CN1240473A - Detergent compositions - Google Patents

Abstract

The present invention relates to detergent compositions having a pH of at least 8.0 in a 0.5 % by weight aqueous solution or components thereof containing cationic surfactants of the formula: R<1>R<2>R<3>R<4>N<+> X<-> in which R<1> is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R<2> and R<3> is independently selected from C1-4 alkyl or alkenyl; R<4> is one or mixtures of more than one of C5-11 alkyl or alkenyl; and X<-> is a counterion which does not substantially exchange with a hydroxide ion at 20 DEG C in a 0.5 % by weight solution of the detergent composition.

Description

Detergent composition

Technical field

The present invention relates to be used for the detergent composition that contains the certain cationic tensio-active agent or its component under the alkaline washing condition.Detergent composition of the present invention can be used for arbitrary washing field, comprises as household cleaners, but more is usually used in washing clothes and tableware, removes greasy dirt performance and cleaning effect so that enhanced to be provided.

Background of invention

As everyone knows, cats product can be used in the detergent composition.For example, GB2040990A has described a kind of granular detergent composition of cation tensio-active agent.

EP-A-121-949 also discloses the cats product that is used for laundry detergent composition.The document has been described various cats products.

Applicant of the present invention finds that specific quaternary ammonium cation tensio-active agent has good clean-up performance, particularly has the ability of excellent removal oil stain.

Have found that cation compound has outstanding especially effect in the detergent composition that also contains anion surfactant in addition.Although do not wish to be bound by any theory, the applicant believes that the specific cats product that is used for detergent composition of the present invention has beat all good solvability.In addition, they form associated complex with the anionic group that exists, produce the negatively charged ion/cationic complexes of beat all solubility, thereby cause the beyond thought impact of performance: cats product can contact with greasy dirt rapidly and effectively, and rapid permeability and disintegrate dirt, thereby remove greasy dirt effectively.And then, it is believed that after oil stain decomposition the cats product of Shi Yonging also can form title complex with the lipid acid that produces and any other electronegative degradation production in the present invention, thereby increased solvability, strengthened and removed greasy dirt performance and total clean-up performance.

Yet, in washing process or be used under the alkalis condition, find that some cats product can make washing liq produce the stench peculiar smell.Do not wish equally to be bound by any theory, applicant of the present invention believes that the generation of foul smell is because exchange has taken place for the counter ion of cats product and the hydroxide ion in the alkaline washing solution.The quaternary ammonium hydroxide product that produces may produce the amine by product that has foul smell.For fear of use this problem that is taken place under alkaline condition, the counter ion of certain cationic tensio-active agent should have the higher relatively selectivity to cats product than the hydroxide ion in the aqueous solution under the working conditions.

All documents of quoting as proof are in the present invention all introduced the present invention as a reference.

Summary of the invention

According to the present invention, a kind of detergent composition or its component are provided, it is that pH value in the aqueous solution of 0.5 weight % is at least 8.0 in concentration, it comprises the cats product of formula I:

R ¹R ²R ³R ⁴N ⁺X ^-(I) wherein, R ¹For having the hydroxyalkyl that is no more than 6 carbon atoms; R ²And R ³Be independently selected from C respectively ₁-C ₄Alkyl or alkenyl; R ⁴Be C ₅-C ₁₁Alkyl or alkenyl; X ^-Be counter ion, it does not exchange with hydroxide ion basically in the 0.5 weight % aqueous solution of 20 ℃ detergent composition.

According to another aspect of the present invention, cats product comprises the mixture of formula I cats product:

R ¹R ²R ³R ⁴N ⁺X ^-(I) wherein, R ¹For having the hydroxyalkyl that is no more than 6 carbon atoms; R ²And R ³Be independently selected from C respectively ₁-C ₄Alkyl or alkenyl; R ⁴Be C ₅-C ₁₁Alkyl or alkenyl; X ^-Be counter ion, it does not exchange with hydroxide ion basically in the 0.5 weight % aqueous solution of 20 ℃ detergent composition, and, wherein, in the mixture of the cats product of formula I, at least 10%, preferred at least 20 weight % or even the cats product of at least 50 weight % in R ⁴Be C ₅-C ₉Alkyl or alkenyl.

According to another aspect of the present invention, cats product comprises the surfactant mixtures of formula I, wherein, exists to have the R that n is n the carbon atom of 8-11 ⁴The long alkyl chain tensio-active agent and have the shorter alkyl chain tensio-active agent of (n-2) individual carbon atom.

Except as otherwise noted, alkyl described in the present invention or alkenyl all can be straight chain, side chain or substituted group.Substituting group can be aromatic group for example, contain the heterocyclic group group or the halogen substituting group of one or more N, S or O atom.

Suitable counter ion are generally the ion bigger than the electronegativity of hydroxide ion.The detailed Description Of The Invention cats product

The amount of the cats product that exists in composition or its component is not more than 60 weight % usually, preferably is not more than 10 weight %, most preferably is not more than 4.5 weight %, or even 3 weight %.The maximum of cats product even can be low to moderate 1 weight %.Also can find effect of the present invention even the amount of the cats product of formula I is considerably less.Usually, in detergent composition of the present invention, comprise at least 0.01 weight %, the cats product of preferred at least 0.05 weight % or at least 0.1 weight %.

R among the formula I ¹Be to have the hydroxyalkyl that is no more than 6 carbon atoms, preferred-OH group and quaternary nitrogen atoms are no more than 3 carbon atoms separate and are opened.Preferred R ¹Group is-CH ₂CH ₂OH ,-CH ₂CH ₂CH ₂OH ,-CH ₂CH (CH ₃) OH and-CH (CH ₃) CH ₂OH.More preferably-CH ₂CH ₂OH and-CH ₂CH ₂CH ₂OH.Most preferably-CH ₂CH ₂OH.Preferred R ²And R ³Be selected from ethyl and methyl respectively, most preferably R ²And R ³Be methyl.Preferred R ⁴Have at least 6 carbon atoms or at least 7 carbon atoms.R ⁴Can contain and be no more than 9 carbon atoms, or even not surpass 8 carbon atoms or 7 carbon atoms.R ⁴Can be C ₅-C ₉Or C ₁₁Preferred R ⁴Be straight chained alkyl.Preferred R ⁴For having the straight chain group of 8-11 carbon atom or 7-9 carbon atom.

The counter ion of exchange do not take place with hydroxide ion in the aqueous solution that it is 0.5 weight % that the counter ion X among the formula I can be any detergent composition at 20 ℃ basically, thereby can avoid the formation of foul smell compound substantially.

Determine whether counter ion are not stated in following document with the proper method of hydroxide ion generation exchange basically: J.PHys.Chem.1986,90,3366-3368, " application of active counter ion type micella in measuring selectivity coefficient " (Maria da Graca Nascimento, Sebastiao A.F.Miranda and Faruk Nome).Being preferred for counter ion of the present invention is, in the time of 25 ℃, in the presence of the cetyltrimethyl ammonium ion, the selectivity coefficient of ion-exchange is at least 2.5, preferably is at least 3, even is at least 3.5 (referring to the tables 1 of above-mentioned document).

Suitable counter ion have bigger electronegativity than hydroxide ion usually.Its preferred embodiment is chlorion, bromide anion and nitrate ion.Preferred especially chlorion.

Although pure or pure substantially cation compound within the scope of the invention, finds that also the mixture of formula I cats product also is effective especially, for example, R wherein ⁴Be blended C ₈And C ₁₀Straight chained alkyl or C ₉And C ₁₁The surfactant mixture of alkyl.According to one aspect of the present invention, the mixture of the cats product of formula I is present in the composition, this mixture comprise formula I shorter alkyl chain tensio-active agent and than the tensio-active agent of long alkyl chain.Cats product than long alkyl chain is preferably selected from wherein R ⁴For having the formula I tensio-active agent that carbonatoms n is the alkyl of 8-11; The cats product of shorter alkyl chain is preferably selected from wherein R ⁴Formula I tensio-active agent for alkyl with (n-2) individual carbon atom.In the blended cationic surfactant system, in the cats product total amount, comprise 5-95 weight % usually, preferred 30-95 weight %, more preferably the long alkyl chain tensio-active agent of at least 50 weight %.Usually comprise 5-95 weight %, preferred 5-70 weight %, the more preferably short alkyl chain tensio-active agent of 35-65 weight %.In detergent composition or its component,, preferably comprise the short alkyl chain tensio-active agent of 40 weight % at least in the cats product total amount.Other detergent component

Detergent composition of the present invention or its component also can comprise other detergent component.The physical form that the definite character of these annexing ingredients and consumption thereof will depend on composition or its component with and the definite character of the washing operation that uses.

Composition of the present invention or its component preferably comprise one or more other detergent components, are selected from other tensio-active agent, washing assistant, sequestrant, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, organic polymer, additional enzymes, suds suppressor, lime soap dispersing agent, other soil-suspending agent and anti redeposition agent, stain remover, spices and corrosion inhibitor.Other tensio-active agent

Detergent composition of the present invention or its component preferably comprise other tensio-active agent, and these tensio-active agents are selected from anion surfactant, nonionogenic tenside, cats product, amphoterics, zwitterionics and its mixture.

US 3,929, and 678 (being issued to Laughlin and Heuring on December 30th, 1975) have provided the general catalogue of negatively charged ion, nonionic, both sexes and zwitterionics and the kind of these tensio-active agents.Other example is also stated in following document: " tensio-active agent and washing composition " (I volume and II volume, Schwartz, Perry and Berch).The catalogue of suitable cats product is stated in 217 (being issued to MurpHy on March 31st, 1981) at US 4,259.

When using amphoterics and zwitterionics, they normally use with one or more negatively charged ion and/or nonionic surfactant combinations.Anion surfactant

In particularly preferred embodiment of the present invention, detergent composition also comprises a kind of anion surfactant.Any anion surfactant that is used for the decontamination purpose all suits, can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant (for example, comprise sodium, potassium, ammonium and substituted ammonium salt, as one, two and triethanolamine salt).The preferred anionic sulfate surfactant.

Other suitable anion surfactant comprises isethionate, as fatty acid amide, alkyl succinate and the alkyl sulfosuccinate of acyl isethinate, N-acyl taurine salt, methyl tauride, the monoesters of sulfosuccinate (particularly saturated and 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 suit, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in butter or obtain by butter.The anion sulfate acid salt surfactant

The anion sulfate tensio-active agent that is applicable to the present composition comprises straight chain and side chain primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide is as the vitriol (compound of nonionic non-sulfuric acid salinization is described hereinafter) of alkyl polyglucoside.

Alkyl ethoxy sulfate surfactant is preferably selected from per molecule by the C of 0.5-20 moles of ethylene oxide ethoxylation ₉-C ₂₂Alkyl-sulphate.More preferably, alkyl ethoxy sulfate surfactant be per molecule by 0.5-7, the C of the oxyethane ethoxylation of preferred 1-5 mole ₁₁-C ₁₈, preferred C ₁₁-C ₁₅Alkyl-sulphate.

The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.This mixture is stated in following document: PCT number of patent application WO93/18124.The anion sulfoacid salt surfactant

Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate and its any mixture.

The particularly preferred composition of the present invention also comprises a kind of anion surfactant, and it is selected from alkyl-sulphate and/or the alkyl benzene sulfonate surfactant of formula II and III respectively:

R ⁵OSO ₃ ^-M ⁺?????????(II)

R ⁶SO ₃ ^-M ' ⁺(III) wherein, R ⁵Be straight or branched alkyl or alkenyl part, it has 9-22 carbon atom, preferred C ₁₂-C ₁₈Alkyl or as seen in secondary alkyl sulfate; R ⁶Be C ₁₀-C ₁₆Alkylbenzene, preferred C ₁₁-C ₁₃Alkylbenzene; M ⁺And M ' ⁺Can change independently of one another, they are selected from basic metal, alkaline-earth metal, alkanol ammonium and ammonium.

The particularly preferred composition of the present invention comprises alkyl sulfate surfactant and alkylbenzene tensio-active agent simultaneously, and the ratio of preferred II and III is 15: 1-1: 2, most preferably 12: 1-2: 1.

In preferred compositions, with composition weight meter, a kind of anion surfactant or can be 1-50 weight %, preferred 5-40 weight % more than a kind of consumption of mixture of anion surfactant.In detergent composition weight, the preferable amount of the alkyl sulfate surfactant of formula II is 3-40 weight %, more preferably 6-30 weight %.In the detergent composition, the preferable amount of the alkyl benzene sulfonate surfactant of formula III is at least 1 weight %, preferably is at least 2 weight %, or even is at least 4 weight %.The preferable amount of alkyl benzene sulfonate surfactant is at most 23 weight %, more preferably no more than 20 weight %, and most preferably 15 weight % at the most, even 10 weight %.

When also using anion surfactant in the composition of the present invention, will produce useful effect, particularly adopt the anion surfactant of long carbon chain lengths, be C as carbon chain lengths ₁₂Or longer, C particularly ₁₄/ ₁₅, even reach C ₁₆-C ₁₈Carbon chain lengths.

Comprise in the preferred embodiment of detergent composition of anion surfactant in the present invention, anion surfactant can be obviously excessive, the weight ratio of preferred anionic tensio-active agent and cats product is 50: 1-2: 1, more preferably 30: 1-8: 1.Yet, be stoichiometry for example 3: 2-4:, also can reach effect of the present invention at 3 o'clock substantially at the ratio of cats product and anion surfactant.

In the preferred embodiment of the invention, in necessary formula I cats product and one or more anion surfactants some or all were mixed before dosing other detergent composition component fully, were easy to dissolved anion surfactant/cats product title complex to provide.Can dose other detergent component, comprise additional any anion surfactant, before with the anion surfactant and the cats product of stoichiometry carry out thorough mixing basically.The anionic carboxylic acid salt surfactant

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

Suitable alkyl ethoxy carboxylate comprises having formula RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Those, wherein, R is C ₆-C ₁₈Alkyl, x are 0-10, and ethoxylate distributes and should make, by weight, x be 0 amount of substance less than 20%, M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises having formula RO-(CHR ₁-CHR ₂-O)-R ₃Those, wherein, R is C ₆-C ₁₈Alkyl, x is 1-25, R ₁And R ₂Be selected from hydrogen, methyl acid group, succsinic acid group, hydroxy succinic acid group and its mixture, R ₃Be selected from hydrogen, have the replacement or the unsubstituted alkyl of 1-8 carbon atom, or its mixture.

Suitable soap class tensio-active agent comprises secondary soap surfactant, and it comprises the carboxyl unit that links to each other with secondary carbon(atom).Being preferred for secondary soap surfactant of the present invention is to be selected from following water-soluble substances: the water-soluble salt that the water-soluble salt of the water-soluble salt of 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, the water-soluble salt of 2-propyl group-1-n-nonanoic acid, 2-butyl-1-are 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 surfactant is formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein, R is C ₅-C ₁₇-straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ion.Preferred embodiment is the myristyl 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 all is applicable to the present invention.Preferred ethoxylation and propoxylation nonionogenic tenside.Straight or branched alkoxylate group suits.

The preferred alkoxylated tensio-active agent can be selected from the condensation product of nonionic condensation product, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, nonionic ethoxylate/propoxylated glycerine and the propylene glycol of alkylphenol, and with the nonionic ethoxylation condensation product of propylene oxide/ethylenediamine adduct.Nonionic alcohol alcoxylates tensio-active agent

Have the 1-25 mole alkylene oxide particularly the condensation product of the Fatty Alcohol(C12-C14 and C12-C18) of ethylene oxide and/or propylene oxide be applicable to the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, and uncle or secondary can comprise 6-22 carbon atom usually.Particularly preferably be the alcohol with the alkyl that comprises 8-20 carbon atom and the condensation product of 2-10 moles of ethylene oxide/mol of alcohol.The nonionic polyhydroxy fatty acid amide surfactant

Be applicable to that polyhydroxy fatty acid amide of the present invention is to have those of following formula: R ²CONR ¹Z, wherein, R ¹Be H, 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 straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is the polyhydroxy alkyl with the straight-chain alkyl that is connected directly to few 3 hydroxyls, or its alkoxy derivative (preferred ethoxylation or propoxylation).Z is preferably obtained in reductive amination process by reducing sugar.More preferably Z is glycosyl (glycityl).The nonionic fatty acid amide surfactant

Suitable fatty acid amide surfactant comprises those with following formula: R ⁶CON (R ⁷) ₂, wherein, R ⁶For comprising 7-21, the alkyl of preferred 9-17 carbon atom, each R ⁷Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and (C ₂H ₄O) _xH, wherein x is 1-3.The nonionic alkyl polysaccharide surfactant

Be applicable to alkyl polysaccharide of the present invention be the US 4565647 of the Llenado that authorized on January 21st, 1986 described those, they have the hydrophobic grouping that contains 6-30 carbon atom, and the hydrophilic polysaccharide group that comprises 1.3-10 sugar unit, for example many glycosides.

Preferred alkyl polyglycoside has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _xWherein, R ²Be selected from: alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein, alkyl comprises 10-18 carbon atom; N is 2 or 3; T is 0-10; X is 1.3-8.Glycosyl is preferably obtained by glucose.Amphoterics

Be applicable to that amphoterics of the present invention comprises amine oxide surfactant and alkyl both sexes carboxylic acid.

Suitable amine oxide comprises formula R ³(OR ⁴) _xN ⁰(R ⁵) ₂Those compounds, wherein, R ³Be selected from the alkyl, hydroxyalkyl, acyl group amido propyl group and the alkyl phenyl that comprise 8-26 carbon atom, or its mixture; R ⁴Be alkylidene group or the hydroxy alkylidene that comprises 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; Each R ⁵Be alkyl or the hydroxyalkyl that comprises 1-3 carbon atom, perhaps comprise the polyoxyethylene group of 1-3 ethylene oxide group.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈Acyl group amidoalkyl dimethyl oxidation amine.

The example of suitable alkyl both sexes dicarboxylic acid is Miranol (TM) C2M Conc., by Miranol, and Inc., Dayton, NJ produces.Zwitterionics

Zwitterionics also can add in detergent composition of the present invention or its component.These tensio-active agents can be described as the derivative of derivative, heterocyclic secondary and the tertiary amine of secondary amine and tertiary amine widely, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the examples that is used for zwitterionics of the present invention.

Suitable trimethyl-glycine is those compounds with following formula: R (R ') ₂N ⁺R ²COO ^-, wherein, R is C ₆-C ₁₈Alkyl, each R ¹Be generally C ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C ₁₂-C ₁₈Dimethylammonio hexanoate and C ₁₀-C ₁₈Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound betaine tensio-active agent also is applicable to the present invention.Other cats product

Composition of the present invention does not preferably comprise wherein R basically ¹, R ², R ³Or R ⁴In one of for being longer than C ₁₁The formula I quaternary ammonium compound of alkyl.Preferred composition should comprise and be less than 1 weight %, preferably is less than 0.1 weight %, and even less than 0.05 weight %, what most preferably be less than 0.01 weight % has 12 or the formula I compound of straight chain (or even side chain) alkyl of more a plurality of carbon atoms.

The another kind of suitable cats product that can be used for detergent composition of the present invention is the cationic ester tensio-active agent.This cationic ester tensio-active agent is a kind of compound with surfactant properties, and it comprises an ester bond at least and (promptly-COO-) and at least comprises a positively charged ion charged group.The preferred cation ester surfactant is a water dispersible.

Suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, and the example is as described in the US4228042,4239660 and 4260529.

In the preferred cation ester surfactant, ester bond and positively charged ion charged group are spaced apart base and are separated from each other in surfactant molecule, described spacer is made up of a kind of chain, this chain comprises at least three atoms (i.e. three atomchain length), preferred 3-8 atom, more preferably 3-5 atom, most preferably 3 atoms.The atom that forms the spacer chain is selected from carbon, nitrogen and Sauerstoffatom and its any mixture, and condition is: any nitrogen-atoms in described chain or Sauerstoffatom only link to each other with carbon atom in the chain.Therefore, eliminating is for example had-O-O-(being superoxide) ,-N-N-and-spacer of N-O-key, and comprise for example having-CH ₂-O-CH ₂-and-CH ₂-NH-CH ₂The spacer of-key.Aspect preferred, the spacer chain only comprises carbon atom, and most preferably described chain is a hydrocarbyl chain.Alkalescence

In detergent composition of the present invention, existing alkaline system to make detergent composition is that pH value in the aqueous solution of 0.5 weight % is at least 8.0 in concentration, or is at least 8.5.Detergent composition can have stronger alkalescence, and in the aqueous solution of 0.5 weight % detergent composition, its pH value is at least 9.0 or be at least 9.5 or 10.0.Alkaline system comprises the component that alkaline matter can be provided in solution.The example of alkaline matter comprises carbonate, supercarbonate, oxyhydroxide, various silicate anion, percarbonate, perborate, superphosphate, persulphate and persilicate.These alkaline matters can be for example by formation that basic salt is dissolved in the water, and described basic salt is selected from carbonate, supercarbonate, oxyhydroxide or silicate (comprising the crystal type layered silicate) and percarbonate, perborate, superphosphate, persulphate and persilicate and any mixture thereof of basic metal or alkaline-earth metal.

The example of carbonate is alkaline-earth metal and alkaline carbonate, comprise yellow soda ash and concentrated crystal soda and with any mixture of calcium carbonate superfine powder, as DE 2,321,001 (on November 15th, 1973 is open) is described.Suitable silicate comprises water-soluble metasilicate, its SiO ₂: Na ₂O is than for 1.0-2.8, preferred 1.6-2.0, most preferably 2.0.Silicate can be anhydrous salt form or salt hydrate form.Most preferred silicate is SiO ₂: Na ₂O is than the water glass that is 2.0.

Be preferred for crystal type layered silicate of the present invention and have following general formula

NaMSi _xO _2x+1YH ₂O wherein, M is sodium or hydrogen, x is 1.9-4, y is 0-20.Such crystal type lamina sodium silicate is disclosed in EP-A-0164514, and its preparation method is disclosed in DE-A-3417649 and DE-A-3742043.Among the present invention, x is preferably 2,3 or 4 in the above general formula, and more preferably 2.Most preferred material is δ-Na ₂Si ₂O ₅, be purchased from Hoechst AG with NaSKS-6.The water soluble detergency promoter compound

Detergent composition of the present invention preferably comprises a kind of water soluble detergency promoter compound, and with composition weight meter, its content is generally 1-80 weight %, preferred 10-70 weight %, more preferably 20-60 weight %.

Suitable water soluble detergency promoter compound comprises multi-carboxylate or its sour form of water-soluble monomer, homopolymerization or copolymerization poly carboxylic acid or its salt, wherein, poly carboxylic acid comprises at least two and is no more than the hydroxy-acid group that two carbon atoms separate are opened each other, described washing-aid compound also comprises borate, phosphoric acid salt, and the mixture of aforesaid compound.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer type or oligomer types, consider the reason of Cost And Performance, usually the multi-carboxylate of preferred monomers type.

The suitable carboxylate salt that comprises a carboxyl comprises the water-soluble salt and the ether derivant thereof of lactic acid, oxyacetic acid.The multi-carboxylate who comprises two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate who comprises three carboxyls comprises particularly water-soluble citrate, aconitate and citraconate, and the succinate derivative, as GB patent 1,379,241 described carboxy methoxy-succinic acid salt, the newborn acyloxy succinate described in the GB patent 1389732, HOII P 7205873 described aminosuccinic acid salt, and GB patent 1,387,447 described oxygen multi-carboxylate materials are as 2-oxa--1,1,3-tricarballylic acid salt.

The multi-carboxylate who comprises four carboxyls comprises: GB patent 1,261,829 described oxygen di-succinates, and 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.Comprise the substituent multi-carboxylate of sulfo group and comprise GB patent 1,398,421 and 1,398,422 and US patent 3,936,448 described sulfo-succinic acid salt derivatives, and GB patent 1,439,000 described sulfonation pyrolysis Citrate trianion.Preferred multi-carboxylate is the hydroxycarboxylate that per molecule comprises 3 carboxyls at the most, Citrate trianion more specifically.

The parent acid of monomer or oligomeric multi-carboxylate's sequestrant or can replenish as builder component with the mixture of its salt, for example, citric acid or Citrate trianion/citric acid mixture.

Borate washing assistant and can all can be used as water soluble detergency promoter of the present invention producing the boratory washing assistant that forms borate substance that contains under the washing composition storage requirement or under the wash conditions.

The suitable example of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and sodium orthophosphate and potassium, partially poly-/sodium phosphate, wherein, the polymerization degree is about 6-21, and phytate.Be partly dissolved or insoluble washing-aid compound

Detergent composition of the present invention or its component can comprise and be partly dissolved or insoluble washing-aid compound, and with composition weight meter, its content is generally 1-80 weight %, preferred 10-70 weight %, most preferably 20-60 weight %.

The example of basic water-insoluble washing assistant comprises sodium silicoaluminate.

The aluminosilicate zeolite that is suitable for has unit structure cell formula Na _z[(AlO ₂) _z(SiO ₂) _y]-xH ₂O, wherein, z and y are at least 6, and the mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.The silico-aluminate material can be hydrated form, and preferred crystal type comprises 10-28%, the water of preferred 18-22% combining form.

Aluminosilicate zeolite can be natural product, but the preferably synthetic product that obtains.Synthetic crystallization type aluminosilicate ion exchange material is zeolite A, zeolite B, zeolite P, X zeolite by name, and zeolite HS and composition thereof buys.Zeolite A has following formula

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein, x is 20-30, particularly 27.X zeolite has following formula:

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆]·276H ₂O

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

With composition weight meter, the content of zeolite MAP is 1-80 weight %, preferred 15-40 weight %.

Zeolite MAP is stated in EP 384070A (Unilever).It is defined as the zeolite P type alkali metal aluminosilicate, and its silica alumina ratio is not more than 1.33, is preferably 0.9-1.33, more preferably 0.9-1.2.

Making us interested especially is that silica alumina ratio is not more than 1.15, the zeolite MAP more preferably no more than 1.07.

Aspect preferred, the particle diameter of zeolite MAP detergent builders is with d ₅₀Value representation is preferably 1.0-10.0 μ m, more preferably 2.0-7.0 μ m, most preferably 2.5-5.0 μ m.

d ₅₀Value is meant that 50 weight % particulate diameters are worth less than this.Particle diameter specifically can be measured or only be measured with laser particle size analysis as the microscope that adopts scanning electron microscope to carry out by the routine analysis technical measurement.Other determines d ₅₀The method of value is stated in EP 384070A.Heavy metal ion chelating agent

Detergent composition of the present invention or its component preferably comprise a kind of heavy metal ion chelating agent as optional ingredient.So-called heavy metal ion chelating agent is meant that at this paper it can play the component of chelating heavy metal ion effect.These components also can have calcium and magnesium sequestering power, but preferably they demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

Detergent composition of the present invention comprises the heavy metal ion chelating agent of 0.005-20 weight % usually, preferred 0.1%-10 weight %, more preferably 0.25-7.5 weight %, most preferably 0.5-5 weight %.

Be applicable to that heavy metal ion chelating agent of the present invention includes organic phosphonates, as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and WSI 3310 salt.

Preferred diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1 in the above-mentioned substance, the 1-diphosphonate.

Other is applicable to that heavy metal ion chelating agent of the present invention comprises complexon I and polyamino carboxylic acid, as ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxy propylidene diamines disuccinic acid or its any salt.Preferred especially quadrol-N, N '-disuccinic acid (EDDS) or its an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, or its mixture.

Other is applicable to that heavy metal ion chelating agent of the present invention is an iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid, and as EP-A-317,542 and EP-A-399, described in 133.The present invention also can adopt as EP-A-516,102 described iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant.The present invention also can adopt EP-A-509,382 described Beta-alanine-N, N '-oxalic acid, the winter propylhomoserin-N that dies young, single acetate of N '-oxalic acid, the winter propylhomoserin of dying young-N-and imino-diacetic succsinic acid sequestrant.

EP-A-476,257 disclose the suitable sequestrant based on amino.EP-A-510,311 disclose the suitable sequestrant that is obtained by collagen, Keratin sulfate or casein.EP-A-528,859 disclose a kind of suitable alkyl imino oxalic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also can adopt.Glycine acid amides-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxy propylidene diamines-N, N '-disuccinic acid (HPDDS) also can adopt.The organic peroxide acid bleach system

The preferred feature of detergent composition of the present invention or its component is the organic peroxide acid bleach system.In preferred embodiments, bleach system comprises hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Produce organic peroxide acid by described precursor and hydrogen peroxide cource situ reaction.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In another preferred embodiment, the ready-formed organic peroxide acid is directly mixed in the composition.Comprising the mixture of hydrogen peroxide cource and organic peroxy acid precursor and the composition of ready-formed organic peroxide acid also can consider.Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

Inorganic perhydrate SYNTHETIC OPTICAL WHITNER is preferred hydrogen peroxide source.These salt add with the form of an alkali metal salt usually, particular certain cancers, and with composition weight meter, its content is 1-40 weight %, more preferably 2-30 weight %, most preferably 5-25 weight %.

The example of inorganic perhydrate salt comprises: perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.Inorganic perhydrate salt is not mixed by the crystalline solid of supplementary protection can.But, for some perhydrate salt, the preferred coated form that adopts described material in the particulate composition, thus good storage stability is provided in particulate product and/or when particulate product contacts with water, postpones to discharge perhydrate salt to described perhydrate salt.The suitable coating material comprises inorganic salt such as alkalimetal silicate, carbonate or borate, and composition thereof, perhaps organic substance such as wax, oil or fatty soap.

Sodium peroxoborate is preferred perhydrate salt, and it can be nominal formula NaBO ₂H ₂O ₂Monohydrate or tetrahydrate NaBO ₂H ₂O ₂3H ₂O.

Alkali metal percarbonate, particularly SPC-D are the preferred perhydrate of the present invention.SPC-D is for having corresponding to 2Na ₂CO ₃3H ₂O ₂The addition compound of chemical formula, it can crystalline solid be purchased.

The peroxide Potassium peroxysulfate is the another kind of inorganic perhydrate salt that is used for detergent composition of the present invention.Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that produces peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually, peroxyacid bleach precursor is expressed from the next:

Wherein, L is a leavings group, and X is substantially for being any functional group, thereby the peroxy acid structure that produces when crossing hydrolysis is

In detergent composition weight, the content of peroxyacid bleach precursor compound is preferably 0.5-20 weight %, more preferably 1-15 weight %, most preferably 1.5-10 weight %.

Suitable peroxyacid bleach precursor compound comprises one or more N-or O-carboxyl groups usually, and this precursor can be selected from all kinds.Such suitable precursor compound comprises the acylated derivatives of acid anhydride, ester, imide, lactan and imidazoles and oxime.The example of the useful matter in these classifications is disclosed in GB-A-1586789.Suitable ester is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386.Leavings group

Leavings group hereinafter referred to as the L group must have enough reactivities to occur in (for example in the cycles of washing) in the Best Times section to crossing hydrolysis reaction.But if L is too active, this activator will be difficult to stably be used for bleaching composition.

Preferred L group is selected from following radicals or its mixture:

Wherein, R ¹Be alkyl, aryl or the alkaryl that comprises 1-14 carbon atom, R ³For comprising the alkyl chain of 1-8 carbon atom, R ⁴Be H or R ³, R ⁵For comprising the alkenyl of 1-8 carbon atom, Y is H or solubilization radical.R ¹, R ³And R ⁴In any all can be replaced by any functional group basically, comprise for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acyl ammonia and ammonium or alkyl ammonium group.

Preferred solubilization radical is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, more preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, wherein, R ³For comprising the alkyl of 1-4 carbon atom, M is for providing deliquescent positively charged ion to bleach-activating agent, and X is for providing deliquescent negatively charged ion to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is halogen, hydroxide radical, methylsulfate or acetic acid anion.Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids when crossing hydrolysis.Preferred the type precursor provides peracetic acid when crossing hydrolysis.

Preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, and N ', N '-tetra-acetylatedization Alkylenediamine, wherein, alkylidene group comprises 1-6 carbon atom, and particularly wherein alkylidene group comprises those compounds of 1,2 and 6 carbon atom.Tetra acetyl ethylene diamine (TAED) most preferably.

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

The alkyl peroxy acids precursor compound that acid amides replaces is applicable to the present invention, comprises the compound of following general formula: Wherein, R ¹For containing the alkyl of 1-14 carbon atom, R ²For containing the alkylidene group of 1-14 carbon atom, R ⁵For H or comprise the alkyl of 1-10 carbon atom, L can be any leavings group basically.The bleach activating immunomodulator compounds that the acid amides of the type replaces is stated in EP-A-0170386.Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.Suitable O-acylations peroxybenzoic acid precursors compound comprises and replacing and unsubstituted benzoyloxy benzene sulfonate; and sorbyl alcohol, glucose and all sugar are carried out benzoylated product with benzoylation reagent; the imide-type compound comprises the urea that N-benzoyl succinimide, four benzoyl ethylene diamines and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.The positively charged ion peroxyacid precursor

Positively charged ion peroxyacid precursor compound produces the positively charged ion peroxy acid when crossing hydrolysis.

Usually, the positively charged ion peroxyacid precursor is by with positively charged functional group such as ammonium or alkyl ammonium group, and preferred ethyl or ammonium methyl group replace the peroxy acid part of suitable peroxyacid precursor compound and form.The positively charged ion peroxyacid precursor has suitable negatively charged ion such as halogen ionic salt is present in the solid detergent composition as a kind of usually.

The peroxyacid precursor compound that this positively charged ion replaces can be the derivative of peroxybenzoic acid or its replacement, precursor compound as the aforementioned.Perhaps, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides as described below replace.

The positively charged ion peroxyacid precursor is stated in following document: US 4,904, and 406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.1,382,594; EP 475,512; 458,396 and 284,292; With JP 87-318,332.

The example of preferred cation peroxyacid precursor is stated in UK number of patent application 9407944.9 and US number of patent application 08/298903,08/298650,08/298904 and 08/298906.

Suitable positively charged ion peroxyacid precursor comprises alkyl that ammonium or alkylammonium replace or in the tetra-acetylated glucose benzoyl peroxide of benzoyloxy benzene sulfonate, N-acidylate hexanolactam and single benzoyl any.Preferred N-acylations hexanolactam cationoid peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.Benzoxazine organic peroxy acid precursor

What also be suitable for is benzoxazine type precursor compound, EP-A-332 for example, and 294 and EP-A-482, those described in 807 particularly have the compound of following formula: Wherein, R ₁Be H, alkyl, alkaryl, aryl or aralkyl.The ready-formed organic peroxide acid

The organic peroxide acid bleach systems is except that comprising organic peroxyacid bleach precursor compound, or the another kind of selection of conduct, also can comprise the ready-formed organic peroxide acid, and with composition weight meter, its content is generally 1-15 weight %, more preferably 1-10 weight %.

A preferred class organic peroxy acid compound is the compound with acid amides replacement of following general formula: Wherein, R ¹Be alkyl, aryl or the alkaryl with 1-14 carbon atom, R ²Be alkylidene group, arylidene and the alkarylene with 1-14 carbon atom, R ⁵For H or have alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy acid compound that such acid amides replaces is disclosed in EP-A-0179386.

Other organic peroxide acid comprises diacyl and four acyl peroxides, particularly diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.The present invention also can adopt list and two to cross nonane diacid, list or two is crossed undecane dicarboxylic acid and the amino oxy hexanoic acid of crossing of N-naphthoyl.Bleaching catalyst

The present composition optionally comprises a kind of bleaching catalyst that contains transition metal.A kind of bleaching catalyst of suitable type is the catalyst system that comprises the active heavy metal cation of bleach catalyst with definition, as copper, iron or manganese positively charged ion, have very little or do not have the active assistant metal positively charged ion of bleach catalyst, as zinc or aluminium cations, with a kind of sequestrant, particularly ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt with catalysis and the defined stability constant of assistant metal positively charged ion.This catalyzer is disclosed in US 4,430,243.

The bleaching catalyst of other type comprises the manganese basigamy compound that is disclosed in the following document: US5,246,621 and US 5,244,594.The preferred embodiment of such 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) ₃And their mixture.Other case description is in european patent application 549272.Other is applicable to that ligand of the present invention comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-trichlorine heterocycle nonane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.

For example, suitable bleaching catalyst is referring to US 4,246, and 612 and 5,227,084.Referring to US5,194,416, the document is pointed out monokaryon manganese (IV) title complex such as Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH ₃) ₃(PF ₆).Another kind of bleaching catalyst (as described in US 5114606) is the water-soluble complexes of the polyol ligand of manganese (III) and/or the non-carboxylate salt that (IV) and at least has three continuous C-OH groups.Other example comprises the double-core Mn title complex that cooperates with four-N-dentate and two-N-dentate ligand, comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄ ⁺[(2,2 '-dipyridyl) ₂Mn ^III(u-O) ₂Mn ^IV(2,2 '-dipyridyl) ₂]-(ClO ₄) ₃

Other suitable bleaching catalyst is disclosed in the following document: EP-A-408,131 (cobalt complex catalyzer), EP-A-384,503 and 306,089 (metal-porphyrin catalyst), US 4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US 4,711,748 and EP-A-224,952 (being adsorbed in the Mn catalyst on the silico-aluminate), US 4,601,845 (being carried on manganese and zinc or magnesium salts on the silico-aluminate), US 4,626,373 (manganese/ligand catalyzer), US 4,119,557 (iron complex catalyzer), DE 2,054,019 (cobalt chelates catalyzer), CA 866,191 (salt that contains transition metal), US4,430,243 (sequestrant) and US4 with manganese positively charged ion and on-catalytic metallic cation, 728,455 (gluconic acid Mn catalysts).Additional enzymes

Composition of the present invention can comprise one or more additional enzymes.

Preferred additional enzymes material comprises the various enzymes that are purchased.Described enzyme comprises and is selected from following enzyme: lipase, cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucose-amylase, amylase, zytase, Phospholipid hydrolase, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme, β-dextran enzyme, arabinofuranosidase/xylosidase, Unidasa, chondroitinase, laccase or its mixture.

The preferably combination of additional enzymes in detergent composition of the present invention comprises the conventional mixture that is suitable for enzyme, as lipase, proteolytic enzyme, amylase, at and/or cellulase in conjunction with one or more plant cell-wall degrading enzymes.The example of suitable enzyme is referring to US 3,519, and 570 and 3,533,139.

The subtilisin (subtilisin BPN and BPN ') that suitable proteolytic enzyme obtains for the specific bacterial strain by Bacillus subtilus and Bacillus licheniformis.A kind of suitable proteolytic enzyme is to obtain from the bacterial strain of bacillus, and it all has maximum activity between pH value 8-12, be by Novo Industries A/S, Denmark, and hereinafter referred to as " Novo ", exploitation and with ESPERASE  sale.The preparation method of this kind of enzyme and similar enzyme states among 784 (Novo) at GB 1,243.Other suitable proteolytic enzyme comprises: available from ALCALASE , DURAZYM  and the SAVINASE  of Novo, available from MAXATASE , MAXACAL , PROPERASE  and the MAXAPEM  (Maxacal of protein engineering) of Gist-Brocades.Proteolytic ferment also comprises the bacterial serine proteolytic enzyme of modification, as the disclosed proteolytic enzyme of EP patent application serial number 87303761.8 (1987.4.28 application) (particularly the 17th, 24 and 98 page), is called as " proteolytic enzyme B " in this article; The EP199 that also comprises Venegas, the disclosed proteolytic enzyme of 404 (announcements on October 29th, 1986), it is a modified bacteria serine stretch protein lytic enzyme, it is called as " protease A " in this article.The proteolytic enzyme that is referred to herein as " proteolytic enzyme C " also suits, this proteolytic enzyme is the varient from the alkaline serine protease of bacillus, wherein, 27 place's Methionins replace arginine in the position, 104 place's tyrosine replace Xie Ansuan in the position, and 123 place's Serines replace l-asparagine in the position, and 274 place's L-Ala replace Threonine in the position, proteolytic enzyme C states in EP90915958:4, corresponding to WO 91/06637 (1991.5.16 is open).Genetically altered varient, particularly proteolytic enzyme C is also included within the scope of the invention.

The preferred protease that is called " proteolytic enzyme D " is a kind of carbonylic hydrolase varient, and it has a kind of at the undiscovered aminoacid sequence of nature, and it is the numbering according to the bacillus amyloliquefaciens subtilisin, obtain with different amino acid a plurality of amino-acid residues being replaced by the precursor carbonylic hydrolase, preferably also be incorporated into and correspondingly be selected from one or more amino acid residue positions of following position and replace :+99 ,+101 corresponding to position+76 places of described carbonylic hydrolase, + 103 ,+104 ,+107, + 123 ,+27 ,+105, + 109, + 126 ,+128 ,+135, + 156, + 166 ,+195 ,+197, + 204, + 206 ,+210 ,+216, + 217, + 218 ,+222 ,+260, + 265 and/or+274, as as described in the WO 95/10591 and the US patent application serial number 08/322,677 (1994.10.13 application) of C.Ghosh etc., be entitled as described in " bleaching composition that contains proteolytic enzyme ".

Be applicable to that also proteolytic enzyme of the present invention is at those proteolytic enzyme described in the following patent: EP251446 and WO 91/06637, and the varient of proteolytic enzyme BLAP  described in the WO 91/02792 and WO 95/23221 disclosed described proteolytic enzyme.

Also referring to the high pH proteolytic enzyme that is disclosed in WO 93/18140A (Novo) from bacillus NCIMB40338 bacterial strain.The enzyme-containing detergent that comprises proteolytic enzyme, one or more other enzymes and a kind of reversible protease inhibitors is stated in WO 92/03529A (Novo).When needs, can adopt to have the proteolytic enzyme that reduces absorption and strengthen hydrolysis, as WO 95/07791 (Procter ﹠amp; Gamble) described.The recombinant trypsin proteinoid enzyme that is applicable to washing composition of the present invention is disclosed in WO 94/25583 (Novo).Other suitable proteolytic enzyme is stated in EP 516 200 (Unilever).

Can mix the mixture of one or more proteolytic ferments in the detergent composition of the present invention, with composition weight meter, content is generally 0.0001-2%, preferred 0.001-0.2%, the more preferably pure enzyme of 0.005-0.1%.

If have lipase in detergent composition of the present invention, in detergent composition weight, the content of lipase is generally the 0.00005-2% organized enzyme, preferred 0.001-1%, more preferably 0.0002-0.05%.

Be applicable to that lipase of the present invention comprises the microorganism by Rhodopseudomonas group, as Situ Ci Shi aeruginosa atcc 19.154 is produced those, as GB1,372,034 is described.Suitable lipase comprises by microorganism Pseudomonas fluorescens IAM 1057 is that produce and demonstrates those lipase of positive immunological cross-reaction with lipase antibody.This lipase can trade(brand)name lipase P " Amano " from Amano PHarmaceutical Co.Ltd., Nagoya (Japan) is purchased, and below is referred to as " Amano-P ".Other suitable commercially available lipase comprises: Amano-CES, and the lipase that obtains by Chromobacter viscosum, for example, the lipase that Chromobacter viscosum mutation lipolyticum NRRLB 3673 obtains, available from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipase, available from U.S.Biochmical Corp., the U.S. and Disoynth Co., Holland, and the lipase that obtains by the gladiolus pseudomonas.Shi Yi lipase is the lipase such as M1 Lipase  and Lipomax  (Gist-Brocades) and Lipolase  and Lipolase Ultra  (Novo) especially, when they and combination of compositions of the present invention are used, finds very effective.Also Shi Yi lipolytic enzyme is stated in following document: EP 258 068, WO 92/05249 and WO 95/22615 (being Novo Nordisk) and WO 94/03578, WO 95/35381 and WO 96/00292 (Unilever).

Also Shi Yi enzyme is at [EC 3.1.1.50], and it is considered to a kind of lipase of particular variety, promptly need not the lipase of interface activation.Adding in detergent composition states in following document: WO-A-88/09367 (Genencor); State among WO 90/09446 (Plant Genetic System) and WO 94/14963 and the WO 94/14964 (Unilever).Be preferred for the LIPOLASE enzyme (referring to EP 341,947) of lipase among the present invention for deriving and be purchased by Novo by Humicola lanuginosa.

It is D96L lipolytic enzyme variant by the natural lipase of fetal hair detritus mould deutero-that another kind is preferred for lipase of the present invention.Most preferably use fetal hair humicola lanuginosa bacteria strain DSM 4106.

The D96L lipolytic enzyme variants is meant the 92/05249 described lipase variants as WO, and wherein, 96 places of putting on the throne become aspartic acid (D) resistates into leucine (L) from the natural lipase of fetal hair detritus mould.According to this nomenclature, described 96 places are substituted by leucine by aspartic acid and are represented as D96L in the position.In order to measure the activity of enzyme D96L, use standard LU test (analytical procedure, intemal Novo Nordisk AF 95/6-GB 1991.02.07).The substrate of D96L is by carrying out emulsification preparation as emulsifying agent to tributyrin (Merck) with gum arabic.The activity of lipase adopts the pH fixing means to measure when pH7.

Also can comprise a kind of amylase (α and/or β) in the detergent composition of the present invention or more than a kind of diastatic mixture.WO 94/02597 (Novo Nordisk A/S, on February 3rd, 1994 is open) discloses a kind of cleaning combination that adds mutant amylase.Also can be referring to WO 95/10603 (Novo Nordisk A/S, April 20 nineteen ninety-five is open).Other known amylase that is used for cleaning combination comprises α-Dian Fenmei and beta-amylase.α-Dian Fenmei is known in the art, comprise following document described those: US patent 5,003,257, EP 252,666, WO 91/00353, FR 2,676,456, EP 285,123, EP 525,610, EP 368,341 and GB 1,296,839 (Novo).Other suitable amylase is stable enhanced amylase, as WO 94/18314 (on August 18th, 1994 open) and WO 96/05295 (on February 22nd, 1996, Genencor) described, and the amylase variants that in direct parent, has additional modification, available from Novo Nordisk A/S, as described in WO 95/10603 (April nineteen ninety-five is open).Also the amylase of Shi Yonging is also as described in EP 277 216, WO 95/26397 and the WO 96/23873 (being Novo Nordisk).

The example that is purchased the α-Dian Fenmei product is: Purafect Ox Am , available from Genencor; Termamyl , Ban , Fungamyl  and Duramyl  are all available from Novo NordiskA/S Denmark.WO 95/26397 has described other suitable amylase: be characterised in that in the temperature 25-55 ℃ scope and pH value under the 8-10 scope, employing PHadebas ^The specific activity of alpha-amylase activity test determination compares Termanyl ^The α-Dian Fenmei of specific activity high at least 25%.What also be fit to is the variant of above-mentioned enzyme, and it is described among the WO 96/23873 (Novo Nordisk).WO 95/35382 has described other preferred starch lytic enzyme, all has the performance of improvement about the live vol of these enzymes and thermostability and high reactivity amount combined aspects.

If mix amylolytic enzyme in detergent composition of the present invention, with composition weight meter, the content of amylolytic enzyme is generally the pure enzyme of 0.0001-2%, preferred 0.00018-0.06%, more preferably 0.00024-0.048%.

Detergent composition of the present invention also can add one or more cellulases in addition.Suitable cellulase comprises the cellulase of bacterium and mould type, and preferably they have the best pH scope of 5-12 and the activity that is higher than 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is at people's such as Barbesgoard US 4,435,307, to state among J 61078384 and the WO96/02653, the document discloses the mould cellulase that is produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum respectively.EP 739 982 has described by the isolated cellulase of novel bacillus.Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275, DE-OS-2247832 and the WO 95/26398.

The example of this cellulase is by Humicola insolens bacterial strain (Humicola griseavar.thermoidea), particularly the cellulase of humicola lanuginosa strain DSM 1800 generations.Other suitable cellulase is that to come from the about 50KDa of molecular weight, iso-electric point be 5.5 and comprises the cellulase of 415 amino acid whose Humicola insolens; By Humicola insolens DSM1800 derive obtain～the 43kD endo-dextranase, it demonstrates cellulase activity; Preferred endoglucanase enzyme has aminoacid sequence described in the PCT of the being disclosed in application WO 91/17243.Same suitable cellulase is the EGIII cellulase from Trichoderma longibrachiatum, and (on September 29th, 1994 is open, and is Genencor) described as WO 94/21801.Shi Yi cellulase is the cellulase with color nursing role especially.The example of this cellulase is the described cellulase of following document: and EP patent application serial number 91202879.2 (application on November 6th, 1991, Novo).Carezyme and Celluzyme (Novo Nordisk A/S) are useful especially.Also referring to WO 91/17244 and WO 91/21801.Other suitable cellulase that is used for fabric nursing and/or cleaning properties is disclosed in WO 96/34092, WO 96/17994 and WO 95/24471.

Peroxidase also can add in the detergent composition of the present invention.Peroxidase can be used in combination with oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc.They are used for " solution bleaching ", prevent promptly that in washing process the dyestuff that comes off from substrate or pigment are transferred on other substrate the washing soln.Peroxidase is known in the art, for example comprises horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro and bromoperoxidase.The detergent composition that contains peroxidase is stated in following document: PCT International Application No. WO 89/099813, WO 89/09813 and EP number of patent application 91202882.6 (application on November 6th, 1991) and EP number of patent application 96870013.8 (application on February 20th, 1996).Same suitable laccase in addition.

Preferred toughener is the thiodiphenylamine of replacement and the cloves acid esters (alkyl ester that syringic acid C3-C5 replaces) and the phenol of phenoxazine, lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-first base phenoxazine (as described in WO 94/12621) and replacement.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.

If exist, the consumption of cellulase described in the composition and/or peroxidase is generally 0.0001-2 weight % organized enzyme in detergent composition weight.

When existing, the consumption of above-mentioned additional enzymes is generally the organized enzyme of 0.0001-2 weight % in detergent composition weight.Additional enzymes can be independent single component (comprising a kind of bead, particle of enzyme, the liquid of stabilization etc.) add, perhaps the mixture with two or more enzymes adds (as composite particles).The oxydasis scavenging agent

Other suitable detergent ingredients that can add is the oxydasis scavenging agent, and it is stated in common pending application application EP92870018.6 (application on January 31st, 1992).The example of this kind of enzyme oxidation scavengers is ethoxylation four ethylidene polyamine.Enzyme material

Various enzyme materials and their methods in the synthetic detergent composition of mixing also are disclosed in WO 9307263A and the WO 9307260A of Genencor International, the WO8908694A of Novo, in the people's such as McCarty that authorized on January 5th, 1971 US 3,553,139.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 US 4,101,457 and the US 4,507,219 of the Hughes that authorized on March 26th, 1985 in.Being used for the method that the enzyme material of liquid detergent formula and they are incorporated in these prescriptions is disclosed among the people's such as Hora that authorized on April 14th, 1981 the US 4,261,868.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology discloses and illustrates the US 3,600,319 the people such as Gedge on August 17th, 1971, among the EP 200,586 of the EP 199,405 and the Venegas on October 29th, 1986.The enzyme stabilization system for example also is described among the US 3,519,570.The useful bacillus AC13 bacterial strain that provides proteolytic enzyme, zytase and cellulase is described among the WO 9401532A of Novo.Organic polymer

Organic polymer is the preferred annexing ingredient of detergent composition of the present invention or its component, and it is the preferred ingredient of any grain fraction of detergent composition, and they play the effect that grain fraction is bonded together.So-called organic polymer is meant any organic polymer that is conventionally used as dispersion agent, anti redeposition agent or soil-suspending agent in detergent composition, is included in any high molecular organic polymer that is described as the clay flocculating agent herein.

With composition weight meter, the consumption of this organic polymer in detergent composition of the present invention is generally 0.1-30 weight %, preferred 0.5-15 weight %, more preferably 1-10 weight %.

The example of organic polymer comprises water-soluble organic homopolymerization or copolymerization poly carboxylic acid or its salt, and wherein, poly carboxylic acid comprises at least two and is no more than the carboxyl that two carbon atoms separate are opened each other.The polymkeric substance of latter's type is disclosed in GB-A-1, in 596,756.The example of this salt be molecular weight be the polyacrylic acid of 1000-5000 or polyacrylate and with the multipolymer of maleic anhydride, for example, molecular weight is 2000-100,000, particularly 40,000-80,000 multipolymer.Polymaleic acid salt or polymaleic acid polymkeric substance and salt thereof also are the examples that suits.

Be used for polyamino compound of the present invention and comprise by aspartate-derived material, comprise poly aspartic acid and EP-A-305282, EP-A-305283 and EP-A-351629 described those.

It is 1 that composition of the present invention also can suit to add the terpolymer that comprises the monomeric unit that is selected from toxilic acid, vinylformic acid, aspartic acid and vinyl alcohol or acetic ester, particularly molecular-weight average, 000-30, and 000, preferred 3,000-10, those of 000.

Other is applicable to that the organic polymer that mixes in the detergent composition of the present invention comprises derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose, Vltra tears, Type 3U and Natvosol.

Other useful organic polymer is that polyoxyethylene glycol, particularly molecular weight are 1000-10000, more preferably 2000-8000, most preferably from about 4000 polyoxyethylene glycol.Cationic soil release/antiredeposition compound

Detergent composition of the present invention or its component can comprise the water-soluble cationic ethoxylation amine compound with removal particulate fouling/clay soil and/or antiredeposition performance.These cation compounds are described in detail among EP-B-111965, US 4659802 and the US 4664848.Particularly preferred these cation compounds are ethoxylation positively charged ion monoamine, diamines or triamine.Particularly preferably be ethoxylation positively charged ion monoamine, diamines and triamine with following formula:

Wherein, X is a non-ionic group, is selected from H, C ₁-C ₄Alkyl or hydroxyalkyl acrylate or ether group and its mixture, a are 0-20, preferred 0-4 (as ethylidene, propylidene, hexa-methylene), and b is 2,1 or 0; For positively charged ion monoamine (b=0), n preferably is at least 16, and general range is 20-35; For cationic diamine or triamine, n is preferably at least about 12, and general range is about 12-42.

When these compounds were present in the composition, its content was generally 0.01-30 weight %, preferred 0.05-10 weight %.Foam inhibition system

When detergent composition of the present invention was mixed with the composition that is used to machine-wash, preferred composition comprised a kind of foam inhibition system, and with composition weight meter, its content is 0.01-15 weight %, preferred 0.05-10 weight %, more preferably 0.1-5 weight %.

Be used for suitable foam inhibition system of the present invention and can comprise any known defoaming compounds basically, for example, comprise siloxanes defoaming compounds and 2-alkyl alkanol defoaming compounds.

Defoaming compounds in this article refers to detergent composition solution, and particularly the foam that produces during stirred solution has for example inhibiting any compound or its mixture.

Being particularly preferred for defoaming compounds of the present invention is the siloxanes defoaming compounds, and it is defined as any defoaming compounds that comprises silicone components.This siloxanes defoaming compounds also comprises silica component usually.Use herein and also be that the term " siloxanes " of industrial common employing comprises various polysiloxane unit and all kinds alkyl and the relative high molecular weight polymers of containing.Preferred siloxanes defoaming compounds is a polysiloxane, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocking.

Other suitable defoaming compounds comprises monobasic aliphatic carboxylic acid and its soluble salt.These substance descriptions are in the US 2954347 of the Wayne St.John of mandate on September 27 nineteen sixty.Generally have as the monobasic aliphatic carboxylic acid of suds suppressor and salt thereof and to contain 10 to 24 carbon atoms, the hydrocarbyl chain of preferred 12 to 18 carbon atoms.The salt that is fit to comprises an alkali metal salt, sodium salt for example, sylvite, and lithium salts and ammonium salt and alkanol ammonium salts.

Other suitable defoaming composition for example comprises high-molecular weight aliphatic ester (as fatty acid triglyceride), monohydroxy-alcohol fatty acid ester, aliphatic C ₁₈-C ₄₀Ketone (as stearone), N-alkylation aminotriazine, as three to six alkyl melamines or two to the tetraalkyl diammonium chloride for triazine, it is to contain the uncle of 1-24 carbon atom or the product of secondary amine forms, propylene oxide, distearyl acid acid amides and single stearyl di(2-ethylhexyl)phosphate basic metal (as sodium, potassium, lithium) salt and phosphoric acid ester as cyanuryl chloride and two or three moles.

The preferred foam system that presses down comprises: (a) defoaming compounds, preferred siloxanes defoaming compounds most preferably comprises the silica of following combination

The alkane defoaming compounds

(i) 50-99 that polydimethylsiloxane, its content account for the siloxanes defoaming compounds is heavy

Amount %, preferred 75-95 weight %; With

The 1-50 that (ii) silicon-dioxide, its content account for siloxanes/silicon-dioxide defoaming compounds is heavy

Amount %, preferred 5-25 weight %;

The incorporation of wherein said silica/silicon oxygen alkane defoaming compounds is 5%-50 weight %,

Preferred 10%-40 weight %; (b) a kind of compound dispersing agent most preferably comprises siloxane glycol rake shape multipolymer (rake

Copolymer), its polyoxyalkylene content is 72-78%, ethylene oxide and propylene oxide

Mol ratio is 1: 0.9-1: 1.1, and its content is 0.5-10 weight %, preferred 1-10 weight %;

Particularly preferred the type siloxane glycol rake shape multipolymer is DCO544, by DOW

Corning company is purchased with trade(brand)name DCO544; (c) a kind of inert support fluid compound, most preferably it comprises C ₁₆-C ₁₈Ethoxylated alcohol, ethoxy

The baseization degree is 5-50, preferred 8-15, and its content is 5-80 weight %, preferred 10-70

Weight %.

Particularly preferred granular suds suppressing system is disclosed in EP-A-0210731, should pressing down foam system, to comprise a kind of siloxanes defoaming compounds and a kind of fusing point be 50-85 ℃ organic carrier material, wherein, the organic carrier material comprises the monoesters of glycerine and a kind of lipid acid, and described lipid acid has the carbochain that comprises 12-20 carbon atom.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein, the organic carrier material is lipid acid or the alcohol with the carbochain that contains 12-20 carbon atom, or its mixture, and its fusing point is 45-80 ℃.The polymeric dye transfer inhibitor

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

The polymeric dye transfer inhibitor is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.And these polymkeric substance all can be cross-linked polymer.A) polyamine N-oxide pllymers

Be applicable to that polyamine N-oxide pllymers of the present invention contains the unit with following structural: Wherein P is a polymerizable unit, and A is: X is 0 or 1; R ¹Be hydrogen or C ₁-C ₆The straight or branched alkyl; Or can form heterocyclic group with R; R is aliphatic group, ethoxylation aliphatic group, aromatic group, heterocyclic group group or alicyclic group or its any combination, and wherein the nitrogen-atoms in the N-O group can be connected with above-mentioned group or the nitrogen of N-O group is the part of these groups.

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

R wherein ₁, R ₂And R ₃Be aliphatic group, aromatic group, heterocyclic group group or alicyclic group or its combination; X or/and y or/and z is 0 or 1; With the part that the nitrogen of N-O group can be connected or wherein the nitrogen of N-O group forms these groups.The N-O group can constitute the part of this polymerizable unit (P) or can link to each other with polymeric skeleton, or can be above two kinds of situations combination.

Wherein the suitable polyamine N-oxide of a N-O group formation polymerizable unit part comprises polyamine N-oxide, and wherein, R is selected from: aliphatic group, aromatic group, alicyclic group or heterocyclic group group.The described polyamine N-oxide of one class comprises following polyamine N-oxide, and wherein the nitrogen of N-O group forms the part of R-group.Preferred polyamine N-oxide compound is following some: wherein, R is a heterocyclic group group, tetramethyleneimine, piperidines, quinoline, acridine and its derivative that pyrroles, imidazoles, the N-that replaces as pyridine, N-replaces.

Other suitable polyamine N-oxide is the polyamine oxide compound that links to each other with polymerizable unit of N-O group wherein.Preferred this class polyamine N-oxide is for to have the polyamine N-oxide of general formula (I), and wherein, R is aromatic group, heterocyclic group group or alicyclic group, and wherein, the nitrogen of N-O functional group is the part of described R group.These examples for compounds are following polyamine oxide compound, and wherein, R is heterogeneous ring compound such as pyridine, N-substituted azole, imidazoles and its derivative.

Polyamine N-oxide can be with almost polymerization degree acquisition arbitrarily.The polymerization degree is unimportant, so long as described material has required water-soluble and dye suspension ability.Usually, average molecular weight range is 500-1000,000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

The molecular-weight average that is suitable for N-vinyl imidazole of the present invention and N-vinylpyrrolidone copolymer is preferably 5,000-100, and 000, or be 5,000-50,000.The N-vinyl imidazole of preferred multipolymer and the mol ratio of N-vinyl pyrrolidone are 1-0.2.C) Polyvinylpyrolidone (PVP)

Detergent composition of the present invention also can adopt Polyvinylpyrolidone (PVP) (" PVP "), and the molecular-weight average of described Polyvinylpyrolidone (PVP) is 2,500-400,000.Suitable Polyvinylpyrolidone (PVP) can be from (the New York of ISP company, NY) and Montreal (Canada) (molecular-weight average is 10 with ProductName PVP K-15,000), (molecular-weight average is 40 to PVP K-30,000), (molecular-weight average is 160 to PVP K-60,000) and PVP K-90 (molecular-weight average is 360,000) be purchased.PVP K-15 also can be purchased from ISP company.Other is suitable is the Polyvinylpyrolidone (PVP) that can be purchased from BASF AG, comprises Sokalan HP 165 and Sokalan HP 12.D) Ju Yi Xi oxazolidinone

Detergent composition of the present invention also can adopt Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidinone is 2,500-400,000.E) polyvinyl imidazol

Detergent composition of the present invention also can adopt polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazol is preferably 2,500-400,000.White dyes

The hydrophilic white dyes that also can randomly contain some type of have an appointment 0.005% to 5% (weight) in the detergent composition of the present invention.

Can be used for hydrophilic white dyes of the present invention and have following structural formula:

R wherein ₁Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; With M be salt-forming cation such as sodium or potassium.

In following formula, R ₁Be anilino, R ₂Be N-2-two-when hydroxyethyl and M were positively charged ion such as sodium, whitening agent was 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal-UNPA-GX commercial.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that can be used in the detergent composition of the present invention.

In following formula, R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino-and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal 5BM-GX commercial.

In following formula, R ₁Be anilino, R ₂Be morpholino and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid sodium salt.Such special whitening agent can be bought from Ciba-Geigy company is commercial according to trade(brand)name Tinopal AMS-GX.The polymeric dirt release agent

Known polymeric dirt release agent (hereinafter referred to as " SRA ") optionally is used for detergent composition of the present invention.If adopt, composition comprises about 0.01-10.0 weight % usually, general 0.1-5 weight %, the SRA ' of preferred 0.2-3.0wt% _S

Preferred SRA ' _SUsually have the hydrophilic segment of the surface hydrophilic that makes hydrophobic fibre such as polyester and nylon and be deposited on the hydrophobic fibre and in whole washing and rinse cycle, all keep hydrophobic part adhered thereto, thereby can be used as the fixation point of hydrophilic segment.This makes handles spot easier the washing in cleaning process afterwards that produces later on SRA.

Preferred SRA ' _SComprise oligomeric terephthalate, normally by comprising the method preparation of following process: adopt a kind of metal catalyst such as titanium alkoxide (IV) to carry out at least a transesterification/oligomerization usually.This ester can adopt the additional monomer that can mix in the ester structure, two, three, four or more a plurality of position to make, and certainly, can not form thick on the whole crosslinking structure.

Suitable SRA ' _SThe sulfonated products that comprises the ester oligomer that is straight chain basically; it is partly formed by the oligomeric or polyester backbone of terephthaloyl and oxyalkylene oxygen repeating unit with the covalently bound allyl group deutero-sulfonation end-blocking of skeleton, for example as described in the US 4968451 of the J.J.Scheibel that authorizes in November 6 nineteen ninety and E.P.Gosselink.This ester oligomer can prepare through the following steps: (a) ethoxylation allyl alcohol; (b) product and terephthalic acid dimethyl ester (" DMT ") and 1 that will (a) in two step transesterification/oligomerization processes, 2-propylene glycol (" PG ") reacts; (c) in water with the product of (b) and sodium metabisulfite reaction.Other SRA ' _SComprise the nonionic end capped 1 among the people's such as Gosselink that authorized on December 8th, 1987 the US 4711730,2-propylidene/polyoxyethylene terephthalic acid polyester, for example product for preparing by the transesterification/oligomerization that gathers (ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other SRA ' _SExample comprise part among the US 4721580 of the Gosselink that authorized on January 26th, 1988-and all-end capped oligomer ester of negatively charged ion, as from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Nonionic end-blocking block polyester oligomeric compound among the US 4702857 of the Gosselink that on October 27th, 1987 authorized, for example by DMT, methyl (Me)-end capped PEG and EG and/or PG preparation, perhaps by DMT, EG and/or PG, the product of the mixture of end capped PEG of Me-and 5-sodium sulfonate dimethyl isophthalate preparation; With the Maldonado that authorized on October 31st, 1989, the negatively charged ion among people's such as Gosselink the US 4877896, the especially end capped terephthalate of sulfo group aroyl, the latter is typical useful SRA ' in laundry and fabric-conditioning product _S, an example be by-sulfosalicylic acid list sodium salt, the ester composition of PG and DMT preparation, but randomly preferably also contain the PEG of adding, for example, PEG3400.

SRA ' _SThe simple copolymerization block thing that also comprises ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate is referring to US 3,959,230 (Hays, 1976.5.25) and US 3,893,929 (1975.7.8, Basadur); Derivatived cellulose such as hydroxy ethers cellulose polymer compound are available from the METHOCEL of Dow company; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose; Referring to US 4,000,093 (Nicol etc., 1976.12.28); And methyl cellulose ether, it serves as about 120 centipoises of about 80-for the soltion viscosity that records with 2% aqueous solution under about 2.3,20 ℃ of about 1.6-that its every unit anhydroglucose has average replacement (methyl) degree.This material can METOLOSE SM100 and METOLOSE SM200 be purchased, they are trade(brand)names of the methyl cellulose ether produced by Shin-etsuKagaku Kogyo KK.

The SRA ' of other classification _SComprise: (I) nonionic terephthalate, use the vulcabond coupler to be connected on the polyester construction, referring to US 4,201,824 (Violland etc.) and US4,240,918 (Lagasse etc.); (II) has the SRA ' of carboxylate salt end group _S, by with 1,2, the 4-benzenetricarboxylic anhydride adds to known SRA ' _SOn, terminal hydroxyl is changed into 1,2, the preparation of 4-benzenetricarboxylic acid ester.Adopt the catalyzer of suitably selecting, by 1,2, the isolated carboxylic acid of 4-benzenetricarboxylic anhydride but not, make 1,2 by opening anhydride bond, the 4-benzenetricarboxylic anhydride forms the key that is connected with polymer ends.Nonionic SRA ' _SOr negatively charged ion SRA ' _SAll can be used as raw material, as long as have can esterified hydroxyl end groups for it.Referring to US 4,525,524 (Tung etc.).Other classification comprises: (III) based on the SRA ' of the connection carbamate kind of negatively charged ion terephthalate _S, referring to US 4,201,824 (Violland etc.).Other selectivity composition

Other selectivity composition that is fit to mix the present composition comprises spices, tinting material and filling salt, and preferred filling salt is a sodium sulfate.The form of composition

Composition of the present invention can be taked various physical form, comprises granule, tablet, small thin slices agent, lozenge and soap bar agent and liquid form.Liquid can be the aqueous solution or non-aqueous solution, can be gel form.Composition can be pretreatment compositions or conventional washing washing composition.The particularly so-called concentrated type granular detergent composition of composition is suitable for adding in the washing machine by the distribution device that is positioned in the washing machine rotating cylinder that accommodates the spot fabric.

This granule type detergent composition of the present invention or its component can adopt prepared in various methods, comprise spraying drying, driedly mix, extrude, agglomeration and granulation etc.The cationic quaternary ammonium tensio-active agent can add in other detergent component by mixing, agglomeration (preferably mixing with carrier substance), granulation or with spray-dired component.

Composition of the present invention also can be used for or with as the bleaching compositions of additives that comprises chlorine bleach be used in combination.

According to one aspect of the present invention, the median size of each component of particulate composition of the present invention should make preferably that diameter is no more than 15% greater than the particle of 1.8mm, and diameter is no more than 15% less than the particle of 0.25mm.Preferred median size makes that its particle diameter of particle of 10-50% is 0.2-0.7mm.

Ding Yi term " median size " is to calculate so herein: on the preferred Tyler sieve of a series of sieves, composition sample is sieved into a plurality of parts (being generally 5 parts).The aperture mapping of the relative sieve of weight of resulting each several part.Median size is to get the bore size that the sample of 50 weight % can pass through.

According to another aspect of the present invention, at least 80 weight %, the composition of preferred at least 90 weight % comprises the median size particle of 0.8mm at least, more preferably 1.0mm at least, most preferably 1.0 or 1.5-2.5mm.Most preferably be that at least 95% particle has this median size.A kind of like this particle preferably makes by extrusion molding.

The tap density of granular detergent composition of the present invention is generally at least 400, preferably 600g/l, more preferably 650-1200g/l at least.Tap density is measured by simple funnel and measuring cup device, be included in the conical funnel that rigidity in the substrate is installed, be provided with a vacuum breaker than low side at it and emit with the content that allows funnel and enter in the cylindrical measuring cup that is arranged at axial array below the funnel.The high 130mm of funnel, the internal diameter that reaches the lower end in the top is respectively l30mm and 40mm.Make its lower end at 140mm place, substrate surface top its installation.The height overall of measuring cup is 90mm, and interior height is 87mm, and internal diameter is 84mm.Its nominal volume is 500ml.

For measuring,, open vacuum breaker and make powder overflow measuring cup by craft powder filler in funnel.Take out measuring cup from support, excessive powder was scraped its upper edge and was removed by straight flange utensil such as knife.Then, the cup after filling is weighed, the value that the double in weight of powder is obtained just is tap density value (g/l).Carry out replicate measurement as required.

The solid of compacting can use any suitable compaction process to produce, and as compressing tablet, briquetting or extrude, preferably adopts pressed disc technique.The tablet that is preferred for the wash dining set method adopts the production of standard rotary tablet machine, and the pressure of employing is 5-13 KN/cm ², preferred 5-11 KN/cm ²Thereby the solid minimum hardness after the compacting is l76N-275N, preferred 195N-245N, and the Cl00 hardness test that adopts I.Hollandinstruments to provide is measured.This method can be used for preparing the even or stratiform tablet of virtually any size or shape.Preferred tablet is symmetric, to guarantee tablet uniform dissolution in washing soln.Clothes washing method

Machine washing method of the present invention is usually included in the washing machine and handles dirty clothing with wash water solution, dissolves or be dispersed with the machine washing detergent composition of the present invention of significant quantity in described solution.The detergent composition of so-called significant quantity is meant that the product with 10-300g is dissolved or dispersed in the washing soln that volume is 5-65L, and they are to be generally used for the common product dosage in the conventional machine washing method and the volume of washing soln.The size of dosage depends on actual conditions, as the degree of fouling of water hardness and dirty clothing.

Detergent composition for example can be distributed by the drawer type divider of washing machine, maybe detergent composition can be sprinkled upon on the dirty clothing that is positioned in the washing machine.

In one application, in washing methods, use distribution device.Distribution device is equipped with Betengent product, is used for before beginning wash(ing)cycle, product is directly added in the cylinder of washing machine, and its capacity should make it possible to be equipped with the Betengent product that is generally used for the q.s in the washing methods.

Before beginning washing, before washing machine installs clothing additional, simultaneously or afterwards, the distribution device that will comprise Betengent product is placed on the inside of rotating cylinder.When the washing machine cycles of washing begins, in rotating cylinder, add entry, make rotating cylinder carry out Periodic Rotating.The setting of distribution device should make and allow to comprise the dry detergent product, discharges this product in response to the stirring with the cylinder rotation then in cycles of washing, and this also is because its result who contacts with washing water.

In order to discharge Betengent product in washing process, device should have the perforate that a plurality of products can pass through.Perhaps, but this device can by sepage but the material that do not ooze solid phase prod make, allow to discharge the dissolved product.Preferably, Betengent product will discharge rapidly when cycles of washing begins, thereby in this cycles of washing stage, provides of short duration high local concentrations product in washing machine drum.

Preferred distribution device is reusable, should design to make container all keep globality in drying regime and cycles of washing.Be particularly preferred for using the distribution device of the present composition in following document, to state: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A--0288345 and EP-A-0288346.The particularly preferred granular laundry product distribution device that is used for also described in the article that J.Bland showed (being disclosed in " Manufacturing Chemist ", 1989.11, the 41-46 pages or leaves), and it is the type that is referred to as " granulette " usually.The preferred distribution device that another kind is used for the present composition is disclosed in PCT patent application WO 94/11562.

Particularly preferred distribution device is disclosed in EP patent application publication number 0343069 ﹠amp; In 0343070.Back one application discloses the device that contains flexible sheath, described sheath is the bag shape, extend from the supporting ring that limits the aperture, described aperture is suitable for allowing the packed once washing round-robin adequate prod that is useful on washing process, the part washing medium flows in the bag by the aperture, dissolved product, and solution outwards enters in the washing medium by the aperture then.Supporting ring is provided with covering appts and goes out to avoid wetting, undissolved product, and this set generally includes the wall that radially extends from the center hub of spoke wheel configuration, or a kind of similar structure, and its mesospore has spirrillum.

Perhaps, distribution device can be flexible container, as bag or pouch.This bag is a fibrous architecture, scribbles the protecting materials that do not seep water, thereby can take content in, as described in EP patent application publication number 0018678.Perhaps, it can be made by the water-insoluble synthetic polymeric material, is provided with banding or sealing so that it breaks in water-bearing media, described in EP patent application publication number 0011500,0011501,0011502 and 0011968.The form that makes things convenient for of the closure that water is frangible comprises the water-soluble binder that is provided with and seals along sack on one side, and described pouch is made by water pressuretightness polymeric membrane such as polyethylene or polypropylene.Machine washing tableware method

Can consider any tableware or clean dirty tableware, the method for particularly dirty silverware of being suitable for machine-washing.

Preferred machine washing tableware method comprises that it is selected from pottery, glass wares, holloware, silverware and cutlery and their mixture with dissolving or being dispersed with the machine-wash dirty goods of liquid, aqueous processing of tableware composition of significant quantity the present invention.The machine washing tableware composition of so-called significant quantity is meant that the product with 8-60g is dissolved or dispersed in the washing soln that volume is 3-10L, and this is to be generally used for the common product dosage in the conventional machine washing method and the volume of washing soln.The packing of composition

The bleaching composition of commercial sale can be packaged in any suitable container, comprises the container that those are constructed by paper, cardboard, plastics and any suitable laminating material.Preferred packing way is stated in EP number of patent application 94921505.7.That adopts among the embodiment writes a Chinese character in simplified form

In detergent composition, write a Chinese character in simplified form the component symbol and have following implication: the LAS straight chain C ₁₂Sodium alkyl benzene sulfonate TAS tallow alkyl sodium sulfate C _XyAS C _1x-C _1ySodium alkyl sulfate C46SAS C ₁₄-C ₁₆Secondary (2,3) sodium alkyl sulfate C _XyE _zS C _1x-C _1yThe condensation of sodium alkyl sulfate and z moles of ethylene oxide is produced

Thing C _XyE _zC _1x-C _1yBe mainly straight chain primary alcohol and average z moles of ethylene oxide

Condensation product QAS1 R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH) Cl ^-, R ₂=C ₉-C ₁₁Straight chained alkyl QAS2 R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH) Cl ^-, about 50% R ₂=C ₈Straight chain

Alkyl, about 50% R ₂=C ₁₀QAS3 R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH) Cl ^-, about 40% R ₂=C ₁₁Straight chain

Alkyl, about 60% R ₂=C ₉Straight chained alkyl.QAS4 R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH) Br ^-, R ₂=C ₆Straight chained alkyl QAS5 R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH) Cl ^-, R ₂=C ₁₀The straight chained alkyl carboxylic that the straight chained alkyl soap is obtained by the mixture of 80/20 butter and cocounut oil

Acid sodium CFAA C ₁₂-C ₁₄-Oleum Cocois alkyl N-methyl grape sugar acid amides TFAA C ₁₆-C ₁₈Alkyl N-methyl glucose amide TPKFA C ₁₂-C ₁₄The full cut lipid acid of topping STPP anhydrous sodium tripolyphosphate TSPP tetrasodium pyrophosphate zeolite A formula Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydrated aluminum silicate of O, just

The level particle diameter is that 0.1-10 μ m zeolite MAP silica alumina ratio is hydrated sodium aluminosilicate zeolite MAP NaSKS-6 formula δ-Na of 1.07 ₂Si ₂O ₅Crystal type layered silicate anhydrous citric acid citric acid borate Sodium Tetraborate carbonate anhydrous sodium carbonate, particle diameter is a 200-900 μ m supercarbonate anhydrous sodium bicarbonate, and size distribution is sodium sulfate anhydrous slufuric acid sodium silicate amorphous sodium silicate (SiO between 400-1200 μ m ₂: Na ₂O=2.0: 1) Citrate trianion citrate trisodium dihydrate, activity 86.4%, size distribution exists

1: 4 toxilic acid/acrylic copolymer of MA/AA between the 425 μ m-850 μ m, molecular-weight average about 70, the plain ether of the polyacrylic acid sodium polymer CMC sodium carboxyme-thylcellulose fibre of 000AA molecular-weight average 4,500 is 650 methyl available from the polymerization degree of Shin Etsu Chemicals

Ether of cellulose protease protein lytic enzyme, by Novo Industries A/S with trade(brand)name

Savinase sells, and activity is the 4KNPU/gAlcalase protease, is sold activity by Novo Industries A/S

Be 3AU/g cellulase cellulolytic enzyme, by Novo Industries A/S with trade(brand)name

Carezyme sells, and activity is 1000 CEVU/g amylase amylolytic enzymes, by Novo Industries A/S with trade(brand)name

Termamyl 120T sells, and activity is a 120KNU/g lipase lipolytic enzyme, by Novo Industries A/S with trade(brand)name

Lipolase sells, and activity is a 100KLU/gEndolase endoglucanase enzyme, is sold activity by Novo Industries A/S

Be 3000CEVU/gPB4 nominal formula NaBO ₂3H ₂OH ₂O ₂Sodium peroxoborate four hydrations

Thing PBl nominal formula NaBO ₂H ₂O ₂Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER percarbonate nominal formula 2Na ₂CO ₃3H ₂O ₂The nonanoly acyloxy benzene sulfonate TAED tetra acetyl ethylene diamine Mn catalyst Mn of SPC-D NOBS sodium-salt form ^IV ₂(m-O) ₃(1,4,7-trimethylammonium-1,4, three nitrogen heterocyclic ninth of the ten Heavenly Stems of 7-

Alkane) ₂(PF ₆) ₂, as US 5,246,621 and US 5,244,594 described DTPA diethylene triaminepentaacetic acid(DTPA) DTPMP diethylenetriamine five (methylene phosphonic acid salt), by Monsanto

Sell the sulfonation zinc phthalocyanine phthalocyanine SYNTHETIC OPTICAL WHITNER whitening agent 14 of encapsulate capsule in the dextrin polymer soluble of photoactivation with trade(brand)name Dequest 2060,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 24,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazine-2-yl) ammonia

Base) stilbene-2:2 '-disulfonic acid disodium HEDP 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid EDDS quadrol-N, the two ((C of N-disuccinic acid QEA ₂H ₅O) (C ₂H ₄O) _n(CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two

((C ₂H ₅O)-(C ₂H ₄O) _n); wherein; n is the 20-30PEGX polyoxyethylene glycol; molecular weight xPEO polyethylene oxide; molecular weight 50, the multipolymer SRP1 of 000TEPAE tetren ethoxylate PVP polyvinylpyrrolidonepolymers polymers PVNO polyvinylpyridine N-oxide compound PVPVI Polyvinylpyrolidone (PVP) and vinyl imidazole has oxygen ethylidene oxygen and to benzene with the sulfo group benzoyl is end capped

The short block of the ester SRP2 diethoxyization of diacyl skeleton poly-(propylene terephthalate)

Polymer siloxane defoamer polydimethylsiloxane foam control agent with as the siloxanes of dispersion agent-

Oxyalkylene copolymers, the ratio of described foam control agent and described dispersion agent

Be 10: 1-100: 1 alabaster wax

In the following embodiments, all content are all represented with the weight percentage of composition: embodiment 1

Following high density granular shape laundry detergent composition A-F is embodiments of the invention, is specially adapted to the machine washing condition in Europe:

	???A	???B	???C	???D	???E	???F
							LAS	??8.0	??8.0	??8.0	??8.0	??8.0	??8.0
C25E3	??3.4	??3.4	??3.4	??3.4	??3.4	??3.4
							C46AS	??1.0	??2.0	??2.5	???-	??3.0	??4.0
C68AS	??3.0	??2.0	??5.0	??7.0	??1.0	??0.5

QAS1	??0.05	???-	???-	????-	????-	??0.8
							QAS2	???-	??0.05	??0.8	????-	????-	???-
QAS3	???-	???-	???-	???1.4	???1.0	???-
							Zeolite A	??18.1	??18.1	??16.1	???18.1	???18.1	??18.1
Zeolite MAP	???-	??4.0	??3.5	????-	????-	???-
							Carbonate	??12.0	??12.0	??13.0	???26.0	???26.0	??26.0
Silicate	??1.4	??1.4	??1.4	???3.0	???3.0	??3.0
							NaSKS-6 (citric acid 79: 21)	??11.0	??6.0	??6.0	????-	????-	??12.5
Sodium sulfate	??26.1	??26.1	??25.0	???17.1	???24.1	??9.1
							MA/AA	??0.3	??0.3	??0.3	???0.3	???0.3	??0.3
CMC	??0.2	??0.2	??0.2	???0.2	???0.2	??0.2
							PB4	??9.0	??9.0	??9.0	???9.0	???9.0	??9.0
TAED	??1.5	??1.5	??1.0	???1.5	????-	??1.5
							Mn catalyst	???-	??0.03	??0.07	????-	????-	???-
DTPMP	??0.25	??0.25	???-	???0.25	???0.2	??0.25
							HEDP	??0.3	??0.3	??0.2	???0.2	???0.3	??0.3
EDDS	???-	???-	??0.4	???0.2	????-	???-
							QEA	??1.0	??0.8	??0.7	???1.2	????-	??0.5
Proteolytic enzyme	??0.85	??0.85	??0.26	???0.85	???0.8	??0.85
							Amylase	??0.1	??0.1	??0.4	???0.3	???0.1	??0.1
Lipase	??0.05	??0.6	??0.7	???0.1	???0.0	??0.1
							The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm)	??15 ??ppm	??15 ??ppm	??15 ??ppm	???15 ???ppm	???15 ???ppm	??15 ??ppm
Whitening agent 1	??0.09	??0.09	???-	???0.09	???0.0	??0.09
							Spices	??0.3	??0.3	??0.3	???0.3	???0.3	??0.3
Silicone antifoam agent	??0.5	??0.5	??0.5	???0.5	???0.5	??0.5
							Other/a small amount of component to 100%
Density (g/l)	??850	??850	??850	???850	???850	??850

Embodiment 2

Following granular laundry detergent compositions G-I is embodiments of the invention, is specially adapted to the machine washing condition in Europe:

	?????G	?????H	?????I
				LAS	????5.3	????5.61	????4.76
TAS	????1.3	????1.86	????1.57
				C45AS	????-	????2.24	????3.89
C25E3S	????-	????0.76	????1.18
				C45E7	????3.3	????-	????5.0
C25E3	????-	????5.5	????-
				QAS1	????0.8	????3.0	????2.5
STPP	????19.7	????-	????-
				Zeolite A	????-	????19.5	????19.5
Zeolite MAP	????2.0	????-	????-
				NaSKS-6/ citric acid (79: 21)	????-	????13.0	????10.6
Carbonate	????5.1	????18.4	????21.4
				Supercarbonate	????-	????2.0	????2.0
Silicate	????6.8	????-	????-
				Sodium sulfate	????37.8	????-	????7.0
MA/AA	????0.8	????1.6	????1.6
				CMC	????0.2	????0.4	????0.4
PB4	????5.0	????12.7	????-
				Percarbonate	????5.0	????-	????12.7
TAED	????0.5	????3.1	????-
				Mn catalyst	????0.04	????-	????-
DTPMP	????0.25	????0.2	????0.2
				HEDP	????-	????0.3	????0.3
QEA	????0.9	????-	????-
				Proteolytic enzyme	????0.85	????2.8	????0.85

Lipase	????0.15	????0.25	????0.15
				Cellulase	????0.28	????0.28	????0.28
Amylase	????0.4	????0.1	????0.1
				PVP	????0.9	????1.3	????0.8
The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm)	????15ppm	???27ppm	???27ppm
				Whitening agent 1	????0.08	????0.19	????0.19
Whitening agent 2	?????-	????0.04	????0.04
				Spices	????0.3	????0.3	????0.3
Silicone antifoam agent	????0.5	????2.4	????2.4
				On a small quantity/other component to 100%	????1.3	????1.1	????0.3

Embodiment 3

Following detergent formulation is embodiments of the invention, is specially adapted to the machine washing condition in Europe:

	????J	????K	????L	????M
					The blowing powder
????LAS	????6.0	????5.0	????11.0	????6.0
					????TAS	????2.0	????-	????-	????2.0
????QAS2	????0.8	????1.0	????-	????-
					????QAS3	????-	????-	????1.5	????0.6
Zeolite A	????-	????27.0	????-	????20.0
					????STPP	????24.0	????-	????24.0	????-
Vitriol	????6.0	????6.0	????9.0	????-
					????MA/AA	????2.0	????4.0	????6.0	????4.0
Silicate	????7.0	????3.0	????3.0	????3.0
					????CMC	????1.0	????1.0	????0.5	????0.6
????QEA	????-	????-	????1.4	????0.5
					Whitening agent	????0.2	????0.2	????0.2	????0.2
Silicone antifoam agent	????1.0	????1.0	????1.0	????0.3

????DTPMP	????0.4	????0.4	????0.2	????0.4
					Be sprayed to
????C45E7	????-	????-	????-	????5.0
					????C45E5	????2.5	????2.5	????2.0	????-
????C45E3	????2.6	????2.5	????2.0	????-
					Spices	????0.3	????0.3	????0.3	????0.2
Silicone antifoam agent	????0.3	????0.3	????0.3	????-
					Dried additive
Vitriol	????3.0	????3.0	????5.0	????10.0
					Carbonate	????6.0	????13.0	????15.0	????11.0
????PB1	????-	????-	????-	????1.5
					????PB4	????18.0	????18.0	????10.0	????18.5
????TAED	????3.0	????2.0	????-	????2.0
					????EDDS	????-	????2.0	????2.4	????-
Proteolytic enzyme	????3.25	????1.0	????3.25	????3.25
					Lipase	????0.4	????0.5	????0.4	????0.2
Amylase	????0.?2	????0.?2	????0.2	????0.4
					The SYNTHETIC OPTICAL WHITNER of photoactivation	????-	?????-	????-	????0.15
On a small quantity/other component to 100%

Embodiment 4

Following detergent granules prescription is embodiments of the invention.Prescription N is specially adapted to the machine washing condition of Japan.Prescription O-S is specially adapted to the machine washing condition of the U.S..

	???N	??O	??P	??Q	??R	??S
							The blowing powder
????LAS	??22.0	??5.0	??4.0	??9.0	??8.0	??7.0
							????C45AS	??7.0	??7.0	??6.0	??-	??-	??-
????C46AS	???-	??4.0	??3.0	??-	??-	??-
							????C45E35	???-	??3.0	??2.0	??8.0	??5.0	??4.0

????QAS1	??0.5	??-	??-	??-	???-	???-
							????QAS2	???-	??0.5	??-	??2.0	???-	??3.5
????QAS3	???-	??-	??0.8	??-	??3.0	???-
							Zeolite A	??6.0	??16.0	??14.0	??19.0	??16.0	??14.0
????MA/AA	??6.0	??3.0	??3.0	??-	???-	???-
							????AA	???-	??3.0	??3.0	??2.0	??3.0	??3.0
Sodium sulfate	??6.0	??3.3	??2.3	??24.0	??13.3	??19.3
							Silicate	??5.0	??1.0	??1.0	??2.0	??1.0	??1.0
Carbonate	??28.3	??9.0	??3.0	??25.7	??8.0	??6.0
							????QEA	??0.4	??0.4	??-	??-	??0.5	??1.1
????PEG?4000	??0.5	??-	??1.5	??1.0	??1.5	??1.0
							Sodium oleate	??2.0	??-	??-	??-	???-	???-
????DTPA	??0.4	??-	??0.5	??-	???-	??0.5
							Whitening agent	??0.2	??0.3	??0.3	??0.3	??0.3	??0.3
Be sprayed to
							????C25E5	??1.0	??-	??-	??-	???-	???-
????C45E7	???-	??2.0	??2.0	??0.5	??2.0	??2.0
							Spices	??1.0	??0.3	??0.3	??1.0	??0.3	??0.3
Agglomerate
							????C45AS	???-	??5.0	??5.0	??-	??5.0	??5.0
????LAS	???-	??2.0	??2.0	??-	??2.0	??2.0
							Zeolite A	???-	??7.5	??7.5	??-	??7.5	??7.5
????HEDP	???-	??1.0	??-	??-	??2.0	???-
							Carbonate	???-	??4.0	??4.0	??-	??4.0	??4.0
????PEG?4000	???-	??0.5	??0.5	??-	??0.5	??0.5
							Other component (water etc.)	???-	??2.0	??2.0	??-	??2.0	??2.0
Dried additive
							????TAED	??1.0	??2.0	??3.0	??1.0	??3.0	??2.0
????PB4	???-	??1.0	??4.0	??-	??5.0	??0.5
							????PB1	??6.0	??-	??-	??-	???-	???-
Percarbonate	???-	??5.0	??12.5	??-	???-	???-

Carbonate	???-	??5.3	??0.8	???-	??2.5	??4.0
							????NOBS	??4.5	???-	??6.0	???-	???-	??0.6
Cumene sulfonic acid	???-	??2.0	??2.0	???-	??2.0	??2.0
							Lipase	??1.6	??0.4	??0.4	??0.1	??0.05	??0.2
Cellulase	???-	??0.2	??0.2	???-	??0.2	??0.2
							Amylase	???-	??0.3	??0.3	???-	???-	???-
Proteolytic enzyme	???-	??1.6	??1.6	???-	??1.6	??1.6
							????PVPVI	???-	??0.5	??-	???-	???-	???-
????PVP	??0.5	???-	??-	???-	???-	???-
							????PVN0	???-	??0.5	??0.5	???-	???-	???-
????SRP1	???-	??0.5	??0.5	???-	???-	???-
							Silicone antifoam agent	???-	??0.2	??0.2	???-	??0.2	??0.2
Other/a small amount of component to 100%

Embodiment 5

Following detergent granules prescription is embodiments of the invention.Prescription W and X are specially adapted to the machine washing condition of the U.S..Prescription Y is specially adapted to the machine washing condition of Japan.

	????T	????U	????V
				The blowing powder
Zeolite A	????30.0	????22.0	????6.0
				Sodium sulfate	????19.0	????5.0	????7.0
????MA/AA	????3.0	????2.0	????6.0
				????LAS	????14.0	????12.0	????22.0
????C45AS	????8.0	????7.0	????7.0
				????QAS1	????0.7	????-	????-
????QAS2	????-	????2.2	????-
				????QAS5	????-	????-	????1.5
Silicate	????-	????1.0	????5.0
				Soap	????-	????-	????2.0

Whitening agent 1	????0.2	????0.2	????0.2
				Carbonate	????7.0	????16.0	????20.0
????DTPMP	????-	????0.4	????0.4
				Be sprayed to	????-	????1.0	????5.0
????C45E7	????1.0	????1.0	????1.0
				Dried additive
????HEDP	????1.0	????-	?????-
				????PVPVI/PVNO	????0.5	????0.5	????0.5
Proteolytic enzyme	????3.225	????3.25	????3.25
				Lipase	????0.4	????0.1	????0.2
Amylase	????0.1	????0.1	????0.1
				Cellulase	????0.1	????0.1	????0.1
????TAED	????-	????6.1	????4.5
				????PB1	????11.0	????5.0	????6.0
Sodium sulfate	????-	????6.0	????-
				Equipoise (moisture and other component)

Embodiment 6

Following granular detergent composition is embodiments of the invention, is specially adapted to the wash conditions in Europe.

	????W	????X
			The blowing powder	????-	????-
Zeolite A	????20.0	????-
			????STPP	????-	????20.0
????LAS	????6.0	????6.0
			????C68AS	????2.0	????2.0
????QAS1	????0.01	????-
			????QAS4	????-	????0.6
Silicate	????3.0	????8.0

????MA/AA	????4.0	????2.0
			????CMC	????0.6	????0.6
Whitening agent 1	????0.2	????0.2
			????DTPMP	????0.4	????0.4
Be sprayed to
			????C45E7	????5.0	????5.0
Silicone antifoam agent	????0.3	????0.3
			Spices	????0.2	????0.2
Dried additive
			Carbonate	????14.0	????9.0
????PB1	????1.5	????2.0
			????PB4	????18.5	????13.0
????TAED	????2.0	????2.0
			The SYNTHETIC OPTICAL WHITNER of photoactivation	????15ppm	????15ppm
Proteolytic enzyme	????1.0	????1.0
			Lipase	????0.2	????0.08
Amylase	????0.4	????0.4
			Cellulase	????0.1	????0.1
Vitriol	????10.0	????20.0
			Equipoise (moisture and other component)	????10.6	????5.12
Density (g/l)	????700	????700

Embodiment 7

Following detergent composition is embodiments of the invention:

	????Y	????Z	????AA
				The blowing powder
Zeolite A	????15.0	????15.0	????15.0
				Sodium sulfate	????0.0	????0.0	????0.0
????LAS	????3.0	????3.0	????3.0

????QAS2	????1.0	????-	????-
				????QAS5	????-	????3.0	????2.0
????DTPMP	????0.4	????0.2	????0.4
				????CMC	????0.4	????0.4	????0.4
????MA/AA	????4.0	????2.0	????2.0
				Agglomerate
????LAS	????5.0	????5.0	????5.0
				????TAS	????2.0	????2.0	????1.0
Silicate	????3.0	????3.0	????4.0
				????QEA	????-	????1.0	????0.6
Mn catalyst	????0.03	????-	????-
				Zeolite A	????8.0	????8.0	????8.0
Carbonate	????8.0	????8.0	????4.0
				Be sprayed to
Spices	????0.3	????0.3	????0.3
				????C45E7	????2.0	????2.0	????2.0
????C25E3	????2.0	????-	????-
				Dried additive
Citrate trianion	????5.0	????-	????2.0
				Supercarbonate	????-	????3.0	????-
Carbonate	????8.0	????12.5	????5.5
				Percarbonate	????-	????7.0	????10.0
????TAED	????6.0	????2.0	????5.0
				????PB1	????14.0	????7.0	????8.0
????EDDS	????-	????2.0	????-
				MW is 5,000,000 polyethylene oxide	????-	????-	????0.2
Wilkinite	????-	????-	????10.0
				Proteolytic enzyme	????1.0	????3.25	????3.25
Lipase	????0.4	????0.1	????1.0
				Amylase	????0.6	????0.6	????-

Cellulase	????0.6	????0.6	????-
				Silicone antifoam agent	????5.0	????5.0	????5.0
Dried additive
				Sodium sulfate	????0.0	????3.0	????0.0
Equipoise (moisture and other component) is to 100%
				Density (g/l)	????850	????850	????850

Embodiment 8

Following detergent formulation is embodiments of the invention:

	????BB	????CC	????DD	????EE
					LAS	????20.0	????14.0	????24.0	????22.0
QAS1	????0.7	????1.0	????0	????0
					QAS2	????-	?????-	????0.08	????-
QAS4	????-	?????-	????-	????1.0
					TFAA	????-	????1.0	????-	????-
C25E5/C45E7	????-	????2.0	????-	????0.5
					C45E3S	????-	????2.5	????-	????-
STPP	????30.0	????18.0	????30.0	????22.0
					Silicate	????9.0	????5.0	????10.0	????8.0
Carbonate	????13.0	????7.5	????-	????5.0
					Supercarbonate	????-	????7.5	????-	????-
Percarbonate	????-	????5.0	????9.0	????15.0
					?DTPMP	????0.7	????1.0	????-	????-
QEA1	????0.4	????1.2	????0.5	????2.0
					QEA2	????0.4	????-	????-	????-
SRP1	????0.3	????0.2	????-	????0.1
					MA/AA	????2.0	????1.5	????2.0	????1.0
CMC	????0.8	????0.4	????0.4	????0.2
					Proteolytic enzyme	????2.6	????3.25	????1.6	????1.6

Amylase	????0.8	????0.4	????-	????-
					Lipase	????0.2	????0.06	????0.25	????0.1
Cellulase	????0.15	????0.05	????-	????-
					The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm)	???70ppm	???45ppm	????-	???10ppm
Whitening agent 1	????0.2	????0.2	????0.08	????0.2
					PB1	????6.0	????2.0	????-	????-
HEDP	????-	????-	????2.3	????-
					TAED	????2.0	????1.0	????-	????-
Equipoise (moisture and other component) is to 100%

Embodiment 9

Following washing soap type detergent composition is embodiments of the invention:

	???FF	???GG	???HH	???II	????JJ	????KK	??LL	???MM
									?LAS	???-	???-	??19.0	??15.0	??21.0	??6.75	??8.8	???-
?C28AS	??30.0	??13.5	???-	???-	????-	??15.75	??11.2	??22.5
									Sodium laurate	??2.5	??9.0	???-	???-	????-	????-	???-	???-
?QAS1	???-	???-	???-	??0.08	????-	????-	??2.0	???-
									?QAS2	??1.5	???-	??0.8	???-	????-	????-	???-	???-
?QAS3	???-	??5	???-	???-	????-	????-	???-	??0.1
									?QAS4	???-	???-	???-	???-	??1.5	??0.04	???-	???-
?QAS5	???-	???-	???-	???-	????-	??0.04	???-	???-
									Zeolite A	??2.0	??1.25	???-	???-	????-	??1.25	??1.25	??1.25
Carbonate	??20.0	??3.0	??13.0	??8.0	??10.0	??15.0	??15.0	??10.0
									Lime carbonate	??21.5	???-	???-	???-	????-	????-	???-	???-
Vitriol	??5.0	???-	???-	???-	????-	????-	???-	???-
									?TSPP	??5.0	???-	??5.0	???-	??5.0	??5.0	??2.5	??5.0
?STPP	??5.0	??15.0	???-	???-	????-	??5.0	??8.0	??10.0
									Wilkinite	???-	??10.0	???-	???-	??5.0	????-	???-	????-

DTPMP	???-	??0.7	??0.6	???-	??0.6	??0.7	????0.7	????0.7
									MA/AA	??0.4	??1.0	???-	???-	??0.2	??0.4	????0.5	????0.4
SRP1	??0.3	??0.3	??0.3	??0.3	??0.3	??0.3	????0.3	????0.3
									Proteolytic enzyme	???-	??0.39	???-	???-	??0.26	???-	?????-	????-
Lipase	??0.07	??0.1	??0.15	??0.1	??0.2	??0.5	????0.1	????0.1
									Amylase	???-	???-	???-	???-	???-	???-	????0.1	????-
Cellulase	???-	??0.15	???-	???-	??0.15	???-	?????-	????-
									PEO	???-	??0.2	???-	??0.2	??0.3	???-	?????-	????0.3
Spices	??1.6	???-	???-	???-	???-	???-	?????-	????-

Claims (18)

1, a kind of is that pH value in the aqueous solution of 0.5 weight % is at least 8.0 detergent composition or its component in concentration, and it comprises the cats product of formula I:

R ¹R ²R ³R ⁴N ⁺X ^-(I) wherein, R ¹For having the hydroxyalkyl that is no more than 6 carbon atoms; R ²And R ³Be independently selected from C respectively ₁-C ₄Alkyl or alkenyl; R ⁴Be C ₅-C ₁₁Alkyl or alkenyl; X ^-Be counter ion, in 20 ℃ the 0.5 weight % detergent composition aqueous solution, it does not exchange with hydroxide ion basically.

2, a kind of is that pH value in the aqueous solution of 0.5 weight % is at least 8.0 detergent composition or its component in concentration, and it comprises the mixture of the cats product of formula I:

R ¹R ²R ³R ⁴N ⁺X ^-(I) wherein, R ¹For having the hydroxyalkyl that is no more than 6 carbon atoms; R ²And R ³Be independently selected from C respectively ₁-C ₄Alkyl or alkenyl; R ⁴Be C ₅-C ₁₁Alkyl or alkenyl; X ^-Be counter ion, in 20 ℃ the 0.5 weight % detergent composition aqueous solution, its basically with hydroxide ion exchange, and, wherein, in the mixture of the cats product of formula I, R in the cats product of at least 10 weight % ⁴Be C ₅-C ₉Alkyl or alkenyl.

3, according to the detergent composition of claim 1 or 2, wherein, counter ion X ^-Be selected from chlorion, bromide anion and nitrate ion.

4, according to the detergent composition of claim 3, wherein, counter ion X ^-Be chlorion.

5, according to the detergent composition of aforementioned each claim, wherein, with composition weight meter, the content of cats product is 0.01-20 weight %.

6, according to the detergent composition of claim 5, wherein, with composition weight meter, the content of cats product is 0.05-5 weight %.

7, according to the detergent composition of aforementioned each claim, wherein, in the cation compound of formula I, R ¹For-CH ₂CH ₂OH or-CH ₂CH ₂CH ₂OH; R ²And R ³The methyl of respectively doing for oneself; R ⁴Be C ₆-C ₁₁Alkyl.

8, according to the detergent composition of aforementioned each claim, wherein, in the cation compound of formula I, R ⁴Be C ₆-C ₉Or C ₁₁Group is preferably C ₆-C ₉Alkyl or alkenyl.

9, according to the detergent composition of aforementioned each claim, it comprises the mixture of the cats product of formula I compound, and described formula I compound comprises wherein R ⁴Be the formula I compound of more senior alkyl with n carbon atom, wherein n is 8-11 and R wherein ⁴For having the formula I compound than low alkyl group of (n-2) individual carbon atom.

10, according to the detergent composition of claim 9, wherein, cats product comprises the formula I compound than low alkyl group of having of the formula I compound with more senior alkyl of 5-95 weight % and 5-95 weight %.

11, according to the detergent composition of aforementioned each claim, it also comprises a kind of anion surfactant, and it is selected from the anion surfactant of formula II or III:

R ⁵OSO ₃ ^-M ⁺?????????????(II)

R ₆SO ₃ ^-M ' ⁺(III) wherein, R ⁵For having the straight or branched moieties of 9-22 carbon atom; R ⁶Be C ₁₀-C ₂₀Alkylbenzene; M ⁺And M ' ⁺Be selected from basic metal, alkaline-earth metal, alkanol ammonium and ammonium separately.

12, according to the detergent composition of claim 11, wherein, anion surfactant comprises the anion surfactant of formula II and the anion surfactant of formula III simultaneously, and weight ratio II: III is 15: 1-1: 2.

13, according to the detergent composition of claim 11 or 12, wherein, anion surfactant II is C ₁₆-C ₁₈Uncle or secondary straight or branched alkyl-sulphate, anion surfactant III is C ₁₁-C ₁₃Alkylbenzene sulfonate.

14, according to the detergent composition of aforementioned each claim, it also comprises a kind of nonionogenic tenside that is selected from alcohol ethoxylate, alkylphenol ethoxylate, polyhydroxy fatty acid amide, the many polyglycosides of alkyl and its mixture.

15, according to each composition among the claim 11-14, it comprises:

(a) cats product of the formula I of 0.25-3 weight %:

R ¹R ²R ³R ⁴N ⁺X ^-(I) wherein, R ¹The phenol that replaces for a kind of selectivity or have the hydroxyalkyl that is no more than 6 carbon atoms; R ²And R ³Be independently selected from C respectively ₁-C ₄Alkyl or alkenyl; R ⁴Be C ₆-C ₁₁Alkyl or alkenyl; X ^-Be counter ion;

(b) straight or branched uncle or the secondary alkane of 3-40 weight % as tensio-active agent (II)

Base vitriol;

(c) the alkylbenzene sulfonate of 6-23 weight % as tensio-active agent III; With

(d) nonionogenic tenside of 0.5-20 weight %.

16, according to the composition of aforementioned each claim, it is substantially free of SYNTHETIC OPTICAL WHITNER.

17, a kind of is that pH value in the aqueous solution of 0.5 weight % is at least 8.0 detergent composition or its component in concentration, and it is that cats product with formula I mixes with the alkaline system that contains one or more selectivity detergent components and obtains,

The cats product of described formula I is:

R ¹R ²R ³R ⁴N ⁺X ^-(I) wherein, R ¹The phenol that replaces for selectivity or have the hydroxyalkyl that is no more than 6 carbon atoms; R ²And R ³Be independently selected from C respectively ₁-C ₄Alkyl or alkenyl; R ⁴Be C ₆-C ₁₁Alkyl or alkenyl; X ^-Be counter ion, in 20 ℃ the 0.5 weight % detergent composition aqueous solution, it does not exchange with hydroxide ion basically.

18, a kind of in the family expenses washing machine method of washing clothes, wherein, before beginning washing, the distribution device of solid detergent composition that will comprise aforementioned each claim of significant quantity adds in the washing machine, wherein, described distribution device allows progressively to discharge described detergent composition during washing and enters in the washings.