in another embodiment of the present invention, clay preferably with a kind or kinds of surface promoting agent, optionally with washing assistant and optionally mixing with water, in this case, this mixture preferably carries out drying subsequently.Preferred this mixture is further processed by spray-drying process, thereby obtains to comprise the spray-dried granules of clay.

Preferably flocculation agent is also contained in particle argillaceous or the pill.

Height preferably clay and optionally also have flocculating polymer is present in the mixture of wax and structural agent.Be applicable to the example of argillaceous particulate structural agent of the present invention, comprise less hydrophobic solid particle, as water drain silica, and higher molecular weight hydrocarbon, as hydrocarbon rubbers.

Water drain silica is a silica dioxide granule, and particle surface has the hydrophobic grouping of chemical attachment.Can pass through to handle silica dioxide granule, and obtain the water drain silica of the organic group modification of siloxanes and so on reactive organosilicon compounds.Example is Cab-O-Sil TS720 and TS530, is supplied by Cabot company; And Aerosil 200, supply by Degussa company.

The hydrophobic pyrogenic silica of submicron, for example by Cabot company with those of trade(brand)name Cab-O-Sil TS720 and TS530 supply, be especially preferred.

High-molecular weight hydrocarbon comprises homopolymerization or the multipolymer of molecular weight between about 50,000～about ethene of 5,000,000, propylene and divinyl.Suitable example comprises the Ortheleium of E.I.Du Pont Company's supply ^The ethylene-propylene rubber(EPR) elastomerics.

Can be present in the particle argillaceous or can comprise (1) paraffin, as Merck 7150, Merck 7151, by E.Merck or the supply of Darmsteadt (Germany) company with the commercial examples of the suitable wax of this clay blended; Boler 1397, and Boler 1538, by Boler (Wayne, Pa) supply; And Ross 115/120 or 1365, supply by Frank D Ross company (Jersey city, New Jersey); (2) beeswax and (3) Japan wax are also supplied by Frank P Ross company (New Jersey); And (4) petrolatum wax, as PetrolatumPereco Snow or Petrolatum Penreco Ultima, supply by Penreco (Pennsylvania).

The blend of paraffin and petrolatum wax is preferably as coating material, in particular for liquid effective constituent, and the dressing of liquid nonionic surfactants for example.Paraffin is the material of highly crystalline.

The intimate mixture that can preferably comprise the sequestrant that hereinafter will mention in addition.Flocculation agent

The present composition can comprise the clay flocculating agent, and its amount is preferably between 0.005%～10% of composition weight, and more preferably 0.05%～5%, 0.1%～2wt% most preferably.

The clay flocculating agent is played with the clay compound particle aggregation in the washing soln together, thereby helps their effects on the fabric face of depositing to that is in the suds.Therefore, the requirement on this kind function is different from the clay dispersion immunomodulator compounds, and the latter is added in the laundry detergent composition normally in order to help clay soil to break away from from fabric, and they are dispersed in the washing soln.

Here preferred clay flocculating agent be molecular-weight average between 100,000～10,000,000, preferred 150,000～5,000,000, more preferably 200,000～2,000,000 organic polymer material.

Suitable organic polymer material comprises containing and is selected from oxyalkylene, especially the homopolymer or the multipolymer of oxyethane, acrylamide, vinylformic acid, vinyl alcohol, vinyl pyrrolidone and ethyleneimine monomeric unit.Homopolymer, particularly oxyethane comprise that also acrylamide and acrylic acid homopolymer are preferred.

With the European patent application EP-A-299 of Procter and Gamble company name application, 575 and EP-A-313,146, introduced that this paper is employed to preferably have the agent of organic polymer clay flocculating.

The inorganic clay flocculation agent here also is suitable for, and its exemplary comprises lime and alum.

This flocculation agent preferably is present in the washing composition basis particle such as detergent agglomerate, extrudate or spray-dried granules, wherein comprises a kind or kinds of surface promoting agent and washing assistant usually.Detergent composition

Cleaning compositions of the present invention is solid preferably, is forms such as particulate state, extrudate, laminar, strip or tablet.

Said composition can be used for washing automatically or hand washing.Also have, said composition can be made and be applicable to pre-treatment or immersion, perhaps is used for the usefulness of the fabric-conditioning that carries out later at main washing process.

The present composition also can comprise the additional detergent composition.The concrete person's character and the add-on thereof of these supplementary components will depend on the physical form of composition or composition, and the particular case of using its washing operation.

The present composition preferably comprises a kind or multiple additional detergent composition, be selected from tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleaching catalyst, alkaline system, additional washing assistant, comprise phosphorous hydrochlorate washing assistant, organic polyhydroxyl compound, enzyme, suds suppressor, soap, calcium soap, dispersion agent, dirt suspension and anti redeposition agent, stain remover, spices, white dyes, optical white and additional anticorrosive agent.

Preferred said composition comprises low levels mineral sulfates, particularly sodium sulfate, preferably is lower than 15%, or even be lower than 10wt%, or more preferably less than 8%, or even be lower than 5wt%.More preferably deliberately do not join the mineral sulfates in the detergent composition basically, be lower than 1% so said composition just comprises, or even be lower than 0.5%, or do not have mineral sulfates basically.

Highly preferred said composition comprises anion surfactant, preferred at least 5% anion surfactant, or even at least 10%, or even at least 15% anion surfactant.The preferred anionic tensio-active agent comprises at least a kind of line style or branching C ₉～C ₂₄, preferred C ₁₁～C ₁₄Alkylbenzene sulfonate.Have now found that anion surfactant has the performance better than other tensio-active agents when having high-content carbonate.Yet, also can comprise into nonionogenic tenside, so that for fabric provides extra flexibility, particularly in the hand washing prescription, they also can provide ramollescence to skin.Highly preferred the existence is equivalent to composition weight 3wt% at least, or even at least 5%, or even the 6wt% alkoxy-based non-ionic surface active agent, or preferred its mixture.Preferred mixture comprises the alkoxylate nonionic alcohol surfactant mixtures with different degree of alkoxylation, and preferred at least a kind of tensio-active agent has 3～5 degree of alkoxylation, and at least a kind have 5.5～11 degree of alkoxylation.

Preferably said composition comprises a kind of being selected from the middle of amorphous silicate, crystalline layered silicate, aluminosilicate or the phosphoric acid salt or multiple, and preferably at least 6%, or even 10wt% at least.Can be preferably at least 6%, or even at least 8%, or even 10wt% phosphoric acid salt at least.

Solid here or granular preparation can comprise water.In preferred embodiments, especially when having spray-dried granules in the washing composition, can there be 5wt% at least, or even the water of 7wt% at least.

Highly preferred supplementary component is a soil release polymer, particularly polyester or glycan or derivatives thereof, cellulose-based polymkeric substance comprises carboxymethyl cellulose, ether of cellulose or ester, or the Mierocrystalline cellulose of acid amides modification, the spices of capsule envelope, the effervesce source is preferably based on carbonate and sour compound, particularly citric acid, oxysuccinic acid or toxilic acid, phosphonate washing assistant, dye transfer inhibitor, and processing aid are as hydrotropic agent.These compositions will be done more detailed description in this article.

Can be highly preferably add the carboxymethyl cellulose compound in composition, its add-on is at least 0.5% of a composition weight, or even 0.75%, or even 1wt%, in addition, can add glycan in addition again, its consumption is 0.5% of composition at least, or even 0.75%, or even 1wt%.

Preferably said composition comprises cationic softener.Highly preferred water-insoluble quaternary ammonium compound is to have 2 C ₁₂～C ₂₄Alkyl or alkenyl chain, optionally replace to go up such as-OH ,-O-,-CONH-, COO-those of functional group.

Substantially water-fast as everyone knows quaternary ammonium compound such as following general formula,

R ₁R ₂R ₃R ₄NX is R wherein ₁And R ₂Represent the alkyl of about 12～about 24 carbon atoms; R ₃And R ₄Represent the alkyl of 1～about 4 carbon atoms; X is a negatively charged ion, is preferably selected from groups such as halide-ions, methylsulfate and ethyl sulphate.The exemplary of these quaternary ammonium softeners comprises Varisoft DHT; The Methylsulfate of two tallow base Dimethyl Ammonium; Two (hexadecyl) alkyl dimethyl ammonium chloride; Two (hydrogenated tallow alkyl) alkyl dimethyl ammonium chloride; Two (octadecyl) alkyl dimethyl ammonium chloride; Two (eicosyl) alkyl dimethyl ammonium chloride; Two (docosyl) alkyl dimethyl ammonium chloride; The Methylsulfate of two (hydrogenated-tallow group) Dimethyl Ammonium; Two (hexadecyl) diethyl ammonium chloride; Two (coconut alkyl) alkyl dimethyl ammonium chloride.The Methylsulfate of Varisoft DHT, two (hydrogenated tallow alkyl) alkyl dimethyl ammonium chloride, two (coconut alkyl) Dimethyl Ammonium is preferred.

Here the tetrahydroglyoxaline fabric sofetening composition in the suitable United States Patent (USP) 4127489 is in addition received the document for referencial use at this.Term " fabric " softening agent used herein " be not included in 20 ℃, pH near the cationic detersive active material of solubleness in about 6 the water greater than 10g/l.

Especially preferred is two tallow base methylamines, is supplied by AKZO NV with trade(brand)name Armeen M2HT on the market; With Genamin SH301 trade(brand)name, sell by FARBWERKE HOECHST; And, supply by CECA company with commodity Noram M2SH.Tensio-active agent

The present composition preferably comprises a kind or kinds of surface promoting agent, is selected from negatively charged ion, nonionic, positively charged ion, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics and composition thereof.

Inventory about the chemical species of typical negatively charged ion, nonionic, both sexes and zwitter-ion classification and these tensio-active agents can be seen in United States Patent (USP) 3,929 678 (1975-12-30 authorizes Laughlin and Heuring).Other examples can be seen in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch chief editor).The inventory of suitable cationic surfactants is at United States Patent (USP) 4,259, provides (1981-03-31 authorizes Murphy) in 217.

If present, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics common and a kind or multiple negatively charged ion and/or nonionic surfactant combinations use.Anion surfactant

The present composition preferably comprises additional anion surfactant.Basically any anion surfactant that is used for soil-removing action all can be included in this detergent composition, can comprise anion sulfate acid, sulfonic acid, carboxylic acid and sarkosine salt (comprise for example ammonium salt of sodium, potassium, ammonium and replacement, as single-, two-and the salt of trolamine) tensio-active agent.Anion sulfate and sulfosalt surfactant are preferred.

The tensio-active agent that highly preferably comprises sulfonate and vitriol, preferred line style described herein or branched-alkyl benzene sulfonate and alkyl ethoxy sulfate preferably are used in combination with cats product described herein.

Other anion surfactants comprise isethionate; for example acyl-hydroxyethyl sulfonate, N-acyl taurine salt; the fatty acid amide of methylamino esilate, alkyl succinate and sulfosuccinate, the monoesters of sulfosuccinate (especially saturated or unsaturated C ₁₂～C ₁₈Monoesters), the diester of sulfosuccinate (particularly saturated and unsaturated C ₆～C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite, and be present in the butter or by its deutero-resinous acid and hydrogenated resin acid.The anion sulfate acid salt surfactant

The primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oleoyl glycerine vitriol, alkylphenol oxygen Vinyl Ether vitriol, the C that are fit to anion sulfate surfactant package vinculum type used herein or branching ₅～C ₁₇Acyl group-N-(C ₁～C ₄Alkyl) and-N-(C ₁～C ₂Hydroxyalkyl) glucosamine sulfate, and the vitriol of alkyl polysaccharide, for example vitriol of alkylpolyglycosides (referring to the compound of nonionic, non-sulfuric acidization here).

The preferred alkyl sulfate surfactant is selected from line style or branching uncle C ₁₀～C ₁₈Alkyl-sulphate, more preferably C ₁₁～C ₁₅Branched chain alkyl vitriol and C ₁₂～C ₁₄The linear chain alkyl-sulphate.

Alkyl ethoxy sulfate surfactant is preferably selected from per molecule carries out ethoxylation with 0.5～20mol oxyethane C ₁₀～C ₁₈Alkyl-sulphate.More preferably this alkyl ethoxy sulfate surfactant be per molecule with 0.5～7, preferred 1～5mol oxyethane carries out the C of ethoxylation ₁₁～C ₁₈, C most preferably ₁₁～C ₁₅Alkyl-sulphate.

The present invention especially preferably adopts the mixture of this preferred alkyl-sulphate and/or sulfonate and alkyl ethoxy sulfate surfactant.This type of mixture is disclosed among the PCT patent application WO93/18124.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 alkyl benzene sulfonate salt, alkyl ester sulfonate, C ₆～C ₂₂Uncle or secondary alkyl sulfonate, C ₆～C ₂₄Sulfonated alkene, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol sulfonate, and their any mixture.The anionic carboxylic acid salt surfactant

Suitable anionic carboxylate tensio-active agent comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate tensio-active agent, and soap (" alkyl carboxyl class "), some secondary soap particularly described herein.

Suitable alkyl ethoxy carboxylate comprises general formula R O (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Those, wherein R is C ₆～C ₁₈Alkyl, x is between 0～10; The distribution of ethoxylate is such, and promptly by weight, this quantity of material of x=0 is less than 20%; And M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises general formula R O-(CHR ₁-CHR ₂-O)-R ₃Those, wherein R is C ₆～C ₁₈Alkyl, x be between 1～25, R ₁And R ₂Be selected from hydrogen, methyl acid group, succsinic acid group, hydroxy succinic acid group and composition thereof, R ₃Be selected from hydrogen, replacement or unsubstituted 1～8 carbon atom hydrocarbon, and their mixture.

Suitable soap class tensio-active agent comprises and contains the unitary secondary soap surfactant of the carboxyl that is connected on the secondary carbon(atom).Secondary soap surfactant used herein is to be selected from following water-soluble cpds: 2-methyl isophthalic acid-undecanoic 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.

Some soap class also can be used as suds suppressor and adds.The basic metal sarcosinate surfactant

Other suitable anion surfactants are general formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅～C ₁₇Line style or branched-alkyl or alkenyl, R ¹Be C ₁～C ₄Alkyl, M are alkalimetal ions.Preferred example is the nutmeg base and the oleoyl methyl sarcosinate of sodium-salt form.Alkoxy-based non-ionic surface active agent

Basically any alkoxy-based non-ionic surface active agent here all is fit to.Ethoxylation and propoxylation nonionogenic tenside are preferred.

The preferred alkoxylated tensio-active agent can be selected from following all kinds of: the condensation product of the nonionic condenses of alkylphenol, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, nonionic ethoxylate/propoxylated glycerine and propylene glycol, and the condensation product of nonionic ethoxylate and propylene oxide/quadrol affixture.Nonionic alcohol alcoxylates tensio-active agent

Fatty alcohol and 1～25mol oxyalkylene particularly with the condensation product of oxyethane and/or propylene oxide, are fit to the present invention and use.The alkyl chain of this fatty alcohol can be straight chain or branching, uncle or secondary alkyl group, and contain 6～22 carbon atoms usually.Especially preferred alkyl contains the every mol of alcohol of 8～20 carbon atoms and the condensation product of 2～10mol oxyethane.The nonionic polyhydroxy fatty acid amide surfactant

The polyhydroxy fatty acid amide that the present invention is fit to use is to have formula R ²CONR ¹Those of Z, wherein R ¹Be hydrogen, C ₁～C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its 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 C ₉～C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁～C ₁₇Alkyl or alkenyl, or its mixture; Z is a polyhydroxy alkyl, has to bring to few 3 line style hydrocarbyl chains that directly are connected the hydroxyl on the chain, or its alkoxy derivative (preferred ethoxylation or propenoxylated).Z preferably is reduced and deutero-in the reductive amination reaction by sugar; More preferably Z is a glycidyl.The nonionic fatty acid amide surfactant

The suitable fatty acids acidamide surfactant comprises general formula R ⁶CON (R ⁷) ₂Those, R wherein ⁶Be 7～21, the alkyl of preferred 9～17 carbon atoms, each R ⁷Be selected from hydrogen, C ₁～C ₄Alkyl, C ₁～C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein x is between 1～3.Nonionic alkyl polysaccharide tensio-active agent

Be fit to the alkyl polysaccharide that the present invention uses and be described in United States Patent (USP) 4,565, in 647 (1986-01-21 authorizes Llenado), have the hydrophobic grouping of 6～30 carbon atoms and a kind of glycan as containing the poly-glycosides hydrophilic radical of 1.3～10 sugar units.

Preferred alkylpolyglycosides such as following general formula:

R ²O (C _nH ₂NO) t (glycosyl) _xR wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein alkyl comprises 10～18 carbon atoms; N is 2 or 3; T is between 0～10, and x is between 1.3～8.This glycosyl is preferably derived by glucose.Amphoterics

The amphoterics that is fit to the present invention's use comprises amine oxide surfactant and alkyl both sexes carboxylic acid.

Suitable amine oxide comprises general formula R ³(OR ⁴) _xNO (R ⁵) ₂Compound, R wherein ³Be selected from alkyl, hydroxyalkyl, amido propyl group and alkyl phenyl, perhaps their mixture wherein comprises 8～26 carbon atoms; R ⁴Be the alkylidene group or the hydroxyl alkylidene group of 2～3 carbon atoms, perhaps its mixture; X is 0～5, preferred 0～3; Each R ⁵Be alkyl or the hydroxyalkyl that comprises 1～3 carbon atom, perhaps contain the polyethylene oxide base of 1～3 ethylene oxide group.Preferred C ₁₀～C ₁₈Alkyl-dimethyl amine oxide, and C ₁₀～C ₁₈Amidoalkyl diformazan amine oxide.

A kind of example of suitable alkyl both sexes dicarboxylic acid is that Miranol (TM) C2M Conc. is made by Miranol company (Dayton, New Jersey).Zwitterionics

Zwitterionics also can join in the detergent composition of the present invention.These tensio-active agents can broadly be described as the derivative of derivative, the heterocycle second month in a season and the tertiary amine of secondary and tertiary amine, the perhaps derivative of quaternary ammonium, quaternary phosphonium or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the typical zwitterionicss that the present invention uses.

Suitable trimethyl-glycine is general formula R (R ') ₂N ⁺R ²COO ^-Compound, wherein R is C ₆～C ₁₈Alkyl, each R ¹The typical case be C ₁～C ₃Alkyl, R ²Be C ₁～C ₅Alkyl.Preferred trimethyl-glycine is C ₁₂～C ₁₈Dimethyl-caproic acid ammonium and C _10～18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound betaine tensio-active agent here also is fit to use.Cats product

The cats product that is fit to use in the washing composition of the present invention comprises quaternary ammonium surfactant.Preferred this quaternary ammonium surfactant is single C ₆-C ₁₆, preferred C ₆～C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein remaining N price is replaced by groups such as methyl, hydroxyethyl or hydroxypropyls.Preferred list-alkoxylate in addition and two-oxyalkylated amine tensio-active agent.

Another kind ofly be applicable to that the cats product in this detergent composition or its composition is the cationic ester tensio-active agent.This cationic ester tensio-active agent preferably water dispersible, the compound of surfactant properties is arranged, comprise at least 1 ester (that is ,-COO-) key and at least 1 positively charged group.

Suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, for example is disclosed in United States Patent (USP) 4228042,4239660 and 4260529.

In the preferred version, in the surfactant molecule between this ester bond and the positively charged group across one by containing at least 3 atoms (i.e. 3 atom chain lengths), preferred 3～8 atoms, more preferably 3～5 atoms, the most preferably spacer formed of the chain of 3 atoms.The atom that constitutes spacer is selected from carbon, nitrogen and Sauerstoffatom and mixes atom arbitrarily, and condition is that any one nitrogen or Sauerstoffatom can only link to each other with the carbon atom in this chain in the described chain.Therefore, such as-O-O-(that is, superoxide) ,-N-N-and-spacer of N-O-key and so on should foreclose, and such as-CH ₂-O-CH ₂-and-CH ₂-NH-CH ₂The spacer of-key is then included.In a kind of preferred version, the spacer chain only comprises carbon atom, and most preferred chain is a hydrocarbyl chain.Cation mono alkoxylated amines tensio-active agent

Here, it is highly preferred that cation mono alkoxylated amines tensio-active agent, preferred formula I: R wherein ¹Be alkyl or alkenyl part, comprise about 6～about 18 carbon atoms, preferred 6～about 16 carbon atoms, most preferably from about 6～about 14 carbon atoms; R ²And R ³Be the alkyl of 1～about 3 carbon atoms independently of one another, preferable methyl, most preferably R ²With R ³It all is methyl; R ⁴Be selected from hydrogen (preferably), methyl and ethyl; X ^-Be negatively charged ion such as chlorine root, bromine root, methylsulfate, sulfate radical or like that, so that electric neutrality to be provided; A is an alkoxyl group, especially oxyethyl group, propoxy-or butoxy; P is 0～about 30, preferred 2～about 15, and most preferably 2～about 8.

ApR among the preferred formula I ⁴P=1 in the group, and ApR ⁴Be the hydroxyalkyl that is not more than 6 carbon atoms, therefore should-being separated by between OH group and the quaternary nitrogen atoms is no more than 3 carbon atoms.Especially preferred ApR ⁴Group is-CH ₂CH ₂OH ,-CH ₂CH ₂CH ₂OH ,-CH ₂CH (CH ₃) OH and-CH (CH ₃) CH ₂OH, wherein-CH ₂CH ₂OH is especially preferred.The line style R of preferred 8～14 carbon atoms ¹Group.

The highly preferred cation mono alkoxylated amines of another kind of this paper tensio-active agent is following general formula, R wherein ¹Be C ₁₀～C ₁₈Alkyl and composition thereof, especially C ₁₀～C ₁₄Alkyl, preferred C ₁₀And C ₁₂Alkyl, X are any negatively charged ion that charge balance is provided easily, preferred chlorine root and bromine root.

The compound that it should be noted that the above-mentioned type comprises contained oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy, isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃O] unit (i-Pr) or positive propoxy unit (Pr) substitute, perhaps by EO and/or Pr and/or the unitary mixture of i-Pr institute alternate situation.

The consumption of this cation mono alkoxylated amines tensio-active agent in detergent composition of the present invention be preferably between 0.1%～20% of composition weight, and more preferably 0.2%～7%, 0.3%～3.0wt% most preferably.Positively charged ion bis-alkoxy amine tensio-active agent

This positively charged ion bis-alkoxy amine tensio-active agent preferred formula II:

R wherein ¹Be 8～18 carbon atoms, preferred 10～about 16 carbon atoms, the most preferably from about alkyl of 10～about 14 carbon atoms or alkenyl part; R ²Be the alkyl of 1～3 carbon atom, preferable methyl; R ³And R ⁴Can change independently, be selected from hydrogen (preferably), methyl and ethyl; X ^-Be negatively charged ion, be enough to provide electroneutral negatively charged ion as chlorine root, bromine root, methylsulfate, sulfate radical etc.A and A ' can change independently, are selected from C separately ₁～C ₄Alkoxyl group, especially oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and composition thereof; P is 1～about 30, preferred 1～about 4, and q is 1～about 30, preferred 1～about 4, most preferably p and q are 1.

Here highly preferred positively charged ion bis-alkoxy amine tensio-active agent such as the following general formula that uses,

R wherein ¹Be C ₁₀～C ₁₈Alkyl and composition thereof, preferred C ₁₀, C ₁₂, C ₁₄Alkyl and composition thereof.X is any negatively charged ion that makes things convenient for that charge balance is provided, preferred chlorine root.Connect with the positively charged ion bis-alkoxy amine formula that provides above and to see, preferred compound is R ¹By (coconut) C ₁₂～C ₁₄The fatty acid derived of moieties, R ²Be methyl, and ApR ³And A ' qR ⁴Each is monosubstituted ethoxy naturally.

Spendable other positively charged ion bis-alkoxy amine tensio-active agent of the present invention comprises the compound of following general formula:

R wherein ₁Be C ₁₀～C ₁₈Alkyl, preferred C ₁₀～C ₁₄Alkyl, independently p be 1～about 3, q is 1～about 3, R ₂Be C ₁～C ₃Alkyl, preferable methyl, X is a negatively charged ion, especially chlorine root or bromine root.

Other compounds of the above-mentioned type comprise contained oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃) O] unit (i-Pr) or positive propoxy unit (Pr) substitute, perhaps by EO and/or Pr and/or i-Pr mixed cell institute alternate compound.The perhydrate SYNTHETIC OPTICAL WHITNER

A kind of preferred supplementary component of said composition is the perhydrate SYNTHETIC OPTICAL WHITNER, for example metal perborate, metal percarbonate, especially sodium salt.Perborate is singly-or tetrahydrate.The structural formula of SPC-D is equivalent to 2Na ₂CO ₃.3H ₂O ₂, on market, sell as crystalline solid.

Cross sulfate mono potassium, and sodium salt, be the optional inorganic perhydrate salts that another kind can be used for detergent composition of the present invention.The organic peroxide acid bleach system

A preferred feature of said composition is a kind of organic peroxide acid bleach system.In a kind of embodiment preferred, this bleach system comprises hydrogen peroxide cource and organic peroxide acid bleach precursor compound.React on the spot by this precursor and hydrogen peroxide cource, generate organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER, perborate bleach for example of the present invention.In another kind of preferred embodiment, the organic peroxide acid that generates is in advance directly joined in the composition.The composition that the mixture that contains hydrogen peroxide cource and organic peroxy acid precursor combines and forms with pregenerated organic peroxide acid again is also at the row of consideration.Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that can generate peroxy acid with the reaction of hydrogen peroxide generation peroxidation hydrogenolysis.Generally speaking, peroxyacid bleach precursor can be expressed as follows,

Wherein L is a leavings group, and X can be any functional group basically, and like this, the structure of the peroxy acid that generates after reacting through the peroxidation hydrogenolysis will be:

The preferable amount of peroxyacid bleach precursor compound is between 0.5%～20wt% of detergent composition weight, more preferably 1%～15wt%, most preferably 1.5%～10wt%.

Suitable peroxyacid bleach precursor compound is comprising one or more N-or O-carboxyl groups in typical case, and this precursor can be selected from diversified type.Suitable type comprises acid anhydrides, ester, imide, lactan, and the acylated derivatives of imidazoles and oxime.The example that belongs to the useful materials of these types is described among the GB-A-1586789.Suitable ester be disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.Leavings group

Leavings group to call the L group in the following text, must have sufficient activity, takes place so that the peroxidation hydrogenolysis is reflected in the Best Times scope (for example washing the phase).Yet if the L hyperergy, this activator will be difficult to stablize, so be not suitable in the bleaching composition.

Preferred L group is selected from down array structure,

And mixed base, wherein R ¹Be alkyl, aryl or the alkylaryl group of 1～14 carbon atom, R ³Be the alkyl chain of 1～8 carbon atom, R ⁴Be hydrogen or R ³, Y is hydrogen or solubilizing group.R ¹, R ³And R ⁴In the middle of any one can replace any basically functional group, for example comprise alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl, acid amides and groups such as ammonium or alkylammonium.

Preferred solubilizing group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, most preferably-SO ₃ ^-M ⁺And-CO ₂ ^-M ⁺, R wherein ³It is the alkyl chain of 1～4 carbon atom, M provides deliquescent positively charged ion for this bleach-activating agent, X provides deliquescent negatively charged ion for this bleach-activating agent, M is basic metal, ammonium or replaces ammonium cation, the most preferred with sodium and potassium, X is halide-ions, hydroxide radical, methylsulfate or acetic acid anion.Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor generates percarboxylic acids later on through the peroxidation hydrogenolysis.Preferred this type precursor is providing peracetic acid later on through the peroxidation hydrogenolysis.

Preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, N ¹, N ¹Tetrem acidylate Alkylenediamine, wherein alkylidene group comprises 1～6 carbon atom, and especially its alkylidene group comprises those compounds of 1,2 and 6 carbon atom.Tetra acetyl ethylene diamine (TAED) is especially preferred.TAED preferably is not present in the agglomerated particle of the present invention, comprises in this particulate detergent composition but preferably be present in.

Other preferred alkyl peroxycarboxylic acid precursors comprise 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (iso-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and pentacetylglucose.The alkyl peroxy acids precursor that acid amides replaces

The alkyl peroxy acids precursor compound that is fit to acid amides replacement used herein comprises those of following general formula:

R wherein ¹Be the alkyl of 1～14 carbon atom, R ²Be the alkylidene group of 1～14 carbon atom, R ⁵Be the alkyl of hydrogen or 1～10 carbon atom, L can be any leavings group basically.The bleach activating immunomodulator compounds that the acid amides of this type replaces is described among the EP-A-0170386.Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid later in the peroxidation hydrogenolysis.Suitable O-acidylate peroxybenzoic acid precursors compound comprises and replacing and unsubstituted benzoyloxy benzene sulfonate; and the benzoylation product of sorbyl alcohol, glucose; and the product of all carbohydrates and benzozlating agent; and those of imide-type, comprise the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzoglyoxaline.The peroxybenzoic acid precursors that contains the N-acyl group that other are useful comprises N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.Pregenerated organic peroxide acid

This organic peroxide acid bleach system, except that organic peroxide acid bleach precursor compound, also can comprise pregenerated hydrophobicity organic peroxide acid, or with its alternative organic peroxide acid bleach precursor, its typical amounts is between 0.05%～20wt% of composition weight, more preferably 1%～10wt%.

The compound that the acid amides that a kind of hydrophobic organic peroxy acid compound of preferred type is following general formula replaces: R wherein ¹Be the aryl or aralkyl of 1～14 carbon atom, R ²Be alkylidene group, arylidene and the alkarylene of 1～14 carbon atom, R ⁵Be alkyl, aryl or the alkaryl of hydrogen or 1～10 carbon atom.R ¹Preferably comprise about 6～12 carbon atoms.R ²Preferably comprise about 4～8 carbon atoms, R ¹Can be straight chain or branched-alkyl, the aryl of replacement or alkaryl comprise side chain, substituting group or the two, and can for example comprise tallow from synthetic source or natural source.For R ², also allowing is similar structural variant.R ²Can comprise alkyl, aryl, wherein said R ²Also can comprise halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferably hydrogen or methyl.R ¹And R ⁵Should comprise and be no more than 18 carbon atoms altogether.The bleach activating immunomodulator compounds that this type acid amides replaces is described among the EP-A-0170386.The suitable example of examples of such additives comprises (6-is hot amino)-6-oxo-caproic acid, (6-amino in the ninth of the ten Heavenly Stems)-6-oxo-caproic acid, (6-amino in the last of the ten Heavenly stems)-6-oxo-caproic acid, monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxygen base Perbutyric Acid and diperoxy dodecanedioic acid.This type of SYNTHETIC OPTICAL WHITNER is disclosed in United States Patent (USP) 4,483, and 781, among United States Patent (USP) 4,634,551, EP 0,133,354, United States Patent (USP) 4,412,934 and the EP 0,170,386.The preferred hydrophobic pre-generation peroxy acid bleach compound of the present invention is single nonanoyl amidoperoxycarboxylic acid.

Other suitable organic peroxide acids comprise the diperoxy chain docosandioic acid that has more than 7 carbon atoms, for example diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.

Other suitable organic peroxide acids comprise the diamino peroxy acid, are disclosed among the WO 95/03275, have following general formula:

Wherein: R is selected from C ₁～C ₁₂Alkylidene group, C ₅～C ₁₂Cycloalkylidene, C ₆～C ₁₂The combination of arylidene and these groups;

R ₁And R ₂Be independently selected from H, C ₁～C ₁₆Alkyl and C ₆～C ₁₂Aryl, and energy and R ³Constitute C together with 2 nitrogen-atoms ₃～C ₁₂The group of ring; R ³Be selected from C ₁～C ₁₂Alkylidene group, C ₅～C ₁₂Cycloalkylidene and C ₆～C ₁₂Arylidene; Each satisfies the integer that makes sum of the two equal 1 naturally n and n '; M and m ' each to satisfy sum of the two naturally be 1 integer; And

M is selected from H, basic metal, alkaline-earth metal, ammonium, alkanol ammonium cation and free radical, and combination.

Other suitable organic peroxide acids comprise disclosed amido peroxy acid among the WO 95/16673, have following general formula:

X-Ar-CO-NY-R (Z)-CO-OOH wherein X represents hydrogen or compatible substituting group, and Ar is an aryl, and R represents (CH ₂) _n, n=2 or 3 wherein, Y and Z represent the substituting group that is selected from hydrogen or alkyl or aryl or alkaryl independently of one another, and perhaps representative has replaced compatible substituent aryl, and condition is as if n=3, and then Y and Z are not hydrogen one of at least.Substituent X on the benzene nucleus is hydrogen preferably, or a position or para-orienting group, is selected from halogen, is typically the chlorine atom, perhaps certain other non-release type, glitch-free chemical species, for example alkyl, be maximum C6 easily, for example methyl, ethyl or propyl group.In addition, X can represent the second amido-percarboxylic acids substituting group of following general formula:

-CO-NY-R (Z)-CO-OOH wherein R, Y, Z and n with top definition.

MOOC-R ¹CO-NR ²-R ³-NR ⁴-CO-R ⁵COOOM is R wherein ¹Be selected from C ₁～C ₁₂Alkylidene group, C ₅～C ₁₂Cycloalkylidene, C ₆～C ₁₂Arylidene, and moiety combinations; The highly preferred phthalyl amido peroxyacid (PAP) of R.Bleaching catalyst

Said composition can comprise the bleaching catalyst that contains transition metal.

A kind of bleaching catalyst of adequate types is to include the catalyst system that limits the active transition-metal cation of bleach catalyst, for example contain positively charged ions such as copper, iron or manganese, also contain seldom or do not have an active assistant metal positively charged ion of bleach catalyst, for example zinc or aluminium cations, and the sequestrant that catalyzer and assistant metal positively charged ion is had the regulation stability constant, ethylenediamine tetraacetic acid (EDTA) particularly, ethylenediamine tetraacetic (methylene phosphonic acid) and water-soluble salt thereof.This type of catalyzer is disclosed in United States Patent (USP) 4,430, in 243.

The other types bleaching catalyst comprises and is disclosed in United States Patent (USP) 5,246,621 and United States Patent (USP) 5,244,594 in the manganese base complex.The preferred example of this type of catalyzer comprises Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-O) 1 (u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃, and their mixture.Other example then is described in the European patent application publication No. 549,272.Other are fit to part used herein and comprise 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and composition thereof.

Following useful bleaching catalyst also can select to be used for the present invention rightly.The example of relevant suitable bleaching catalyst can be referring to United States Patent (USP) 4,246, and 612 and United States Patent (USP) 5,227,084.Also can be referring to United States Patent (USP) 5,194,416, the document discloses a kind of monokaryon manganese (IV) complex compound, for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃-(PF ₆).

Another class bleaching catalyst, as be disclosed in United States Patent (USP) 5,114 in 606, is a manganese (III) and/or (IV) and the water soluble complex that forms of certain non-carboxylate polyol part with at least 3 continuous C-OH groups.Preferred part comprises sorbyl alcohol, iditol, melampyrum, mannitol, Xylitol, arabitol, adonitol, meso tetrahydroxybutane, meso-inositol, lactose, and their mixture.

United States Patent (USP) 5,114,611 disclose a kind of bleaching catalyst, and it comprises transition metal, comprises the complex compound of Mn, Co, Fe or Cu and a kind of non-(greatly)-ring-type part.Described part has following general formula: R wherein ¹, R ², R ³And R ⁴Be selected from the alkyl and the aryl of hydrogen, replacement separately, so that each R ¹-N=C-R ²And R ³-C=N-R ⁴Constitute 5 or 6 yuan of rings, described ring also can further be substituted.B is a bridged group, is selected from O, S, CR ⁵R ⁶, NR ⁷And C=O, wherein R ⁵, R ⁶And R ⁷Can each hydrogen, alkyl or aryl naturally, comprise replacement or unsubstituted group.Preferred part comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole lopps.Optionally described ring can replace the substituting group such as alkyl, aryl, alkoxyl group, halogenide and nitro.Especially preferred part 2,2 '-two pyridyl amine.Preferred bleaching catalyst comprise Co, Cu, Mn, Fe ,-two pyridyl methane and-two pyridyl amine complexes.Highly preferred catalyzer comprises Co (2,2 '-two pyridyl amine) Cl ₂, the two pyridyl amine-cobalts of two (isothiocyanatos) (II), three (two pyridyl) amine-cobalts (II) perchlorate, Co (2, the two pyridyl amine of 2-) ₂O ₂ClO ₄, two (2,2 '-two pyridyl amine) copper (II) perchlorate, three (two-2-pyridyl amine) iron (II) perchlorate, and their mixture.

Other examples comprise with the double-core Mn of four-N-dentate and two-N-dentate part complexing, comprise N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Other bleaching catalysts are described in for example European patent application publication No. 408,131 (cobalt complex catalysts), European patent application publication No. 384,503 and 306,089 (catalysis of metalloporphyrin agent), United States Patent (USP) 4,728,455 (manganese/polygamy position ylidene ligands catalyzer), United States Patent (USP) 4,711,748 and European patent application publication No. 224,952 (being absorbed in the manganese on the aluminosilicate catalyzer), United States Patent (USP) 4,601,845 (manganese on the aluminosilicate carrier and zinc or magnesium salts), United States Patent (USP) 4,626,373 (manganese/ligand catalysts), United States Patent (USP) 4,119,557 (iron complex catalyzer), German patent specification 2,054,019 (cobalt sequestrant catalyzer), Canadian Patent 866,191 (salt that contains transition metal), United States Patent (USP) 4,430,243 (sequestrant and manganese positively charged ion and on-catalytic metallic cations) and United States Patent (USP) 4,728,455 (managanese gluconate catalyzer).

This bleaching catalyst is being used in the present composition and the method with catalytically effective amount in typical case.So-called " catalytically effective amount " is meant such amount, no matter promptly adopt which kind of contrast experiment's condition, it all is enough to impel bleaching, and a kind or the multiple color spot of desiring to remove are removed from target substrate.This test conditions will and change along with the type of used washing plant and user's custom.Some user selects the very hot water of use, and other then use warm water, or even cold water carry out laundry operations.Certainly, the catalytic performance of bleaching catalyst will be subjected to the influence of this class factor, and therefore, the consumption of bleaching catalyst in full formula washing and bleaching composition can be done suitable adjusting.Illustrate as actual, rather than as restriction, the present composition and method can approximately be at least per active bleaching catalyst of 1/10000000th by the concentration of regulating to be provided in the aqueous cleaning solution, and about 1ppm～about 200ppm preferably is provided.As to further the illustrating of this point, about 3 micromole's Mn catalysts under European wash conditions, adopt perborate and bleach precursor, are effective under 40 ℃, the condition of pH10.Under American wash conditions, reach identical effect may need to improve 3～5 times of this concentration.The water soluble detergency promoter compound

Present composition preferred package contains water-soluble washing-aid compound, and its typical content in detergent composition is between 1%～80wt% of composition weight, preferred 10%～60wt%, most preferably 15%～40wt%.

Detergent composition of the present invention preferably comprises phosphatic washing assistant material, and it is measured preferably between 0.5%～60%, and more preferably 5%～50%, more preferably 8%～40%.

This phosphatic washing assistant material preferably comprises tetrasodium pyrophosphate, or even more preferably anhydrous sodium tripolyphosphate.

Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or its sour form, all-or copolymerization poly carboxylic acid or its salt, wherein poly carboxylic acid comprises at least 2 carboxyls, is separated by each other to be no more than 2 carbon atoms, borate, and above-mentioned any mixture.

This carboxylate or many carboxylates washing assistant can be haplotype or polymer-type, and but, the many carboxylates of monomer are normally preferred, because consider from cost and aspect of performance.

The suitable carboxylate that contains 1 carboxyl comprises the water-soluble salt of lactic acid and oxyacetic acid, and ether derivant.The many carboxylates that contain 2 carboxyls comprise the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid etc. and ether carboxylate and sulfinyl carboxylate.The many carboxylates or its acid, particularly water-soluble citrate, equisetic acid and the citraconate that contain 3 carboxyls, and even succinic acid derivative, as English Patent 1,379, carboxymethyl oxygen base succinate, the English Patent 1 described in 241, the lactyl succinate of describing in 389,732, and the aminosuccinic acid salt of describing in Holland's application 7205873, and oxygen Quito carboxylate material, for example English Patent 1,387, the 2-oxa-of describing in 447-1,1,3-propane three carboxylates.The most preferred poly carboxylic acid that contains 3 carboxyls is a citric acid, and preferably with 0.1～15% of composition weight, more preferably the content of 0.5%～8wt% exists.

The many carboxylates that contain 4 carboxyls comprise and are disclosed in English Patent 1,261, the oxygen di-succinate in 829; 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent many carboxylates of sulfo group and comprise English Patent 1,398,421 and 1,398,422 so that United States Patent (USP) 3,936,448 in disclosed sulfosuccinic acid derivative, and sulfonation, the pyrolytic Citrate trianion described in the English Patent 1,439,000.Preferred many carboxylates are hydroxyl carboxylate, the especially Citrate trianions that per molecule contains maximum 3 carboxyls.

The mixture of the parent acid of monomer or oligomeric many carboxylates sequestrant or itself and its salt, for example citric acid or Citrate trianion/citric acid mixture also are considered as useful washing assistant composition.

The borate washing assistant, and contain the washing assistant that generates borate material, promptly under washing composition storage or wash conditions, can produce boratory washing assistant, here also be useful water soluble detergency promoter.

The suitable example of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, the pyrophosphate salt of sodium, potassium and ammonium, the pyrophosphate salt of sodium and potassium and ammonium, the partially poly-/phosphoric acid salt of the orthophosphoric acid salt of sodium and potassium, sodium, wherein the polymerization degree is between about 6～21, and the salt of phytinic acid.Be partly dissolved or undissolved washing-aid compound

The present composition can comprise and is partly dissolved or undissolved washing-aid compound, and the typical content in detergent composition is between 0.5%～60wt% of composition weight, preferred 5%～50wt%, most preferably 8%～40wt%.

Substantially water-fast washing assistant example comprises sodium aluminium silicate.

The general formula of the unit structure cell of suitable aluminosilicate zeolites is Na _z[(AlO ₂) _z(SiO ₂) _y] .xH ₂O, wherein z and y are 6 at least; The mol ratio of z and y is between 1.0～0.5, and x is 5 at least, and is preferred 7.5～276, and more preferably 10～264.Aluminosilicate material is in its hydrated form, and crystalline preferably, contains 10%～28%, more preferably 18%～22% combination water.

This aluminosilicate zeolites can be naturally occurring material, but preferably by synthetic deutero-.The synthesising crystal aluminium silicate ion-exchange material can be buied by trade(brand)name zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and composition thereof.Zeolite A general formula is:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] .xH ₂O wherein x between 20～30, especially 27.The X zeolite general formula is:

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆].276H ₂O。

Another kind of preferred aluminosilicate zeolites is a zeolite MAP builder.

The content of zeolite MAP can account for 1～80% of composition weight, more preferably 15%～40wt%.

Zeolite MAP is described among the EP 384070A (Unilever).It is defined as the zeolite P type alkali metal aluminosilicate, and wherein the ratio of silicon and aluminium is not more than 1.33, preferably in 0.9～1.33 scope, more preferably in 0.9～1.2 scope.

Particularly importantly silicon/aluminum ratio is not more than 1.15, especially is not more than 1.07 zeolite MAP.

In a kind of preferred version, zeolite MAP builder is with d ₅₀The granularity of value representation is between 1.0～10.0 μ m, more preferably 2.0～7.0 μ m, most preferably 2.5～5.0 μ m.

d ₅₀Its diameter of 50wt% is arranged less than this numerical value in the value representation particle.This granularity specifically can be determined by the traditional analysis technology, for example adopts the measurement microscope method of scanning electronic microscope, perhaps adopts the laser particle size meter.Other determine d ₅₀The method of numerical value is disclosed among the EP 384070A.Heavy metal ion chelating agent

The present composition preferably contains the heavy metal chelant as optional member.So-called heavy metal chelant is meant the composition that plays the effect of chelating heavy metal here.These compositions also can have the ability of chelating calcium and magnesium, yet they show the selectivity of the heavy metal ion of combination such as iron, manganese and copper according to qualifications.

The amount of heavy metal ion chelating agent accounts for 0.005%～10% of correspondent composition or composition, and is preferred 0.1%～5%, and more preferably 0.25～7.5%, 0.3～2wt% most preferably.

The heavy metal ion chelating agent that is fit to the present invention's use comprises Organophosphonate, for example poly-(alkylene phosphonic acids ester), basic metal ethane 1-hydroxyl bisphosphonates and nitrilo trimethylene phosphonic ester of amino alkylidenyl.

Preferred diethylenetriamine five (methene phosphonate ester), ethylene diamine three (methene phosphonate ester), hexamethylene-diamine four (methene phosphonate ester) and hydroxyl-ethylidene 1 in the middle of the above-mentioned chemical species, the 1-bisphosphonates, and 1,1-hydroxyl ethane dimethylene phosphonic acids.It is highly preferred that 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid.

The heavy metal ion chelating agent that other suitable the present invention use comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, for example ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or their any salt.

The heavy metal ion chelating agent that other suitable the present invention use is the iminodiacetic acid derivative, and for example 2-hydroxyethyl diacetic acid or glyceryl iminodiacetic acid are described in EP-A-317, in 542 and EP-A-399,133.Amino diacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2 hydroxypropyl-3-sulfonic acid sequestrant is described in EP-A-516, in 102, also be fit to use here.Beta-alanine-N, N '-diacetic acid, aspartic acid-N, sequestrants such as single acetate of N '-diacetic acid, aspartic acid-N-and the two succsinic acids of imino-are described in EP-A-509, in 382, also are suitable.

EP-A-476,257 have described the suitable sequestrant based on amino.EP-A-510,331 have described by collagen, Keratin sulfate or casein derived suitable sequestrant.EP-A-528,859 have described suitable alkyl imino diacetic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2,4-tricarboxylic acid also are suitable.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is suitable.

Especially preferred is diethylene triaminepentaacetic acid(DTPA), quadrol-N, N '-disuccinic acid (EDDS) and 1, the ammonium salt of 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or their basic metal, alkaline-earth metal, ammonium or replacement, perhaps their mixture.Enzyme

The preferred composition that uses is a kind or multiple additional enzymes in the another kind of present composition.

Preferred additional enzymes material comprises commercially available lipase, M-Zyme, amylase, neutrality and Sumizyme MP, cellulase, endoenzyme, esterase, polygalacturonase, Sumylact L and peroxidase, and these join composition in the detergent composition traditionally.Suitable enzyme can be referring to United States Patent (USP) 3,519, and 570 and 3,533,139.

Preferred commercially available proteolytic enzyme comprises those that sold by Novo industrial (Denmark) with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase; Sell by Gist-Brocades with trade(brand)name Maxatase, Maxacal and Maxapem; Those that sell by Genencor international corporation; And sell by Solvay enzyme company with trade(brand)name Opticlean and Optimase those.The add-on of proteolytic enzyme in composition of the present invention by organized enzyme, is equivalent to 0.0001%～4% of composition weight.

Preferred amylase for example comprises the α-Dian Fenmei of being produced by the special bacterial strain of lichens bacillus, and details is described in GB-1, in 269,839 (the Novo companies).Preferred commercially available amylase comprises, for example those that sold with trade(brand)name Rapidase by Gist-Brocades; And sell with trade(brand)name Termanyl, Duramyl and BAN by Novo industrial those.Highly preferred amylase can be to be described among PCT/US 9703635 and WO 95/26397 and the WO 96/23873 those.

The add-on of amylase in the present composition by organized enzyme, is equivalent to 0.0001%～2wt% of composition weight.

The amount of lipolytic enzyme by active lipolytic enzyme, is equivalent to 0.0001%～2wt% of composition weight, preferred 0.001%～1wt%, most preferably 0.001%～0.5wt%.

Lipase can be obtained by following fungi or bacterial origin: for example plant Pseudomonas (Humicola sp.), thermomycetin genus or Rhodopseudomonas by the bacterial strain corruption that produces lipase, comprise Pseudomonas alcaligenes (Pseudomonas pseudoalcaligenes) or Pseudomonas fluorescens (Pseudomas fluorescens).The lipase that these bacterial strains obtain by chemical process or obtain by genetically engineered modification variant also is useful.A kind of preferred lipase is that it is described among the European patent EP-B-0218272 that has authorized by false unit cell (the Pseudomonas pseudo alcaligenes) deutero-of product alkali.

Here preferred another kind of lipase is to plant Pseudomonas gene (Humicola Lanuginosa) by the clone from thin erion corruption, and this gene expressed in rice paddy aspergillus tubigensis (Aspergillus oryza) as the host obtain as being described among European patent application EP-A-0258068, commercially available by Novo industrial (Bagsvaerd, Denmark) with trade(brand)name Lipolase.This lipase also is described in United States Patent (USP) 4,810, in 414 (people such as Huge-Jensen, 1989-03-07 authorizes).Additional organic polyhydroxyl compound

Organic polyhydroxyl compound is the preferred supplementary component of the present composition, preferably exists with the composition in any particle, and promptly they can play the effect that particulate component is bonded together in particle.So-called organic polyhydroxyl compound is meant in the detergent composition any basically usually as dispersion agent and the polymerizable organic compound that uses as anti redeposition agent and soil-suspending agent here.

The typical add-on of organic polyhydroxyl compound in detergent composition of the present invention is equivalent to 0.01%～30% of composition weight, and be preferred 0.1%～15%, most preferably 0.5%～10wt%.

The example of organic polyhydroxyl compound comprises water-soluble organic homopolymerization or copolymerization poly carboxylic acid or its salt, and wherein poly carboxylic acid comprises at least 2 carboxyls, apart therebetween no more than 2 carbon atoms.Back one type polymer is disclosed in GB-A-1, in 596,756.The example of this type of salt be molecular weight equal (MWt) 1000～5000 polyacrylic ester and with the multipolymer of maleic anhydride, the molecular weight of this analog copolymer is between 2000～100,000, especially 40,000～80,000.

The polyamino compound also is an available here, comprises by aspartate-derived those, for example is disclosed among EP-A-305282, EP-A-305283 and the EP-A-351629.

The terpolymer that contains the monomeric unit that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, especially molecular-weight average are between 5,000～10, and those of 000 here also suit.

Other organic polyhydroxyl compounds that are fit to join in the detergent composition of the present invention comprise derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.

Other useful organic polyhydroxyl compounds are polyoxyethylene glycol, and particularly molecular weight equals 1000～10000, more especially 2000～8000, and those of 4000 most preferably from about.

Polyethylene oxide is preferred supplementary component, especially exists as wetting agent with particle form with clay described herein, preferably also combines with wax or oil.

Here highly preferred component of polymer is according to United States Patent (USP) 4,968,451 (people such as Scheibel) and United States Patent (USP) 5,415,807 (people such as Gosselink), and particularly according to U. S. application number 60/051517 described cotton or non-cotton soil release polymers.

, can be the ethoxylation positively charged ion monoamine and the diamines of following general formula here preferably as the another kind of organic compound of clay suspending agent/anti redeposition agent: Wherein X is a non-ionic group, is selected from H, C ₁～C ₄Group such as alkyl or hydroxy alkyl ester or ether, and mixed base, a be between 0～20, preferred 0～4 (for example ethylidene, propylidene, hexa-methylene), and b is 1 or 0; Under the situation of positively charged ion monoamine (b=0), n is 16 at least, and its typical range is 20～35; Under the situation of cationic diamine (b=1), it is about 12 that n is at least, and typical range is between about 12～about 42.

Other dispersion agent/anti redeposition agents used herein are described in EP-B-011965 and US4,659,802 and US 4,664,848 in.Press down foam system

Detergent composition of the present invention when being mixed with when being used to machine-wash composition, can comprising and press down foam system, and its content is equivalent to 0.01%～15% of composition weight, and is preferred 0.02%～10%, most preferably 0.05%～3wt%.

Be fit to the foam system that presses down used herein and can comprise any basically known defoaming compounds, comprise for example siloxanes defoaming compounds and 2-alkyl chain triacontanol (alcanol) defoaming compounds.

So-called defoaming compounds here is meant and plays any compound of foamy that inhibition causes by detergent composition solution or the mixture, the particularly foam that is produced of compound when solution is subjected to stirring.

The especially preferred here defoaming compounds that uses is any siloxanes defoaming compounds that comprises silicone component that this paper defines.This kind siloxanes defoaming compounds also contains silica composition usually.Term " siloxanes " includes various higher molecular weight polymer that contains siloxane unit and all kinds alkyl in the implication that this paper and industry member generally adopt.Preferred siloxanes defoaming compounds is a siloxanes, especially has the unitary polydimethylsiloxane of trimethyl silyl end-blocking.

Other suitable defoaming compounds comprise mono carboxylic lipid acid and soluble salt thereof.This class substance description is at United States Patent (USP) 2,954, in 347 (1960-09-27 authorizes Wayne St.John).Mono carboxylic lipid acid and salt thereof have 10～24 carbon atoms, the hydrocarbyl chain of preferred 12～18 carbon atoms usually when as suds suppressor.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts, and ammonium and alkanol ammonium salts.

Other suitable defoaming compounds comprise, for example high molecular weight fatty acid ester (for example glycerine fatty acid three esters), the fatty acid ester of monohydroxy-alcohol, aliphatic C ₁₈～C ₄₀Ketone (for example stearone) N-alkylation aminotriazine, for example three～six alkyl melamines or two～tetraalkyl diammonium chloride triazine, be as cyanuric chloride and 2 or the product of the primary and secondary amine of 1～24 carbon atom of 3mol generate; Also comprise propylene oxide, bis-stearamides and single octadecyl two basic metal (for example sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.

The preferred foam system that presses down comprises: (a) defoaming compounds, and preferred siloxanes defoaming compounds most preferably contains the siloxanes defoaming compounds that following composition combines,

(i) polydimethylsiloxane accounts for 50%～99% of siloxanes defoaming compounds weight, preferred 75%～95wt%; And

(ii) silicon-dioxide accounts for 1%～50% of siloxanes/silicon-dioxide defoaming compounds weight, preferred 5%～25wt%; The add-on of wherein said siloxanes/silicon-dioxide defoaming compounds is between 5%～50%, preferred 10%～40wt%; (b) compound dispersing agent, most preferably contain siloxanes-glycol rake formula (rake) multipolymer, wherein polyoxyalkylene content equals 72～78%, and the ratio between oxyethane and the propylene oxide was between 1: 0.9～1: 1.1, add-on is between 0.5%～10%, preferred 1%～10wt%; Especially preferred this type siloxanes-glycol rake formula multipolymer is DCO544, is supplied by trade(brand)name DCO544 by DOW Corning company; (c) the liquid carrier compound of inertia most preferably comprises C ₁₆～C ₁₈Ethoxylated alcohol, its ethoxylation degree be between 5～50, and be preferred 8～15, and add-on is between 5%～80%, preferred 10%～70wt%;

A kind of highly preferred granular foam system that presses down is described among the EP-A-0210731, comprise a kind of siloxanes defoaming compounds and a kind of fusing point between 50 ℃～85 ℃ organic support material, wherein organic support material comprises the monoesters of the lipid acid of glycerine and 12～20 carbon atoms.EP-A-0210721 discloses the another kind of preferred granular foam system that presses down, and wherein organic support material is the lipid acid or the alcohol of 12～20 carbon atoms, or its mixture, and fusing point is between 45 ℃～80 ℃.

The highly preferred mixture that foam system comprises polydimethylsiloxane or siloxanes, for example polydimethylsiloxane, aluminosilicate and multi-carboxy acid copolymer, for example laic and the acrylic acid multipolymer of pressing down of another class.

Also highly preferably having soap in addition exists.The polymeric dye transfer inhibitor

The present composition also can comprise 0.01%～10%, preferred 0.05%～0.5wt% polymeric dye transfer inhibitor.

The polymeric dye transfer inhibitor preferably is selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its combination of N-oxidation polyamine polymer, N-vinyl pyrrolidone and N-vinyl imidazole, and like this, these polymkeric substance just can be crosslinked polymkeric substance.White dyes

The also optional hydrophilic white dyes of some type of about 0.005%～5wt% that comprises of the present composition.

Here useful hydrophilic white dyes comprises those of following structural:

R wherein ₁Be selected from anilino, N-2-double hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-double hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chloro and amino; M is the salt-forming cation of sodium or potassium and so on.

R in following formula ₁Be anilino, R ₂Be the N-2-double hydroxyethyl, and M is when being the positively charged ion of sodium and so on, this white dyes is 4,4 '-two [(4-anilino-6-(N-2-double hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene sulfonic acid and disodium salt.Concrete white dyes material can be buied by Ciba-Geigy company by trade(brand)name Tinopal-UNPA-GX.Tinopal-CBS-X and Tinopal-UNPA-GX are the hydrophilic white dyess that detergent composition of the present invention preferably uses.

R in following formula ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino-, and M is when being the positively charged ion of sodium and so on, this white dyes is 4,4 '-two [(4-anilino-6-(N-2-double hydroxyethyl-N-methylamino-)-s-triazine-2-yl) amino]-2,2 '-stilbene sulfonate sodium.This concrete fluorescent bleaches material can be buied by Ciba-Geigy company by trade(brand)name Tinopal-5BM-GX.

R in following formula ₁Be anilino, R ₂Be morpholino and M when being the positively charged ion of sodium and so on, this white dyes is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-stilbene sulfonate sodium.This concrete fluorescent bleaches material can be buied by Ciba-Geigy company by trade(brand)name Tinopal-DMS-X and Tinopal-AMS-GX.The deflocculate polymkeric substance

The preferred deflocculation agent that can be present in here comprises hydrophilic monomer, this monomer polymerizable generates and comprises a kind of water-soluble monomer or monomer mixture, the perhaps water-soluble and relative hydrophilic polymer segment that makes up between the monomer of water that is not dissolved in, thus in the polymkeric substance water at normal temperatures that generated solubleness greater than about 10g/L.The monomeric example of suitable this type of comprises the olefinic unsaturated amides, the derivative that replaces of acrylamide, Methacrylamide and fumaramide and N-thereof for example, as 2-acrylamido-2-methyl propane sulfonic acid, N-(dimethylaminomethyl) acrylamide, so N-(trimethyl ammonium methyl) acrylamide chlorination thing and N-(trimethyl ammonium propyl group) Methacrylamide muriate; Ethylenically unsaturated carboxylic acids or dicarboxylic acid are as vinylformic acid, toxilic acid, methacrylic acid, methylene-succinic acid, fumaric acid, Ba Dousuan, equisetic acid and citraconic acid; And the unsaturated quaternary ammonium compound of other olefinics, for example vinyl-benzyl trimethyl ammonium chloride; The sulfo group alkyl ester of unsaturated carboxylic acid, for example 2-sulfo group ethyl-methyl acrylate; The aminoalkyl ester of unsaturated carboxylic acid, the for example methacrylic ester of 2-aminoethyl, dimethylaminoethyl (methyl) acrylate, diethyl aminoethyl (methyl) acrylate, dimethylaminomethyl (methyl) acrylate, diethyl amino methyl (methyl) acrylate, and their quaternary ammonium salt; Vinyl or allyl amine, for example vinyl pyridine and vinyl morpholine or allyl amine; Diallyl amine and diallyl ammonium compound, for example diallyldimethylammonium chloride; Vinyl heterocycle acid amides, for example vinyl pyrrolidone; Ethenyl aromatic yl sulfonate, for example vinyl benzyl sulfonate; The vinyl alcohol of producing by the vinyl acetate between to for plastic hydrolysis; Propenal; Vinyl carbinol; Vinylacetic acid; Sodium vinyl sulfonate; Sodium allyl sulfonate and above-mentioned monomeric salt.These monomers can use separately or use with its form of mixtures.

Optionally this hydrophilic polymer segment can comprise a small amount of hydrophobic relatively unit, for example by solubleness in the water less than those of the polymer-derived of 1g/l, as long as the overall solubility of this hydrophilic polymer still satisfy above the solubleness requirement of defined.The example of water-insoluble polymer is polyvinyl acetate (PVA), polymethylmethacrylate, polyethyl acrylate, polyethylene, polypropylene, polystyrene, polybutylene oxide, poly(propylene oxide) and polyacrylic acid hydroxypropyl ester relatively.

These polymkeric substance are the end capped polymkeric substance of alkyl sulfide preferably, or with sulfoxide or sulfuryl as end group, perhaps by the end capped polymkeric substance of the hydrophobic sulfydryl of structure RSH mercaptan deutero-, wherein R is the alkyl or the aralkyl of 4～28 carbon atoms.R should have sufficiently long chain length to show the oleophylic performance, and promptly it can be miscible each other with the oiliness stratiform droplet or the micellar phase of detergent composition.Preferred this mercaptan is the alkyl or the aromatic alkyl thioalcohol of 6～18 carbon atoms, for example hexylmercaptan, decyl mercaptan, dodecylbenzyl mercaptan, lauryl mercaptan and Stearyl mercaptan.

The molecular-weight average of preferred this type deflocculate polymkeric substance, by the gel permeation chromatography art is that standard substance is measured with the polyacrylic ester, between about 200～50,000, more preferably from about 200～25,000, for being polymer based with polyacrylic acid and polymethyl acrylic acid, most preferably between about 3,000～10,000.Most preferred polymkeric substance is hydrophilic homopolymer, for example polyacrylic acid or polymethyl acrylic acid, and acrylic or methacrylic acid and the multipolymer that is less than 50wt% toxilic acid (acid anhydride), wherein the body of polymer chain by one by lauryl mercaptan institute deutero-hydrophobic segment end-blocking.

This base polymer and preparation method thereof is disclosed in the common unsettled US application serial No. 08/212611 in more detail, and (1994-03-14 submission) receives its full content for referencial use at this.The polymkeric substance stain remover

The polymkeric substance stain remover to call " SRA " in the following text, can optionally be used for the present composition.Use, SRA will account for 0.01%～10.0% of composition weight usually, representative value 0.1%～5%, preferred 0.2%～3.0wt%.

Typical preferred SRA has hydrophilic segment, so that make the hydrophobic fiber surface such as polyester and nylon become hydrophilic, and have hydrophobic segment, keep adhesion thereon so that be deposited on the hydrophobic fiber and, thereby play anchorage effect hydrophilic segment in the whole cycle of washing and cleaning.This can make the spot of handling with SRA, easier removing in washing procedure subsequently.

Preferred SRA comprises low polyterephthalate, and typical preparation method relates at least 1 transesterify/oligomerization, usually adopts metal catalyst, as the alkoxide of titanium (IV).This kind ester can prepare like this: utilize the additional monomer can be incorporated in this ester structure, by 1,2,3,4 or more a plurality of position in conjunction with entering, do not generate fine and close crosslinked one-piece construction certainly.

Suitable SRA comprises by paraphenylene terephthalamide and the multiple unitary oligomer ester main chain of oxyalkylene oxygen basic weight, and the sulfonated products of the substantial linear ester oligomer partly formed of the allyl group deutero-sulfonation end group of covalent bonding on main chain, for example be described in United States Patent (USP) 4, (1990-11-06 authorizes J.J.Scheibel and E.P.Gosseink) in 968,451.This type of ester oligomer can prepare like this: (a) vinyl carbinol is carried out ethoxylation; (b) make product and dimethyl terephthalate (DMT) (DMT) and 1 of (a), 2-propylene glycol (PG) reacts with two step method transesterify/oligomeric program: and (c) make the product of (b) in water, react with sodium metabisulfite.Another kind of SRA comprises the end capped poly terephthalic acid 1 of nonionic, 2-propylidene/ethylene oxide polyester, be disclosed in United States Patent (USP) 4,711, in 730 (1987-12-08 authorizes people such as Gosselink), those that generate through transesterify/oligomerization by Polyethylene glycol dimethyl ether, DMT, PG and polyoxyethylene glycol (PEG) for example.The example of other SRA comprises: partly-and the end capped oligomer ester of complete negatively charged ion, be disclosed in United States Patent (USP) 4,721, in 580 (1988-01-26 authorizes Gosselink), for example by ethylene glycol (EG), PG, DMT and 3, the oligopolymer that 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate generates; The end capped block polyester oligomeric compound of nonionic, be disclosed in United States Patent (USP) 4,702,857 (1987-10-27 authorizes Gosselink) are for example by DMT, the end capped PEG of methyl (Me) and EG and/or PG or by those of DMT, EG and/or PG, Me end-blocking PEG and Na-dimethyl-5-sulfoisophthalic acid salt preparation; And negatively charged ion, especially the end capped terephthalate of sulfo group virtue acyl, be disclosed in United States Patent (USP) 4, in 877,896 (1989-10-31 authorizes people such as Maldonado, Gosselink), the back is a kind of to be the typical SRA that laundry and the dual-purpose product of fabric-conditioning use, an example is by a sulfosalicylic acid one sodium salt, PG and DMT, optionally (but preferred) also comprises PEG, PEG3400 for example, the ester composition of making.

SRA also comprises: the simple copolymer block of the terephthalate of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) etc., and for example referring to United States Patent (USP) 3,959,230 (1976-05-25 authorizes Hays); And United States Patent (USP) 3,893,929 (1975-07-08 authorizes Basadur); Derivatived cellulose is for example by the hydroxy ethers cellulose polymer compound of Dow chemical company with trade(brand)name METHOCEL supply; C ₁～C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose, referring to United States Patent (USP) 4,000,093 (1976-12-28 authorizes people such as Nicol); And methyl cellulose ether, each dehydration glucose unit of its average substitution degree (methyl) is between about 1.6～about 2.3, and by 2% aqueous solution at the soltion viscosity of 20 ℃ of mensuration between about 80～about 120cp.This kind material can be buied with trade(brand)name METOLOSE SM100 and METOLOSE SM200 from Shin-etsu KagakuKogyo KK, belongs to methyl cellulose ethers.Highly preferred glycan polymkeric substance in addition.

An other class SRA comprises: (I) utilize the vulcabond coupling agent to connect the nonionic terephthalate that the polymer esters structure forms, and referring to United States Patent (USP) 4,201,824 people such as () Violland, and United States Patent (USP) 4,240,918 people such as () Lagasse; And the SRA that (II) has the carboxylate end group, by being added to, trimellitic acid 1,2-anhydride makes terminal hydroxy group be converted into trimellitate on the known SRA to make.Under the situation of appropriate selecting catalyst, the key of trimellitic acid 1,2-anhydride and this polymer terminal group is to form ester by that isolated carboxylic acid of trimellitic acid 1,2-anhydride, rather than form by the anhydride bond open loop.No matter nonionic or negatively charged ion SRA all can be used as raw material, but as long as they have the terminal hydroxy group of esterification.Referring to United States Patent (USP) 4,525,524 (people such as Tung).Another type comprises: (III) the SRA that connects of ammonia ester based on negatively charged ion terephthaldehyde acid group, and referring to United States Patent (USP) 4,201,824 people such as () Violland; The composition that other optionally add

Other be fit to add that compositions that depend on the needs in present compositions comprise spices, tinting material and as other filling salts of vitriol filling salt surrogate.

Highly preferred composition comprises about 2%～about 10wt% organic acid, optimization citric acid, oxysuccinic acid, toxilic acid, acetate, tartrate, pentanedioic acid or amino acid.

Also can there be minor constituent (for example being less than about 20wt%) preferred and that carbonate combines, comprise neutralizing agent, buffer reagent, phase modifier, hydrotropic agent, enzyme stabilizers, polyprotonic acid, foaming regulator, opacifying agent, antioxidant, sterilant, optical white, variegation, dyestuff, as United States Patent (USP) 4,285,841 (1981-08-25 authorizes people such as Barrat, and is for referencial use in these receipts) those disclosed.The form of composition

The present composition can comprise that all cpds that will comprise in the detergent ingredients carries out dry blending, agglomeration, compacting or spraying drying, the perhaps combination of these technology by various method manufacturings.

The composition here can be taked various physical form, comprises liquid, but preferred solid form, for example tablet, thin slice, lozenge and strip, preferred particulates form.

The present composition also can be used for bleaching in the compositions of additives, as in the composition of chlorine bleaching agent or combine with it.

Detergent composition of the present invention, especially detergent for washing clothes preferably have the bulk density of 280g/l～200g/l, or preferred 300g/l, or even 350g/l, perhaps 420g/l～2000g/l, or more preferably to 1500g/l or 100g/l, or even 700g/l at most.SYNTHETIC OPTICAL WHITNER based on chlorine

This detergent composition can comprise the SYNTHETIC OPTICAL WHITNER based on chlorine as supplementary component.Yet in view of the preferred detergent composition of the present invention is a solid, so most liquid chloro SYNTHETIC OPTICAL WHITNER will be not suitable for these detergent composition, it is suitable to have only granular or Powdered chloro SYNTHETIC OPTICAL WHITNER to be only.

In addition, this detergent composition can be mixed with the form with the chloro bleach-compatible, thus guarantee the chloro SYNTHETIC OPTICAL WHITNER can the beginning of washing process or during, all can join in the detergent composition by the user.

This chloro SYNTHETIC OPTICAL WHITNER, for example the hypochlorite chemical substance forms in the aqueous solution.Hypochlorite ion's chemistry formula OCl ^-Representative.

Those SYNTHETIC OPTICAL WHITNER that produce the hypochlorite chemical substance in the aqueous solution comprise basic metal and alkaline-earth metal hypochlorite, hypochlorite adduct, chloramines, chlorimide, chloro-acid amide and chlorine imide.The object lesson of this type compound comprises clorox, potassium hypochlorite, monovalence hypochlorous acid calcium salt, divalence hypochlorous acid magnesium salts, 12 hydration Efficacious Disinfeitants, DCCK, dichloroisocyanuric acid sodium, two hydration dichloroisocyanuric acid sodiums, trichlorocyanuric acid, 1,3-two chloro-5,5-T10, N-chloro sulphonamide, chloramine-T, dichloramine-T, chloramine B and dichloramine B.The SYNTHETIC OPTICAL WHITNER that is preferred for the present composition is clorox, potassium hypochlorite and composition thereof.Preferred chloro SYNTHETIC OPTICAL WHITNER is Triclosan (trade(brand)name).

Most of in the middle of the SYNTHETIC OPTICAL WHITNER of generation hypochlorite described above with solid or conc forms supply, and during the preparation of the present composition, be dissolved in the water.Some is supplied with aqueous solution form in the middle of the above-mentioned materials.Clothes washing method

Typical case's machine washing method here is to handle soiled clothes with wash water solution in washing machine, dissolving or distribute significant quantity the present invention detergent composition of machine-washing in this solution.So-called significant quantity detergent composition is meant 10g～300g product dissolving or is dispersed in the washing soln of 5～65L volume, in tradition machine washing method normally used typical products dosage and the washing soln volume.

The composition here both can be used for conventional washer and also can be used in the low water injection rate washing machine.

In the advantageous applications scheme, said composition is in hand washing.In another preferred version, this detergent composition is pre-treatment or soaks composition, prepares to be used for pre-treatment and soaks the fabric of making dirty or being stained with color spot.

The abbreviation of using among the embodiment

In detergent composition, the composition title implication of abbreviation is as follows: LAS: line style C _11-13Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate CxyAS: C _1x～C _1ySodium alkyl sulfate C46SAS: C ₁₄～C ₁₆Secondary (2,3) sodium alkyl sulfate CxyEzS: C _1x～C _1yThe condenses CxyEz of sodium alkyl sulfate and z moles of ethylene oxide: C _1x～C _1yThe primary alconol of substantial linear and average z moles of ethylene oxide

Condenses QAS: R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH), R wherein ₂=C ₁₂～C ₁₄QAS1: R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH), R wherein ₂=C ₈～C ₁₁SADS: C ₁₄～C ₂₂Alkyl two sodium sulfate, general formula 2-(R) .C ₄H ₇.-1,4-

(SO ₄ ^-) ₂, R=C wherein ₁₀～C ₁₈SADE2S: C ₁₄～C ₂₂Alkyl two sodium sulfate, general formula 2-(R) .C ₄H ₇.-1,4-

(SO ₄ ^-) ₂, R=C wherein ₁₀～C ₁₈, with contracting of z moles of ethylene oxide

Compound MES: C ₁₈The x-sulfo methyl ester APA of lipid acid: C ₈～C ₁₀Aminopropyl dimethylamine soap: the linear alkyl carboxylic acid sodium, mix by 80/20 tallow and coconut fatty acid

Compound is derived and is come STS: toluenesulfonic acid sodium salt CFAA: C ₁₂～C ₁₄(coconut) alkyl N-methyl glucose amide TFAA: C ₁₆～C ₁₈Alkyl N-methyl glucose amide TPKFA: C ₁₆～C ₁₈The full cut lipid acid of topping STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: aquation sodium aluminium silicate, general formula Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O, just

The grade particles granularity (is pressed the anhydrous state weighting table between 0.1～10 μ m

Show) NaSKS-6: crystalline layered silicate, general formula δ-Na ₂Si ₂O ₅Citric acid: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: anhydrous sodium carbonate, granularity is between 200 μ m～900 μ m supercarbonates: anhydrous sodium bicarbonate, size-grade distribution are between 400 μ m～1200 μ m silicate: amorphous sodium silicate (SiO ₂: Na ₂O=2.0: 1) vitriol: anhydrous sodium sulphate sal epsom: anhydrous magnesium sulfate Citrate trianion: two hydration trisodium citrates, effective constituent 86.4%, size-grade distribution

Between 425 μ m～850 μ mMA/AA: 1: 4 toxilic acid/acrylic copolymer, molecular-weight average about 70,000MA/AA (1): 4: 6 toxilic acid/acrylic copolymer, molecular-weight average about 10,000AA: polyacrylic acid sodium polymer, molecular-weight average 4,500CMC: the plain ether of sodium carboxyme-thylcellulose fibre: methyl cellulose ether, the polymerization degree 650, Shin Etsu chemistry is public

Department's product proteolytic enzyme: proteolytic ferment, effective enzyme content 3.3wt%, Novo industry is public

Department sells proteolytic enzyme I with trade(brand)name Savinase: proteolytic ferment, effectively enzyme content 4wt% is described in WO

In 95/10591, supply Alcalase by Genencor international corporation: proteolytic ferment, effective enzyme content 5.3wt%, Novo industry is public

The plain enzyme of department's delivery of fibers: cellulolytic enzyme, effective enzyme content 0.23wt%, Novo worker

Industry company, trade(brand)name Carezyme amylase: amylolytic enzyme, effective enzyme content 1.6wt%, Novo industry is public

Department, trade(brand)name Termamyl 120T amylase II: amylolytic enzyme is disclosed in lipase among the PCT/US 9703635: lipolytic enzyme, effective enzyme content 2.0wt%, Novo industrial,

Trade(brand)name Lipolase lipase II: lipolytic enzyme, effective enzyme content 2.0wt%, Novo industrial,

Trade(brand)name Lipolase Ultra endoenzyme: endogenous dextranase, effective enzyme content 1.5wt%, Novo industry

The supply PB4 of company: four hydrated sodium perborates, nominal molecular formula NaBO ₂.3H ₂O.H ₂O ₂PB1: anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, nominal molecular formula NaBO ₂.H ₂O ₂Percarbonate: SPC-D, nominal molecular formula 2Na ₂CO ₃.3H ₂O ₂DOBS: the last of the ten Heavenly stems acyloxy benzene sulfonate, sodium-salt form DPDA: diperoxy dodecanedioic acid NOBS: nonanoly acyloxy benzene sulfonate, sodium-salt form NACA-OBS: (the amino hexanoyl of 6-nonanoyl) oxygen base Phenylsulfonic acid (ester) PAP: phthalyl amido peroxyacid LOBS: dodecane acyl-oxygen base benzene sulfonate, sodium-salt form DOBS: the last of the ten Heavenly stems acyloxy benzene sulfonate, sodium-salt form DOBA: caprinoyl aminobenzoic acid TAED: tetraacetyl ethylene diamine DTPA: diethylene triaminepentaacetic acid(DTPA) DTPMP: diethylenetriamine five (methylene phosphonic acid), Monsanto Company is with the merchant

Name of an article Dequest 2060 supply EDDS: quadrol-N, N '-disuccinic acid, (S, S) isomer, sodium salt shape

Formula photoactivation thing: sulfonation zinc phthalocyanine, capsule are enclosed in SYNTHETIC OPTICAL WHITNER (1) dextrin soluble poly

Photoactivation thing in the compound: sulfonation phthalocyanine aluminium, capsule are enclosed in SYNTHETIC OPTICAL WHITNER (2) dextrin soluble poly

Whitening agent is 1: 4 in the compound, 4 '-two (2-sulfo group styryl) biphenyl sodium whitening agent 2: 4,4 '-two (4-anilinos-6-morpholino-1,3,5-triazines-2-

Base) stilbene-2 amino), 2 '-sodium disulfonate HEDP: 1,1-hydroxyl ethane disulfonic acid PEGx: polyoxyethylene glycol, molecular weight is an x (representative value 4,000) PEO: polyethylene oxide, molecular-weight average 50,000TEPAE: tetren ethoxylate PVI: polyvinyl imidazol, molecular-weight average 20,000PVP: polyvinylpyrrolidonepolymers polymers, molecular-weight average 60,000PVNO: poly-N-oxyethylene group pyridine polymers, molecular-weight average

50,000PVPVI: the multipolymer of Polyvinylpyrolidone (PVP) and polyvinyl imidazol is flat

Average molecular weight 20,000QEA: two ((C ₂H ₅O) (C ₂H ₄O) _n) CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two

((C ₂H ₅O)-(C ₂H ₄O)) _n, n=20～30PEI wherein: polymine, molecular-weight average 1800, and it is former to have each nitrogen

The average degree of ethoxylation clay I of 7 oxygen ethene residues of son: POLARGEL NF II: terre verte flocculation agent I: polyethylene oxide, molecular-weight average 200,000～400,000 flocculation agent II: polyethylene oxide, molecular-weight average 400,000～1,000,000 flocculation agent III: acrylamide and/or polymerizing acrylic acid thing, molecular-weight average

200,000～400,000SRPI: the end capped polyester soil release polymers SRPII of negatively charged ion: glycan soil release polymer SRP1: nonionic end capped polyesters SRP2: the short embedding of diethoxyization poly-(terephthalic acid 1,2-propylene glycol ester)

Section polymer siloxane defoamer: polydimethylsiloxane Foam Control and siloxanes-oxyalkylene are common

The polymers dispersion agent, the ratio of described Foam Control and described dispersion agent

Routine between 10: 1～100: 1 opacifying agents: the single styrene latex mixture of water-based, BASF AG is with trade(brand)name

Lytron 621 supply waxes: paraffin variegation: painted carbonate or organic carboxyl acid/salt

In following examples, all content all provide with the wt% of composition weight:

Example 1 following washing composition formulation is according to of the present invention.

	????A	????B	????C	????D
					Foaming powder (blown powder)
Clay I or II	????7.0	????10.0	????6.0	????2.0
					Flocculation agent I or II	????0.3	????1.0	????1.0	????0.5
?????LAS	????16.0	????5.0	????11.0	????6.0
					?????TAS	????-	????5.0	????-	????2.0
Zeolite A	????-	????20.0	????-	????10.0
					?????STPP	????24.0	????-	????14.0	????-
Vitriol	????-	????2.0	????-	????-
					?????MA/AA	????-	????2.0	????1.0	????1.0
Silicate	????4.0	????7.0	????3.0	????-
					?????CMC	????1.0	????-	????0.5	????0.6
Whitening agent	????0.2	????0.2	????0.2	????0.2
					Yellow soda ash	????10.0	????10.0	????20.0	????-
?????DTPMP	????0.4	????0.4	????0.2	????-
					In the spraying
Whitening agent	????0.02	????-	????-	????0.02
					C45E7 or E9	????-	????-	????2.0	????1.0
C45E3 or E4	????-	????-	????2.0	????4.0
					Spices	????0.5	????-	????0.5	????0.2
Silicone antifoam agent	????0.3	????-	????-	????-
					Dried additive
?????QEA	????-	????-	????-	????1.0
					?????HEDP/EDDS	????0.3	????-	????-	????-

Vitriol	????2.0	????-	????-	????-
					Carbonate	????20.0	????13.0	????15.0	????24.0
Citric acid	????2.5	????-	????-	????2.0
					????QAS	????-	????-	????0.5	????0.5
????SKS-6	????3.5	????-	????-	????5.0
					Percarbonate	????-	????-	????-	????9.0
????PB4	????-	????-	????5.0
					????PAP/NOBS	????-	????-	????-	????1.3
????TAED	????-	????-	????2.0	????1.5
					Proteolytic enzyme	????1.0	????1.0	????1.0	????1.0
Lipase	????-	????0.4	????-	????0.2
					Amylase	????0.2	????0.2	????0.2	????0.4
Whitening agent	????0.05	????-	????-	????0.05
					Spices	????1.0	????0.2	????0.5	????0.3
Variegation	????1.2	????0.5	????2.0	????-
					Other/trace ingredients to be to gather together enough 100%

Example 2 following granulated detergent formulations are according to product of the present invention.

	??E	??F	????G	????H	????I	????J
							Foaming powder (blown powder)
????LAS	??23.0	??8.0	????7.0	????9.0	????7.0	????7.0
							????QAS	???-	???-	?????-	?????-	????1.0	?????-
????C45AS	??6.0	??6.0	????5.0	????8.0	?????-	?????-
							????C45AE3S	???-	??1.0	????1.0	????1.0	?????-	?????-
????MES	???-	???-	?????-	?????-	????2.0	????4.0
							STTP/ zeolite A	??10.0	??18.0	????18.0	????20.0	????10.0	????10.0
????MA/AA	???-	??0.5	?????-	?????-	?????-	????2.0
							????MA/AA(1)	??7.0	???-	?????-	?????-	?????-	?????-
????AA	???-	??3.0	????3.0	????2.0	????3.0	????3.0
							Vitriol	??2.0	??6.0	????1.0	?????-	?????-	?????-
Silicate	??10.0	???-	????2.0	????7.0	????1.0	????1.0
							Carbonate	??25.0	??20.0	????10.0	????20.0	????14.0	?????-
????PEG4000	??0.4	??1.5	????1.5	????1.0	????1.0	????1.0
							????DTPA	???-	??0.9	????0.5	?????-	?????-	????0.5
Whitening agent	??0.3	??0.2	????0.3	?????-	????0.1	????0.3
							Flocculation agent I or III	??0.5	??0.1	????0.2	????0.8	????1.5	????0.2
In the spraying
							????C45E7	???-	??2.0	????-	?????-	????2.0	????2.0
????C25E9	??3.0	???-	????-	?????-	?????-	?????-
							????C23E9	???-	???-	????1.5	????2.0	?????-	????2.0
Spices	??0.3	??0.3	????0.3	????2.0	????0.3	????0.3
							Agglomerate
????C45AS	???-	??5.0	????5.0	????2.0	?????-	????5.0

????LAS	???-	????2.0	????2.0	?????-	?????-	????2.0
							STPP/ zeolite A	???-	????7.5	????7.5	????8.0	?????-	????7.5
Carbonate	???-	????4.0	????4.0	????5.0	?????-	????4.0
							????PEG4000	???-	????0.5	????0.5	?????-	?????-	????0.5
Other (water etc.)	???-	????2.0	????2.0	????2.0	?????-	????2.0
							Agglomerate
Clay I or II	??10.0	????4.0	????3.0	????15.0	????7.0	????6.0
							Wax	??0.7	?????-	?????-	????1.0	????0.5	????1.0
Dried additive
							????QAS(I)	???-	?????-	?????-	?????-	????1.0	?????-
Citric acid	???-	?????-	?????-	?????-	????2.0	?????-
							????PB4	???-	????3.0	?????-	?????-	?????-	?????-
????PB1	???-	?????-	????4	????1.0	?????-	?????-
							Percarbonate	??12.0	?????-	?????-	????1.0	?????-	????2.0
Carbonate	???-	????5.3	????20.0	????5.0	????14.0	????24.0
							????NOBS	??0.5	?????-	????0.4	????0.3	?????-	????0.6
????DOBS/PAP	???-	????0.9	?????-	?????-	????0.3	?????-
							????TAED	??0.6	????0.4	????0.6	????0.3	????0.9	????0.5
Methylcellulose gum	??0.2	?????-	?????-	?????-	?????-	????0.5
							????DTPA	??0.7	????0.5	????1.0	????0.5	????0.5	????1.2
Variegation	??0.3	????0.2	????2.0	?????-	????0.7	????0.5
							????SKS-6	??8.0	?????-	?????-	?????-	?????-	?????-
????STS	???-	?????-	????2.0	?????-	????1.0	?????-
							Cumene sulfonic acid	???-	????1.0	?????-	?????-	?????-	????2.0
Lipase	??0.2	?????-	????0.2	?????-	????0.2	????0.4
							Cellulase	??0.2	????0.2	????0.2	????0.3	????0.2	????0.2
Amylase II	??0.2	?????-	????0.1	?????-	????0.2	?????-

Proteolytic enzyme	????0.5	????0.5	????0.5	????0.3	????0.5	????0.5
							????PVPVI	?????-	?????-	?????-	?????-	????0.5	????0.1
????PVP	?????-	?????-	?????-	?????-	????0.5	?????-
							????PVNO	?????-	?????-	????0.5	????0.3	?????-	?????-
????QEA	?????-	?????-	?????-	?????-	????1.0	?????-
							SRPI, II, or III	????0.2	????0.5	????0.3	?????-	????0.2	?????-
Silicone antifoam agent	????0.2	????0.4	????0.2	?????-	????0.1	?????-
							Sal epsom	?????-	?????-	????0.2	?????-	????0.2	?????-
Other/trace ingredients gathers together enough 100%

Example 3 following granulated detergent formulations are according to product of the present invention.

	????K	????L	????M	????N
					Base particle
????STPP	?????-	????22.0	?????-	????15.0
					Zeolite A	????30.0	?????-	????24.0	????5.0
Vitriol	?????-	?????-	????2.0	????5.0
					????MA/AA	????3.0	?????-	?????-	?????-
????AA	?????-	????1.6	????2.0	?????-
					Flocculation agent I or II	????0.2	????0.1	????0.5	?????-
????LAS	????14.0	????10.0	????19.0	????26.0
					????C45AS	????8.0	????7.0	????2.0	?????-
????C45AE3S	????2.0	????1.0	?????-	?????-
					????MES	?????-	????4.0	?????-	?????-
Clay I or II	????12.5	????8.0	????10.0	????5.0
					Silicate	????4.0	????1.0	?????-	????10.0
Soap	?????-	????2.0	????2.0	????3.0
					Whitening agent 1	????0.2	????0.2	????0.2	????0.2
Carbonate	????16.0	????19.0	????10.0	????20.0
					????PEG4000	?????-	????1.0	????1.5	??????-
C25E3 or E4	????2.0	?????-	????3.0	??????-
					C45E5 or E7	????2.0	?????-	?????-	??????-
????DTPA	?????-	????0.4	?????-	??????-
					In the spraying
C25E3 or E4	?????-	?????-	?????-	????2.0
					C45E5 or E7	?????-	?????-	?????-	????2.0
Whitening agent/optical white	?????-	?????-	????0.5	????0.5
					Spices	????0.2	????0.3	????0.3	?????-
Dried additive

Carbonate	????15.0	????10.0	????13.0	????5.0
					????PVPVI/PVNO	????0.5	?????-	????0.3	?????-
Proteolytic enzyme	????1.0	????1.0	????1.0	????0.5
					Lipase	????0.4	?????-	?????-	????0.4
Amylase	????0.1	?????-	?????-	????0.1
					Cellulase	????0.1	????0.2	????0.2	????0.1
????DTPA	????0.5	????0.3	????0.5	????1.0
					Clay I or II (wax)	?????-	?????-	?????-	????5.0
????PB1	????5	????3.0	????10	????4.0
					????PAP/DOBA	????1.0	?????-	????0.4	?????-
????TAED	????0.5	????0.3	????0.5	????0.6
					Vitriol	????4.0	????5.0	?????-	????5.0
SRPI, II or III	????0.2	????0.4	????1.0	????0.5
					Suds suppressor	?????-	????0.5	?????-	?????-
Variegation	????1.8	????0.8	????0.7	????1.2
					Flocculation agent	?????-	?????-	????0.1	????0.2
Spices (starch)	?????-	????0.2	????0.3	????0.5
					Other/trace ingredients to be to gather together enough 100%

Example is the composition of tablet of the present invention or granular preparation form below 4.

	??O	??P	??R	??S	??T	??U	??V	??W	??X	??Y	??Z
												?C 11-C 13Sodium alkyl benzene sulfonate	??12.0	??16.0	??23.0	??19.0	??18.0	??20.0	??16.0	??8.5	??5	??20.0	??6.0
?C 14-C 15The sodium sulfate of alcohol		??4.5	???-	???-	????-	???-	??4.0	???-	???-	???-	???-
												?C 14-C 15The vitriol of alcohol ethoxylate (0.5)	???-	???-	???-	???-	????-	???-	???-	???-	???-	???-	???-
?C 14-C 15The vitriol of alcohol ethoxylate (3)	???-	???-	??2.0	???-	???1.0	??1.0	??1.0	???-	???-	???-	???-
												?C 14-C 15Alcohol ethoxylate (or mixture of different ethoxylation degrees)	??2.0	??2.0	???-	??1.3	????-	???-	??5.0	??5.5	??4.0	???-	???-

C 9-C 14The alkyl dimethyl ethoxyl quaternary ammonium salt			???-	???-	??1.0	??0.5	??2.0	???-	???-	???-	???-
												Tallow fatty acids			???-	???-	???-	???-	??1.0	???-	???-	???-	???-
Tallow alcohol ethoxylate (50)	???-	???-	???-	???-	???-	???-	???-	???-	???-	???-	???-
												Tripoly phosphate sodium STPP/zeolite	??23.0	??25. ??0	??14.0	??22,0	??20.0	??10.0	??20.0	??30.0	??20.0	??25.0	??25.0
Yellow soda ash	??25.0	??22. ??0	??35.0	??20.0	??28.0	??41.0	??30.0	??30.0	??25.0	??45.0	??24.0
												Sodium polyacrylate (45%)	??0.5	??0.5	??0.5	??0.5	???-	???-	???-	???-	???-	???-	???-
Sodium polyacrylate/sodium maleate polymkeric substance	???-	???-	??1.0	??1.0	??1.0	??2.0	??0.5	??0.5	??1.0	???-	???-
												Water glass (NaO/SiO 2Ratio 1: 6) (46%)	??3.0	??6.0	??9.0	??8.0	??9.0	??6.0	??8.0	??5.0	??6.0	??8.0	??5.0

Sodium sulfate	???-	???-	?????-	???-	???-	??2.0	??3.0	?????-	?????-	????-	???8.0
												Sodium peroxoborate/SPC-D	??5.0	??5.0	???10.0	???-	??3.0	??1.0	???-	????20.0	????14.0	????-	????-
4000 (50%) of poly-(ethylene glycol) Mw	??1.5	??1.5	???1.0	??1.0	???-	???-	??0.5	?????-	?????-	????-	???0.5
												Xylo-Mucine	??1.0	??1.0	???1.0	???-	??0.5	??0.5	??0.5	????0.5	????0.5	????-	???0.5
Citric acid	???-	???-	????-	???-	???-	???-	???-	?????-	?????-	????-	????-
												NOBS/ DOBS	???-	??1.0	????-	???-	??1.0	??0.7	???-	?????-	?????-	????-	????-
TAED/PAP	??1.5	??1.0	???2.5	???-	??3.0	??0.7	???-	????4.5	????5.0	????-	????-
												Sequestrant	??0.5	??0.5	???0.5	???-	??1.0	???-	???-	????0.5	????0.5	????-	????-
SRP	??1.5	??1.5	???1.0	??1.0	???-	??1.0	???-	????1.0	????1.0	????-	????-
												Clay I or II	??5.0	??6.0	???12.0	??7.0	??10.0	??4.0	??3.0	????7.0	????10.0	???6.0	???8.0
Flocculation agent I or II	??0.2	??0.2	???3.0	??2.0	??0.1	??1.0	??0.5	????2.0	????0.5	???1.0	???0.5
												Wetting agent	??0.5	??1.0	???0.5	??1.0	??0.5	??0.5	???-	????1.0	????0.5	????-	????-
Wax	??0.5	??0.5	???1.0	???-	???-	??0.5	??0.5	????0.3	????0.5	???0.5	????-
												Water capacity	??7.5	??7.5	???6.0	??7.0	??5.0	??3.0	??5.0	????5.0	????5.0	???8.0	???10.0
Sal epsom	???-	???-	????-	???-	???-	??0.5	??1.5	?????-	?????-	????-	????-
												Soap/suds suppressor	???-	???-	???0.5	??0.5	??0.8	??0.6	??1.0	????1.0	????0.8	???0.5/ ???0.0	???1.0/ ???0.0

Enzyme comprises amylase, cellulase, proteolytic enzyme and lipase	???-	???-	???-	???-	??2.0	??1.5	??2.0	??0.5	??1.0	??1.0	??1.0
												Variegation	??2.5	??1.1	??0.5	??1.4	???-	???-	??2.2	??1.0	??1.6	??1.0
Trace ingredients, as spices, PVP, PVPVI/PVNO, whitening agent, optical white	??2.0	??1.0	??1.0	??1.0	??2.5	??1.5	??1.0	??1.0	??0.5	??0.5	??0.5

Example is the composition of tablet of the present invention, strip, extrudate or particle form below 5.

	AA	BB	CC	DD
					C 11-C 13Sodium alkyl benzene sulfonate	23.0	13.0	20.0	18.0
C 14-C 15The sodium sulfate of alcohol	?-	4.0	?-	?-
					Clay I or II	5.0	10.0	14.0	6.0
Flocculation agent I or II	0.2	0.3	0.1	0.9
					Wax	0.5	0.5	1.0	?-
Wetting agent (glycerine/silicon-dioxide)	0.5	2.0	1.5	?-
					C 14-C 15Alcohol ethoxylate vitriol	?-	?-	?-	2.0
C 14-C 15The sodium alkoxide ethoxylate	2.5	3.5	?-	?-
					C 9-C 14The alkyl dimethyl ethoxyl quaternary ammonium salt	?-	?-	?-	0.5
Tallow fatty acids	0.5	?-	?-	?-
					Tallow alcohol ethoxylate (50)	?-	?-	?-	1.3
Tripoly phosphate sodium STPP	?-	41.0	?-	20.0
					Zeolite A, hydrate (0.1～10 μ m granularity)	26.3	?-	21.3	?-
Yellow soda ash	24.0	22.0	35.0	27.0
					Sodium polyacrylate (45%)	2.4	?-	2.7	?-
Sodium polyacrylate/sodium maleate polymkeric substance	?-	?-	1.0	2.5

Water glass NaO/SiO 2) ratio is 1.6 or 2 or 2.2) (46%)	4.0	7.0	2.0	6.0
					Sodium sulfate	?-	6.0	2.0	?-
Sodium peroxoborate/SPC-D	8.0	4.0	?-	12.0
					Poly-(ethylene glycol), 4000 (50%) of Mw	1.7	0.4	1.0	?-
Xylo-Mucine	1.0	?-	?-	0.3
					Citric acid	?-	?-	3.0	?-
NOBS/DOBS	1.2	?-	?-	1.0
					TAED	0.6	1.5	?-	3.0
Spices	0.5	1.0	0.3	0.4
					Soil release polymer	?-	1.5	1.0	1.0
Water capacity	7.5	3.1	6.1	7.3
					Sal epsom	?-	?-	?-	1.0
Sequestrant	?-	?-	?-	0.5
					Variegation	1.0	0.5	0.2	2.7
Enzyme comprises amylase, cellulase, proteolytic enzyme and lipase	?-	1.0	?-	1.5
					Trace ingredients, for example whitening agent, optical white	1.0	1.0	1.0	1.0

Example 6 following detergent composition are according to product of the present invention.

	????EE	????EE	????FF	????GG	????HH
						Foaming powder
STPP/ zeolite A	????9.0	????15.0	????15.0	????9.0	????9.0
						Flocculation agent II or III	????0.5	????0.2	????0.9	????1.5	?????-
LAS	????7.5	????23.0	????3.0	????7.5	????7.5
						QAS	????2.5	????1.5	?????-	?????-	?????-
DTPMP	????0.4	????0.2	????0.4	????0.4	????0.4
						HEDP or EDDS	?????-	????0.4	????0.2	?????-	?????-
CMC	????0.1	????0.4	????0.4	????0.1	????0.1
						Yellow soda ash	????5.0	????20.0	????20.0	????10.0	?????-
Whitening agent	????0.05	?????-	?????-	????0.05	????0.05
						Clay I or II	?????-	????10.0	?????-	?????-	?????-
STS	????0.5	?????-	?????-	????0.5	????0.5
						MA/AA	????1.5	????2.0	????2.0	????1.5	????1.5
Agglomerate	?????-	?????-	?????-	?????-	?????-
						Suds suppressor (silicon)	????1.0	????1.0	?????-	????2.0	????0.5
Agglomerate	?????-	?????-	?????-	?????-	?????-
						Clay	????9.0	?????-	?????-	????4.0	????10.0
Wax	????0.5	?????-	?????-	????0.5	????1.5
						Glycerine	????0.5	?????-	?????-	????0.5	????0.5
Agglomerate	?????-	?????-	?????-	?????-	?????-
						LAS	?????-	????5.0	????5.0	?????-	?????-
TAS	?????-	????2.0	????1.0	?????-	?????-
						Silicate	?????-	????3.0	????4.0	?????-	?????-
Zeolite A	?????-	????8.0	????8.0	?????-	?????-

Carbonate	?????-	????8.0	????4.0	?????-	?????-
						In the spraying
Spices	????0.3	?????-	?????-	????0.3	????0.3
						C45E7 or E9	????2.0	?????-	?????-	????2.0	????2.0
C25E3 or E4	????2.0	?????-	?????-	????2.0	????2.0
						Dried additive
Citrate trianion or citric acid	????2.5	?????-	????2.0	????2.5	????2.5
						Clay or II	?????-	????5.0	????5.0	?????-	?????-
Flocculation agent I or II	?????-	?????-	?????-	?????-	????0.2
						Supercarbonate	?????-	????3.0	?????-	?????-	?????-
Carbonate	????15.0	?????-	?????-	????25.0	????31.0
						????TAED	????1.0	????2.0	????5.0	????1.0	?????-
Sodium peroxoborate or SPC-D	????6.0	????7.0	????10.0	????6.0	?????-
						SRPI, II or III	????0.2	????0.1	????0.2	????0.5	????0.3
CMC or nonionic cellulose ether	????1.0	????1.5	????0.5	?????-	?????-
						Proteolytic enzyme	????0.3	????1.0	????1.0	????0.3	????0.3
Lipase	?????-	????0.4	????0.4	?????-	?????-
						Amylase	????0.2	????0.6	????0.6	????0.2	????0.2
Cellulase	????0.2	????0.6	????0.6	????0.2	????0.2
						Silicone antifoam agent	?????-	????5.0	????5.0	?????-	?????-
Spices (starch)	????0.2	????0.3	????1.0	????0.2	????0.2
						Variegation	????0.5	????0.5	????0.1	?????-	????1.0
SKS-6 (silicate 2R)	????3.5	?????-	?????-	?????-	????3.5
						Optical white	????0.1	?????-	?????-	????0.1	????0.1
Soap	????0.5	????2.5	?????-	????0.5	????0.5
						Sodium sulfate	?????-	????3.0	?????-	?????-	?????-
Other/trace ingredients to be to gather together enough 100%	????100.0	????100.0	????100.0	????100.0	????100.0
						Density (g/l)	????850	????850	????850	????850	????850

Claims (15)

1. detergent composition comprises:

A) clay;

B) flocculation agent;

C) basic metal of 18wt% carbonic acid and/or alkaline earth salt at least.

2. the composition of claim 1, wherein flocculation agent be molecular-weight average between 150,000～3,000,000 polyethylene oxide.

3. claim 1 or 2 composition, its medium clay soil comprises terre verte.

4. the composition of any one wherein contains and is less than 10% in the above claim, preferably is less than 5wt% inorganic base metal or alkaline earth metal sulphate.

5. the composition of any one in the above claim wherein contains 5wt% anion surfactant at least.

6. the composition of any one contains 6wt% amorphous silicate, crystalline layered silicate, aluminosilicate or phosphoric acid salt in the above claim, perhaps their mixture.

7. the solids composition of any one comprises 5wt% water at least in the above claim.

8. the composition of any one comprises the fabric maintenance composition in the above claim, is selected from soil release polymer, cellulose polymer compound, dye transfer inhibitor, cationic softener or their mixture.

9. the solids composition of any one comprises the foaming source in the above claim.

10. the composition of any one in the above claim, its medium clay soil and optionally additional flocculation agent exist with particle, preferably spray drying particle or agglomerated particle, wherein the preferred package content of wax.

11. a detergent composition comprises the fragrance component and carrier or the coating that contain spice mixt, preferably includes starch.

12. the detergent composition of any one in the above claim is tablet form.

13. the detergent composition of any one comprises nonionogenic tenside in the above claim.

14. the detergent composition of any one comprises clay mixture in the above claim.

15. clay and flocculation agent are comprising 18wt% inorganic base metal at least or alkaline earth metal carbonate and are being less than application in the detergent composition of 5% mineral sulfates.