CN1148868A - Detergent composition comprising lipoxidase enzymes - Google Patents

Abstract

There is provided a detergent composition comprising lipoxidase enzymes. The lipoxidase enzyme is preferably incorporated into the composition at a level of from 0.0001% to 2% active enzymes by weight of the composition.

Description

The detergent composition that comprises lipoxygenase

The present invention relates to comprise the detergent composition of lipoxygenase, it comprises wash dining set and laundry composition.

Be used to wash or purging method is judged by various factors as total performance of the Betengent product of laundry or wash dining set method, these factors comprise the soil removability to article in the washing, with the ability that stops soil redeposition, the perhaps breakdown products of dirt.

The food dirt often is difficult to remove from contaminated dirt-carrying body effectively.Be derived from the complicated dirt that the dirt bleached of fruit and/or vegetables juice especially will be removed.But the object lesson of this class dirt comprises hydrophobic bleaching of food products dirt, and particularly those have the chromophoric dirt of carotenoid, hereinafter are called the carotenoid dirt.The carotenoid dirt can be derived from Radix Dauci Sativae and tomato and any processed products and some tropical fruit and Stigma Croci that contains these components.

Lipoxygenase is used in the roasting industry with the naturally occurring yellow carotene pigment in the oxidation flour.Lipoxygenase is at detergent formulations, and particularly those use value that are designed in laundry, wash dining set and the family expenses cleaning operation also were not realized in the past.

The applicant finds that now when being included as the detergent composition component, lipoxygenase provides the stain/dirt that can bleach to remove benefit.Especially, but can make hydrophobic bleaching of food products dirt, especially those dirts that comprise carotenoid are removed.

Another problem that in some washing operation, occurs be from washing soln painted/can float the food soil redeposition to the washing in other article on or deposit to again on the container that comprises washing soln.When washing methods was artificial wash dining set method, said container can be bowl or kitchen sink, perhaps can be washing machine or automatic dish washer in addition.When substrate comprised the article of the food contamination that is contained a large amount of highly colored carotenoid dirts natively, this problem was especially outstanding.

The interior region of plastics during the applicant finds to wash and the washing container made by plastic material is subject to the deposition from the colouring foods dirt of washing soln especially.Said dirt can produce the stain of extremely difficult removal with the surface interaction of this plastics dirt-carrying body.

The terms of settlement that can float food dirt deposition problem generally is to bleach them before the fugitive dirt in washing soln is had an opportunity to be transferred on other goods in the washing.The applicant find now lipoxygenase can be used for providing this fugitive painted/can float the bleaching benefit of food dirt, thereby and suppress these soil transfer to the object of other existence.Also openly be not used for the application of the lipoxygenase of this purpose in the art.

The applicant also finds lipoxygenase is mixed the bleaching that helps any foreign pigment in the colourless liquid detergent composition, thereby helps to keep the colourless property and the transparency of composition.

An object of the present invention is to provide the detergent composition that contains lipoxygenase, said composition provides dirt/stain to remove benefit when being used to cleaning and washing operation.

A related objective of the present invention provides laundry and the wash dining set detergent composition that contains lipoxygenase, and it strengthens the removal of carotenoid dirt/stain.

But another target of the present invention provide lipoxygenase should be used for suppress from the bleaching of food products soil transfer of the wash water solution object in the washing procedure.

Summary of the invention

The invention provides and comprise at least a detergent composition that is selected from the detergent component of tensio-active agent and washing-aid compound, it is characterized in that said composition comprises lipoxygenase.Lipoxygenase

The necessary component of detergent composition of the present invention is a lipoxygenase.Lipoxygenase preferably is the 0.0001%-2% of composition weight with the organized enzyme, 0.0005%-0.5% more preferably, and more preferably the amount of 0.001%-0.05% is impregnated in the present composition.

Lipoxygenase is meant the enzyme that polybasic unsaturated fatty acid is oxidized to its corresponding hydroperoxide form in this article.Sometimes lipoxygenase is called linolic acid, oxygen oxydo-reductase.Carotinase is an object lesson of lipoxygenase.

This paper lipoxygenase comprises naturally occurring lipoxygenase and any variant by obtaining as gene engineering.Can ad hoc design any this variant according to the optimization of performance validity in detergent composition of the present invention.For example can design variable make enzyme that the stability of these composition component of running into is usually increased.In addition, can design variable make the best pH of enzyme variants or temperature performance scope satisfy special washing composition purposes.

Lipoxygenase can be obtained by soybean.The lipoxygenase that commerce is buied comprises the enzyme that those are sold by ICNBiochemicals.But bleaching of food products soil transfer restraining effect

According to a further aspect in the invention, but but lipoxygenase is used for transferring to washing methods on the dirt-carrying body surface in order to suppress the bleaching of food products dirt from the water-based washing soln.

Can bleach dirt mainly be meant any can be by the coloured food products dirt of bleaching action decolouring.But The present invention be more particularly directed to prevent the transfer of hydrophobicity bleaching of food products dirt, particularly those have the chromophoric dirt of carotenoid, and such as β-Hu Luobusu, Lyeopene, zeaxanthin or capsanthin, hereinafter the carotenoid dirt is made in common name.The carotenoid dirt can be from Radix Dauci Sativae and tomato and any processed goods and some tropical fruit and Stigma Croci that contains these components.

The Substrate material that the applicant finds to be easy to most to be subjected to bleach soil transfer is a plastic substance, such as polypropylene, polyethylene, polystyrene (comprising the alkyl butylstyrene) or PVC., these plastic object materials produce the lasting stain of this object but can interacting with any bleaching of food products dirt on the dirt-carrying surface.This stain visible especially on the translucent plastic material, this plastic substance is generally used for food storage case and storage tank.Detergent component

The present composition comprises at least a detergent component that is selected from tensio-active agent and washing-aid compound.

Detergent composition of the present invention also can comprise additional detergent components.The definite character of these annexing ingredients and its incorporation will depend on the physical form of composition and with the character of its cleaning operation that carries out.

The present composition for example can be formulated into craft and machine wash dining set composition, craft and machine laundry detergent composition, it comprises the laundry additive composition and is applicable to the pretreated composition of staining fabric, water washing assistant and water composition and be usually used in the composition of family expenses cleaning operation.

When being formulated into the composition that is applicable in machine-washing method such as machine laundry and the machine-washing tableware method, the present composition preferably comprises tensio-active agent and washing-aid compound, and additional one or more are preferably selected from the detergent component of organic polymer, SYNTHETIC OPTICAL WHITNER, additional enzymes, suds suppressor, lime soap dispersion agent, dirt suspension and anti redeposition agent and sanitas.Laundry composition also can comprise the softening agent as additional detergent components.

When being formulated into the composition that is used for the manually washing tableware method, the present composition preferably contains tensio-active agent and preferred other is selected from organic polymer, profoamer, II family metal ion, solvent, hydrotropic agent and additional enzymes.Surfactant system

Detergent composition of the present invention can comprise the tensio-active agent as main detergent component, and it is selected from negatively charged ion, positively charged ion, nonionic, amphoteric (ampholytic), amphoteric (amphoteric) and zwitterionics and composition thereof.

Tensio-active agent generally exists with the amount of 0.1%-60% (weight).Preferred incorporation is the 0.5%-35% of machine-washing tableware of the present invention, laundry and water lotion-aid combination weight, most preferably the 5%-60% of 0.5%-20% and manually washing tableware composition weight of the present invention, more preferably 15%-45%.

Tensio-active agent preferably be configured to composition in the enzyme component compatibility that exists.In liquid or gelatinous composition, most preferably tensio-active agent is prepared like this, make its raising or do not reduce the stability of any enzyme in these compositions at least.

The classification of one row typical negatively charged ion, nonionic, both sexes and zwitterionics and kind thereof are authorized the U.S.P.3 of Laughlin and Heuring on December 30th, 1975, be listed in 929,678.Other example is presented in " tensio-active agent and washing composition " (Schwartz, Perry and Berch, Vol.I and II).Authorized the U.S.P.4 of Murphy on March 31st, 1981,259,217 have provided the suitable cats product of row.

When existing, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics are used in combination with one or more negatively charged ion and/or nonionogenic tenside usually.Anion surfactant

Basically any anion surfactant that is used for washing purposes all can be included in composition.These tensio-active agents can comprise the salt (ammonium salt that comprises for example sodium, potassium, ammonium and replacement as one, two and triethanolamine salt) of anion sulfate acid, sulfonic acid, carboxylic acid and sarkosine tensio-active agent.

Other anion surfactant comprises fatty acid amide, alkyl succinate and sulfosuccinate, sulfosuccinic acid monoesters (especially saturated and the undersaturated C of 2-isethionate such as acyl group 2-isethionate, N-acyl taurine salt, methylamino esilate ₁₂-C ₁₈Monoesters), sulfosuccinic acid diesters (especially saturated and undersaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenation resin acid also are fit to, such as rosin, hydrogenation rosin be present in or derived from the resinous acid and the hydrogenation resin acid of butter.The anion sulfate acid salt surfactant

The anion sulfate tensio-active agent that is applicable to this paper comprises straight chain and chain primary alkyl sulfate, alkyl ethoxy sulfate, fatty oil thiazolinyl glycerine vitriol, alkyl phenol epoxy ethane ether salt, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) glucosamine sulfate and alkyl polysaccharide vitriol such as alkyl polyglycoside vitriol (non-ionic non-sulfuric acid compound described herein).

Alkyl ethoxy sulfate is preferentially selected oneself by the C that has every mole of about 20 moles of ethylene oxide of about 0.5-of ethoxylation ₆-C ₁₈Alkyl-sulphate.Preferred alkyl ethoxy sulfate surfactant for by ethoxylation to have every mole of about 0.5-about 20, the C of about 5 moles of ethylene oxide of preferably about 0.5- ₆-C ₁₈Alkyl-sulphate.The anion sulfoacid salt surfactant

Be applicable to that anionic sulphonate tensio-active agent herein comprises C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary alkyl sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil thiazolinyl glycerol sulfonate and its arbitrary mixture.The anionic carboxylic acid salt surfactant

Be applicable to that anionic carboxylate tensio-active agent herein comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap class (' alkyl carboxyl '), some secondary soap especially as herein described.

The preferred alkyl ethoxy carboxylate that is used for herein comprises those formulas RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Material, wherein R is C ₆-C ₁₈Alkyl, x are that 0-10 and b-oxide are distributed as on weight basis, and it is about 20% that x is that 0 amount of substance is less than, and x is less than about 25% greater than 7 amount of substance, when R mean value is C ₁₃Or more hour x mean value is about 2-4, when R mean value greater than C ₁₃The time the about 3-10 of x mean value and M be positively charged ion, be preferably selected from basic metal, alkaline-earth metal, ammonium, list, two and triethanol ammonium, most preferably be selected from sodium, potassium, ammonium and with the mixture of magnesium ion.Preferred alkyl ethoxy carboxylate be those wherein R be C ₁₂-C ₁₈The material of alkyl.

Be applicable to that herein alkyl polyethoxye multi-carboxylate tensio-active agent comprises the material of following formula:

RO-(CHR ₁-CHR ₂-O) _x-R ₃Wherein R is C ₆-C ₁₈Alkyl, x are 1-25, R ₁And R ₂Be selected from hydrogen, methyl acid group, succsinic acid group, hydroxy succinic acid group and composition thereof, wherein at least one R ₁Or R ₂Be succsinic acid group or hydroxy succinic acid group, and R ₃Be selected from the hydrocarbon of hydrogen, replacement or the unsubstituted 1-8 of a having carbon atom, and composition thereof.The secondary soap surfactant of negatively charged ion

Preferred soap surfactant is to comprise a unitary secondary soap surfactant of linking on the secondary carbon of carboxyl.Secondary carbon can be in the ring structure, for example in to the octyl group phenylformic acid, or in the cyclohexane carboxylic acid salt that alkyl replaces.Secondary soap surfactant should be preferably not ether-containing key, do not contain ester bond and hydroxyl not.In end group (amphiphilic moieties), should preferably there be nitrogen-atoms.Secondary soap surfactant contains 11-15 total carbon atom usually, although more more a little (for example reaching 16) allow, for example to the octyl group phenylformic acid.

Following formula further illustrates some preferred secondary soap surfactants: A. one class secondary soap very preferably comprises formula R ³CH (R ⁴) the secondary carboxyl material of COOM, wherein R ³Be CH ₃(CH ₂) _xAnd R ⁴Be CH ₃(CH ₂) _y, wherein y can be 0 or the integer of 1-4, x is that integer and the sum (x+y) of 4-10 is 6-10, preferred 7-9, most preferably 8.B. another kind of preferred secondary soap comprises those the wherein carboxylic compound of carboxyl substituent on the cyclic hydrocarbon unit, i.e. formula R ⁵-R ⁶The secondary soap of-COOM, wherein R ⁵Be C ⁷-C ¹⁰, preferred C ⁸-C ⁹Alkyl or alkenyl and R ⁶Be ring structure, (annotate: R such as benzene, pentamethylene and hexanaphthene ⁵Can with respect to the ring on carboxyl the neighbour, or contraposition).C. also have another kind of preferred secondary soap to comprise formula

CH ₃(CHR) _k-(CH ₂) _m-(CHR) _n-CH (COOM) (CHR) _o-(CH2) _p-(CHR) _q-CH ₃Secondary carboxylic compound, wherein each R is C ₁-C ₄Alkyl, wherein k, n, o, q are the integers of 0-8, its condition is that the total number of carbon atoms (comprising carboxylate salt) is 10-18.

In each following formula A, B and C, M can be any suitable, particularly water-soluble counter ion.

The secondary soap surfactant that is particularly preferred for herein is a water-soluble substances, and it is selected from 2-methyl isophthalic acid-undeeanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.The basic metal sarcosinate surfactant

Other suitable anion surfactant is formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl and M are alkalimetal ions.Preferred examples is the myristyl and the oleyl methyl sarcosinate of its sodium-salt form.Nonionogenic tenside

Any anion surfactant that is used for washing purposes can be included in composition basically.The useful nonionogenic tenside of exemplary non-limiting classification is listed below.The nonionic polyhydroxy fatty acid amide surfactant

Be applicable to that polyhydroxy fatty acid amide herein is that those have formula R ²CONR ¹The material of Z, wherein R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁-C ₂Alkyl, most preferably C ₁Alkyl (being methyl); And 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; With Z is to have to have at least 3 polyhydroxy alkyls of directly linking the straight-chain alkyl chain of the hydroxyl on the chain, or the derivative of its alkoxide (the preferred ethoxyquin or third oxidation).Z is preferably derived from the reducing sugar in the reductive amination process; More preferably Z is a glucosyl.The nonionic alkylphenol condensation

The polyethylene of alkylphenol, polypropylene and polybutene oxide compound condenses are applicable to herein.Usually, polyethylene oxide condensate is preferred.These compounds comprise the alkylphenol of about 18 carbon atom alkyls of about 6-with straight or branched configuration and the condensation product of alkylene oxide.The nonionic ethoxylated alcohol tensio-active agent

Fatty alcohol is applicable to the present invention with the alkyl ethoxylated condensation product of about 25 moles of ethylene oxide of about 1-.The alkyl chain of fatty alcohol can be straight or branched, uncle or secondary, comprise 6-22 carbon atom usually.Particularly preferably be the alcohol with the alkyl that contains 8-20 carbon atom and the condensation product of about 10 moles of ethylene oxide of the about 2-of every mol of alcohol.The fatty alcohol surfactant of nonionic ethoxylated/propoxylated

The C of ethoxylation ₆-C ₁₈Fatty Alcohol(C12-C14 and C12-C18) and C ₁₆-C ₁₈Mixed ethoxylated/propenoxylated Fatty Alcohol(C12-C14 and C12-C18), particularly water miscible, be the tensio-active agent that is applicable to herein.The Fatty Alcohol(C12-C14 and C12-C18) of preferred ethoxylation is that ethoxylation degree is the C of 3-50 ₁₀-C ₁₈Ethoxylized fatty alcohol, most preferably ethoxylation degree is the C of 3-40 ₁₂-C ₁₈Ethoxylized fatty alcohol.Preferred mixed ethoxylated/propenoxylated Fatty Alcohol(C12-C14 and C12-C18) has the alkyl chain length of 10-18 carbon atom, the ethoxylation degree of 3-30 and the propoxylation degree of 1-10.Nonionic EO/PO condenses with propylene glycol

Oxyethane is applicable to the present invention with the condensation product of the hydrophobic group that forms by propylene oxide and propylene glycol condensation.The molecular weight that the hydrophobic part of these compounds preferably has is about 1800 for about 1500-, and the demonstration water-insoluble.The example of this compounds comprises that some is by the PluronicTM tensio-active agent BASF sale, that can commercial buy.Nonionic EO condensed products with propylene oxide/ethylenediamine adduct

Oxyethane is applicable to herein with condensation product from the product of the reaction of propylene oxide and quadrol.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and has the molecular weight of about 2500-about 3000 usually.The example of this class nonionogenic tenside comprises that some is by the Tetronic BASF sale, that can commercial buy ^TMCompound.The nonionic alkyl polysaccharide surfactant

Be applicable to that alkyl polysaccharide herein is disclosed in the United States Patent (USP) 4 of authorizing Llenadao on January 21st, 1986,565, in 647, it has and contains about 30 carbon atoms of about 6-, the hydrophobic grouping and the polysaccharide of preferred about 16 carbon atoms of about 10-, for example many glycosides, and contain about 1.3-about 10, preferred about 1.3-is about 3, most preferably from about the hydrophilic radical of about 2.7 sugar units of 1.3-.Can use any reducing sugar that comprises 5 or 6 carbon atoms, for example glucose, semi-lactosi and half glycosyl part can replace the glucosyl part.(can at random hydrophobic grouping be connected positions such as 2-, 3-, 4-, therefore provide glucose or semi-lactosi) corresponding to glucoside or galactoside.Key between the carbohydrate can be between a position and 2-, 3-, 4-and/or 6-position on the aforementioned sugar unit of for example other sugar unit.

Preferred alkyl polyglycoside has following formula:

R ²O (C _nH _2nO) _t(glucosyl) _xR wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein alkyl group comprises 10-18, preferred 12-14 carbon atom; N is 2 or 3; T is 0-10, preferred 0; With x be 1.3-8, preferred 1.3-3, most preferably 1.3-2.7.Glycosyl is preferably derived from glucose.The nonionic fatty acid amide surfactant

Be applicable to that fatty acid amide surfactant herein is that those have formula R ⁶CON (R ⁷) ₂Material, R wherein ⁶Be to contain 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.Amphoterics

Be applicable to that amphoterics herein comprises amine oxide surfactant and alkyl both sexes carboxylic acid (amphocarboxylic acids).

An example that is applicable to alkyl both sexes dicarboxylic acid (amphodicarboxylic acid) herein is by Miranol, Inc., Dayton, Miranol (TM) the C2M Conc that NJ makes.Amine oxide surfactant

The amine oxide that is useful on herein comprises those formulas R ³(OR ⁴) _xNO (R ⁵) ₂Compound, R wherein ³Be selected from alkyl, hydroxyalkyl, amido propyl group and alkyl phenyl or its mixture, it comprises 8-26 carbon atom, preferred 8-18 carbon atom; R ⁴Be to comprise 2-3 carbon atom, the alkylidene group of preferred 2 carbon atoms or hydroxyl alkylidene group, or its mixture; X is 0-5, preferred 0-3; With each R ⁵Be to contain 1-3, the alkyl or the hydroxyalkyl of preferred 1-2 carbon atom, or contain 1-3, the polyoxyethylene groups of preferred 1 Oxyranyle.Radicals R ⁵Can be interconnection, for example by a Sauerstoffatom or a ring structure of nitrogen-atoms connection formation.

These amine oxide surfactants specifically comprise C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₈Alkoxyethyl dihydroxy ethyl amine oxide.These examples of substances comprise dimethyloctylamine oxide, diethyl decyl amine oxide, two-(2-hydroxyethyl) dodecyl amine oxide, dimethyl dodecyl amine oxide, dipropyl tetradecyl amine oxide, methylethyl hexadecyl amine oxide, dodecanoyl aminopropyl dimethyl oxidation amine, cetyl dimethyl amine oxide, stearyl dimethyl oxidation amine, butter dimethyl oxidation amine and dimethyl-2-hydroxyl octadecyl amine oxide.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide, and C ₁₀-C ₁₈Amidoalkyl dimethyl oxidation amine.Zwitterionics

Zwitterionics also can be impregnated in the detergent composition of the present invention.These tensio-active agents can broadly be described as the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the exemplary zwitterionicss that is used for herein.Beet alkali surface activator

The trimethyl-glycine that is used for herein is that those have formula R (R ¹) ₂N+R ²COO ^-Compound, wherein R is C ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl or C ₁₀-C ₁₆Amidoalkyl, each R ¹Generally be C ₁-C ₃Alkyl, preferable methyl, and R ²Be C ₁-C ₅Alkyl, preferred C ₁-C ₃Alkylidene group, more preferably C ₁-C ₂Alkylidene group.The example of suitable trimethyl-glycine comprises coconut acyl aminopropyl dimethyl betaine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C _12-14Acyl aminopropyl trimethyl-glycine; C _8-14Acyl ammonia hexyl diethyl betaines; 4[C _14-16Acyl group methyl acyl ammonia diethylamino]-1-carboxyl butane; C _16-18The amido dimethyl betaine; C _12-16Amido pentane diethyl betaines; [C _12-16Acyl group methyl amido dimethyl betaine.Preferred trimethyl-glycine is C _12-18Dimethyl-amino caproate and C _10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The title complex beet alkali surface activator also is applicable to herein.The sultaine tensio-active agent

Here useful sultaine is that those have formula (R (R ¹) ₂N ⁺R ²SO ₃ ^-Compound, wherein R is C ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl, more preferably C ₁₂-C ₁₃Alkyl, each R ¹Generally be C ₁-C ₃Alkyl, preferable methyl, and R ²Be C ₁-C ₆Alkyl, preferred C ₁-C ₃Alkylidene group and preferred hydroxyl alkylidene group.Amphoterics

Amphoterics can be impregnated in the detergent composition of the present invention.These tensio-active agents can broadly be described as the aliphatic derivatives of the second month in a season or tertiary amine, or heterocycle is secondary and the aliphatic derivatives of tertiary amine, and wherein aliphatic group can be a straight or branched.Cats product

Cats product also can be used for detergent composition of the present invention.Suitable cats product comprises and is selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀The quaternary ammonium surfactant of N-alkyl or alkenyl ammonium surfactant, wherein residual N position is replaced by methyl, hydroxyethyl or hydroxypropyl.Washing-aid compound

Detergent composition of the present invention can comprise the washing-aid compound as main detergent component.Washing-aid compound is the preferred ingredient of machine-washing tableware of the present invention and laundry composition, and usually with the 1%-80% of composition weight, preferred 10%-70%, most preferably the amount of 20%-60% exists.

The composition that is used for the manually washing tableware method comprises a spot of washing-aid compound at the most.Preferably, washing-aid compound is impregnated in manual washing in the dish composition with 1.5% amount of no more than composition weight.

Washing-aid compound can be water miscible or most of water-insoluble.When composition is when being used for wash dining set, particularly when machine-washing tableware composition and rinse aids composition, water soluble detergency promoter is preferred.

Suitable washing-aid compound comprises the water-soluble monomer multi-carboxylate, or its sour form, homopolymerization or copolymerization poly carboxylic acid or its salt, wherein poly carboxylic acid comprises at least two kinds by the mixture of no more than two carbon atom carboxyls spaced apart from each other, carbonate, supercarbonate, borate, phosphoric acid salt, silicate and any aforementioned substances.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligomer types, although because cost and performance, the monomer multi-carboxylate is normally preferred.

The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt and the ether derivant thereof of lactic acid, oxyacetic acid.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing three carboxyls comprises, particularly Citrate trianion, aconitate (aconitrates) and citraconate, and the succinate derivative is such as in English Patent 1,379, carboxymethyl oxygen base succinate described in 241, in English Patent 1,389, newborn oxygen base succinate described in 732 and at the aminosuccinic acid salt described in the Holland application 7205873 and oxygen Quito carboxylate salt material as in English Patent 1,387,2-oxa--1,1 described in 447,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls is included in English Patent 1,261, the oxygen base disuccinate, 1,1,2 described in 829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and be included in English Patent 1,398, disclosed sulfo-succinic acid salt derivative and in English Patent 1,439 in 421 and 1,398,422 and at United States Patent (USP) 3,936,448, the sulfonated pyrolysis Citrate trianion described in 000.

Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene acid anhydride pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane-hexacarboxylic acid salt and polyvalent alcohol such as sorbyl alcohol, mannitol and Xylitol.Aromatic multi-carboxy acid's salt is included in English Patent 1,425, disclosed mellitic acid, 1,2,4,5-pyromellitic acid and phthalic acid derivative in 343.

In the above-claimed cpd, preferred multi-carboxylate is the hydroxycarboxylate that per molecule contains three carboxyls at most, the Citrate trianion of more specifically saying so.

The parent acid of the mixture of monomer or oligomeric multi-carboxylate's sequestrant or itself and its salt, for example citric acid or Citrate trianion/citric acid mixture also are considered to useful builder component.

Borate washing assistant and contain the washing assistant that can under washing composition storage or wash conditions, produce boratory one-tenth borate substance and also can be used, but be lower than about 50 ℃, particularly be lower than under about 40 ℃ wash conditions not preferred.

The example of carbonate builders is alkaline earth and alkaline carbonate, it comprise yellow soda ash and concentrated crystal soda and with the mixture of the thin lime carbonate of disclosed spy on November 15th, 1973 disclosed German patent application 2,321,001.

The object lesson of phosphate builders is alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, Sodium polymetaphosphate, and wherein the polymerization degree is about 6-21, and phytate.

Suitable silicate comprises ratio SiO ₂: Na ₂O is the water-soluble metasilicate of 1.0-2.8, and ratio is that 1.6-2.4 is preferred and ratio is 2.0 to be most preferred.Silicate can be anhydrous salt or salt hydrate form.Ratio SiO ₂: Na ₂O is that 2.0 water glass is most preferred silicate.

Preferably with the 5%-50% of composition weight, more preferably the amount of 10%-40% is present in the machine-washing dish washing detergent compositions of the present invention silicate.

The example of water-soluble lower washing assistant comprises crystalline layered silicate and most of water-insoluble sodium silicoaluminate.

Crystalline layered sodium silicate has general formula:

NaMSi _xO _X+1yH ₂O wherein M is sodium or hydrogen, and x is the number of 1.9-4 and the number that y is 0-20.This class crystalline layered sodium silicate is disclosed among the EP-A-0164514, and its preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.For purposes of the present invention, the x value in the above-mentioned general formula is 2,3 or 4 and preferred 2.Most preferred material is δ-Na ₂Si ₂O ₅, can obtain from Hoechst AG by NaSKS-6.

The crystalline layered sodium silicate material is preferably as particle and a kind of solid, water-soluble ionisable substance uniform mixing and be present in the granular detergent composition.Solid, water-soluble ionisable substance are selected from organic acid, organic and inorganic acid salt and composition thereof.

Suitable aluminosilicate zeolite has unit structure cell formula Na ₂[(AlO ₂) _z(SiO ₂) _y] XH ₂O, wherein z and y are at least 6; Z is that 1.0-0.5 and X are at least 5 to the mol ratio of y, preferred 7.5-276, most preferably 10-264.The silico-aluminate material is a hydrated form, and preferably comprises 10%-28%, more preferably the crystal of 18%-22% crystal water.

The silico-aluminate ion exchange material can be naturally occurring material, but preferably synthetic produce.Synthetic crystallization silico-aluminate ion exchange material can title zeolite A, zeolite B, zeolite P, X zeolite, zeolite MAP, zeolite HS and composition thereof buy.Zeolite A has formula

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

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂The O organic polymer

Organic polymer is the particularly preferred component of detergent composition of the present invention.This polymkeric substance stops be in the suds deposition on the article of enzyme dirt degraded breakdown products.

Organic polymer mainly is meant any organic compound that is used as dispersion agent, antiredeposition and soil-suspending agent in detergent composition usually.

Organic polymer is generally with the 0.1%-30% of composition weight, preferred 0.5%-15%, and most preferably the amount of 1%-10% is mixed in the detergent composition of the present invention.

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 by the spaced-apart carboxylic group of no more than two carbon atom.Back one base polymer is disclosed in GB-A-1, in 596,756.The example of these salt be MWt2000-5000 polyacrylate and with the multipolymer of maleic anhydride, these molecular weight of copolymer are 20,000-100,000, particularly 40,000-80,000.

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

The polyamino compound is useful on herein, and it comprises those materials derived from aspartic acid, such as at EP-A-305282, and disclosed those materials among EP-A-305283 and the EP-A-351629.

Other organic polymer that is fit to mix in the detergent composition of the present invention comprises derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose and Natvosol.

Useful organic polymer in addition is a polyoxyethylene glycol, and particularly those molecular weight are 1000-10000, more particularly molecular weight be 2000-8000 and most preferably molecular weight be about 4000 polyoxyethylene glycol.The lime soap dispersing agent compound

The present composition can comprise the lime soap dispersing agent compound, and it has as hereinafter defining no more than 8, and is preferred no more than 7, most preferably no more than 6 lime soap dispersing power (LSDP).The lime soap dispersing agent compound is preferably with the 0.1%-40% of composition weight, more preferably 1%-20%, and most preferably the amount of 2%-10% exists.

Lime soap dispersing agent is the basic metal that stops lipid acid, and ammonium or amine salt are by calcium or the sedimentary material of magnesium ion.Measure lime soap dispersing power (LSDP) by using the calcium soap distributed test, thereby provided lime soap dispersing agent measure of effectiveness value, as the article of H.C.Borghetty and C.A.Bergman, U.S. oiling association will, the 27th volume is described in the 88-90 page or leaf (1950).This calcium soap distributed test method is by this area professional, the professional's widespread use that for example relates in following comment: W.N.Linfield, tensio-active agent science book series, the 7th volume, page 3; W.N.Linfield, tensio-active agent detects, the 27th volume, 159-161 page or leaf (1990); And M.K.Nagarajan, W.F.Masler, makeup and toiletry, the 104th volume, 71-73 page or leaf (1989).LSDP is a dispersion agent in order to disperse by the 0.025g sodium oleate at 333ppm CaCO ₃(Ca: Mg=3: the weight percent of the sodium oleate that the calcium soap deposition that 2) forms in the 30ml water of equivalent hardness is required.

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

Be used for of the present inventionly having the exemplary surfactants that is not higher than 8 LSDP and comprising C ₁₆-C ₁₈Dimethyl oxidation amine, average degree of ethoxylation are the C of 1-5 ₁₂-C ₁₈Alkyl ethoxy sulfate, particularly ethoxylation degree are the C of about 3 (LSDP=4) ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant and average degree of ethoxylation are the C of 12 (LSDP=6) or 30 ₁₃-C ₁₅Ethoxylated alcohol, it is sold with trade(brand)name LutensolA012 and Lutensol A030 respectively by BASF GmbH.

Be applicable to that polymerization lime soap dispersing agent herein is described in the article of M.K.Nagarajan and W.F.Masler, as seen, makeup and toiletry, the 104th volume, 71-73 page or leaf (1989).The example of these polymerization lime soap dispersing agent comprises the water-soluble salt of multipolymer of the acrylamide of some vinylformic acid, methacrylic acid and composition thereof and acrylamide or replacement, and these polymkeric substance generally have 5,000-20,000 molecular weight.Press down foam system

When being formulated as when being used for the machine-washing composition, detergent composition of the present invention preferably comprises and presses down foam system, and its amount is the 0.01%-15% of composition weight, preferred 0.05%-10%, most preferably 0.1%-5%.

Be applicable to that the foam that presses down herein is to comprise any basically known anti-alveolation compound, comprise as the anti-alveolation compound of siloxanes anti-alveolation compound of 2-alkyl alcohol (alcanol) and the anti-alveolation compound of paraffin.

The anti-alveolation compound here is meant any in order to suppress the solution by detergent composition, particularly the foamy compound that produces in the presence of the stirring of this solution or the mixture of compound.

The anti-alveolation compound that is particularly preferred for herein is the anti-alveolation compound of polysiloxane, is defined as any anti-alveolation compound that contains the polysiloxane component here.The anti-alveolation compound of these polysiloxane generally also comprises silica component.Here comprise the various relative high molecular weight polymers that contain siloxane unit and all kinds of alkyl with the term " polysiloxane " that generally in industry, uses.The preferred anti-alveolation compound of polysiloxane is a polysiloxane, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocks.

Other anti-alveolation compound that is suitable for comprises monobasic carboxylic fatty acids and soluble salt thereof.These materials are authorized in September 27 nineteen sixty in the United States Patent (USP) 2,954,347 of Wayne St.John and are described.Monobasic carboxylic fatty acids and salt thereof as suds suppressor generally have about 24 carbon atoms of 10-, the hydrocarbyl chain of preferred 12-18 carbon atom.Suitable salt comprises an alkali metal salt such as sodium, potassium, lithium salts and ammonium and alkanol ammonium salt.

Other suitable anti-alveolation compound for example comprises high-molecular-weight hydrocarbons such as paraffin, fatty acid ester (as fatty acid glyceryl ester), the fatty acid ester of monohydroxy-alcohol, aliphatic C ₁₈-C ₄₀Product three to six alkyl melamines or two that the alkylating aminotriazine of ketone (as stearone) N-generates as the uncle of containing 1-24 carbon atom as cyanuryl chloride and two or three moles or secondary amine are to tetraalkyl diammonium chloride triazine, 1,2 epoxy prapane, two stearic amide and single stearyl-two basic metal (as sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.Hydrocarbon such as paraffin and chloro paraffin can use with liquid form.Liquid hydrocarbon is liquid under room temperature and normal atmosphere, and has-40 ℃ approximately-Yue 5 ℃ pour point and be not less than the minimum boiling point of 110 ℃ (barometric points).Knownly can also use waxy hydrocarbon, preferred fusing point is lower than about 100 ℃ waxy hydrocarbon.For example authorize people's such as Gando lfo United States Patent (USP) 4,265,779 on May 5th, 1981 and described the hydrocarbon suds suppressor.Therefore, these hydrocarbon comprise the saturated or unsaturated hydrocarbons with heterocycle aliphatic series with about 70 carbon atoms of about 12-, alicyclic, aromatics.The term " paraffin " that uses in this suds suppressor is discussed comprises the real paraffin and the mixture of cyclic hydrocarbon.

The multipolymer of oxyethane and propylene oxide, particularly having alkyl chain length is 10-16 carbon atom, and ethoxylation degree is 3-30, and the blended ethoxylated/propoxylated fatty alcohol of propoxylation degree 1-10 also is to be applicable to anti-alveolation compound of the present invention.

Be applicable to that the anti-alveolation compound of 2-alkyl-pure alcanols herein is described among the DE4021265.Be applicable to that herein 2-alkyl-alcohol (alcanols) is by the C that contains terminal hydroxyl ₆-C ₁₆Alkyl chain and said alkyl chain in a certain position by C ₁-C ₁₀Alkyl chain replaces.The mixture of 2-alkyl-alcohol (alcanols) can be used for the present composition.

The preferred foam system that presses down comprises (a) anti-alveolation compound, the preferred anti-alveolation compound of polysiloxane, and the anti-alveolation compound of polysiloxane most preferably, it comprises

(i) polydimethylsiloxane, its consumption are the 50%-of the anti-alveolation compound of polysiloxane

99%, preferred 75%-95%;

(ii) silicon-dioxide, its consumption are the anti-alveolation compound of polysiloxane/silicon-dioxide weight

1%-50%, preferred 5%-25%;

The anti-alveolation compound of wherein said silicon-dioxide/polysiloxane is with 5%-50%, and is preferred

The amount of 10%-40% (weight) is impregnated in; (b) compound dispersing agent, comprise that most preferably having polyoxyalkylene content is that 72-78% and oxyethane are 1 to the 1,2 epoxy prapane ratio: 0.9-1: polysiloxane 1,2-ethylene glycol comb copolymer of 1.1, its amount is 0.5%-10%, preferred 1%-10% (weight);

Particularly preferred this class polysiloxane 1 comb copolymer is DC0544, can

Buy with trade(brand)name DC0544 commerce from DOW Corning; (c) inert support fluid compound comprises that most preferably ethoxylation degree is 5-50, preferred 8-15 C ₁₆-C ₁₈Ethoxylated alcohol, its amount is 5%-80%, preferred 10%-70% (weight);

Be used for preferred granular suds suppressing system of the present invention and comprise the alkylating polysiloxane of top disclosed type and the mixture of solid silica.

Solid silica can be silicon-dioxide, the pyrogenic silica by the preparation of gel formation technology, or precipitated silica.It is the 0.1-50 micron that suitable silica dioxide granule has median size, preferably 1-20 micron and 50cm at least ²The surface-area of/g.These silica dioxide granules can have hydrophobicity by being bonded directly on the silicon-dioxide with dialkyl group silyl and/or trialkylsilkl or handling by polyorganosiloxane resin.The preferred use become hydrophobic silica dioxide granule with dimethyl and/or trimethyl silyl.Being added on the amount that the anti-alveolation compound of preferred particulates in the detergent composition of the present invention suitably comprises silicon-dioxide is silicon-dioxide: the polysiloxane anharmonic ratio is 1: 100-3: 10, preferred 1: 50-1: 7.

Another kind of suitable granular suds suppressing system is that 10 nanometers-20 nanometer and specific surface area are greater than 50m to have particle diameter ²/ g, equably with have about 200,000, the weight ratio polysiloxane of the about 500-of molecular weight: the silicon-dioxide of silanization is about 1: the silicon-dioxide of the hydrophobic silanization of the dimethyl silicone fluids that 1-is about 1: 2 (most preferably trimethyl silicone hydride) is representative.

A kind of granular suds suppressing system very preferably is described among the EP-A-0210731, and comprising the anti-alveolation compound of siloxanes and having fusing point is 50 ℃-85 ℃ organic carrier material, and wherein the organic carrier material comprises glycerine and has the monoesters of the lipid acid of the carbochain that contains 12-20 carbon atom.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein the organic carrier material is that fusing point is 45 ℃-80 ℃ lipid acid with the carbochain that contains 12-20 carbon atom or an alcohol, or its mixture.

Other granular suds suppressing system very preferably is described in the Procter and GambleCompany European application that awaits the reply 91870007.1 under one's name, its system comprises the anti-alveolation compound of polysiloxane, carrier substance, organic coating material and glycerine, anharmonic ratio glycerine: the anti-alveolation compound of polysiloxane is 1: 2-3: 1.The European application 91201342.0 that awaits the reply also discloses granular suds suppressing system very preferably, it comprises the anti-alveolation compound of polysiloxane, carrier substance, organic coating material and crystalline form or amorphous aluminosilicate, its anharmonic ratio silico-aluminate: the anti-alveolation compound of polysiloxane is 1: 3-3: 1.Preferred vector material in above-mentioned two kinds of granular foam control agents very preferably is a starch.

Being used for exemplary granular suds suppressing system of the present invention is the particle agglomerates component for preparing by agglomeration method, it comprises the 5%-30% of (i) composition weight, the preferred anti-alveolation compound of 8%-15% polysiloxane preferably contains polydimethylsiloxane and silicon-dioxide simultaneously; The (ii) 50%-90% of composition weight, preferred 60%-80% carrier substance, the preferred shallow lake

Powder; The (iii) 5%-30% of composition weight, preferred 10%-20% agglomeration binder compound,

Wherein this compound can be generally as any compound of agglomerate tackiness agent or its

Mixture, most preferably said agglomerate binder compound comprise that ethoxylation degree is 50

-100 C ₁₆-C ₁₈Ethoxylated alcohol; (iv) 2%-15%, preferred 3%-10% (weight) C ₁₂-C ₂₂Hydrogenated fatty acid.SYNTHETIC OPTICAL WHITNER

Detergent composition of the present invention can comprise the SYNTHETIC OPTICAL WHITNER that is selected from chlorine bleach, inorganic perhydrate salt, peroxyacid bleach precursor and organic peroxide acid.

SYNTHETIC OPTICAL WHITNER is the preferably combination of laundry of the present invention and machine-washing tableware composition.Manually washing tableware of the present invention and rinse aids composition preferably do not contain SYNTHETIC OPTICAL WHITNER.

Chlorine bleach comprises alkaline metal hypochlorite and mauguinite urate.In the present composition, preferably use chlorine bleach less as far as possible, and more preferably said composition chlorine bleaching agent not.Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

Machine-washing tableware of the present invention and laundry detergent composition preferably include inorganic perhydrate salt, sodium-salt form normally, and its amount is the 1%-40% of composition weight, more preferably 2%-30% and most preferably 5%-25%.

The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.This inorganic perhydrate salt can be used as the crystalline solid adding and not have extra protection.Yet concerning some perhydrate salt, the preferred embodiment of these granular compositions is used the material of coated form, and it provides better stability in storage for the perhydrate salt in the particulate product.

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

SPC-D is the perhydrate that preferably is added in the detergent composition of the present invention, and it is to have corresponding to 2Na ₂CO ₃3H ₂O ₂The ancillary compound of formula, and can be used as crystalline solid commerce and buy.Percarbonate most preferably mixes in these compositions with coated form.Most preferred coating substance comprises the mixing salt of alkali metal sulfates and carbonate.These coating materials are with the former GB-1 that authorized Interox on March 9th, 1977 that has been described in of coating method, in 466,799.The mixing salt coating substance is 1 to the anharmonic ratio of percarbonate: 200-1: 4, more preferably 1: 99-1: 9 and most preferably 1: 49-1: 19.Preferred mixing salt is sodium sulfate and yellow soda ash, and it has general formula Na ₂SO ₄.n.Na ₂CO ₃, wherein n is 0.1-3, preferred n be 0.3-1.0 and most preferably n be 0.2-0.5.

Another kind of suitable coated substance is SiO ₂: Na ₂CO ₃Ratio is 1.6: 1-3.4: 1, and preferred 2.8: 1 water glass uses and to the silicate solid of output as the 2%-10% of percarbonate weight (3%-5% usually) with its aqueous solution form.Magnesium Silicate q-agent also can be included in the coat.Other suitable coated substance comprises basic metal and alkaline earth metal sulphate and carbonate.

Permonosulphuric acid potassium is another kind of inorganic perhydrate salt useful in detergent composition.Peroxyacid bleach precursor

Machine-washing tableware of the present invention and laundry detergent composition also preferably include peroxyacid bleach precursor (bleach-activating agent).Peroxyacid bleach precursor is usually with the 1%-20% of composition weight, more preferably 1%-10%, most preferably the amount admixture of 1%-7%.

The peroxyacid bleach precursor that is contained in the machine-washing dish washing detergent compositions of the present invention generally contains one or more N-or O-carboxyl groups, and its precursor can be selected from very wide class scope.

Suitable kind comprises the acylated derivatives of acid anhydrides, ester, imide and imidazoles and oxime, and GB-A-1586789 discloses useful examples of substances in these classifications.Most preferred classification is as disclosed ester in GB-A-836988,864798,1147871 and 2143231, and as disclosed imide in GB-A-855735 and 1246338.

Particularly preferred bleach precursor compound is the N of following formula, N, N ', N ' tetrem acylated compounds

(CH ₃CO) ₂-(CH ₂) _x-(CH ₃CO) ₂Wherein x can be 0 or the integer of 1-6.

Example comprises tetrem acyl methylene diamine (TAMD), wherein x=1, tetraacetyl ethylene diamine (TAED), wherein x=2 and tetrem acyl hexanediamine (TAHD), wherein x=6.GB-A-907356 has described these compounds and similar compound.Most preferred peroxyacid bleach precursor is TAED.

Another kind of preferred peroxy acid bleach activator compound is the compound that replaces at the acyl ammonia described in the EP-A-0170386.

Other peroxyacid bleach precursor compound comprises for example at the acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems described in the EP-A-0341947, trimethyl acetyl oxygen base benzene sulfonic acid sodium salt, acetoxyl group benzene sulfonic acid sodium salt and benzoyloxy benzene sulfonic acid sodium salt.Organic peroxide acid

But machine-washing tableware and laundry detergent composition also amount are the 1%-15% of composition weight, more preferably the organic peroxide acid of 1%-10%.

Useful organic peroxide acid is included in the peroxy acid that the acyl ammonia described in the EP-A-0170386 replaces.

Other organic peroxide acid comprises as disclosed diperoxy base laurostearic acid in EP-A-0341947, diperoxy base four sebacic acid, diperoxy base palmitic acid, list and two nonane diacid, list and two undecane dicarboxylic acid, single peroxide phthalic acid, peroxybenzoic acid and salt thereof crossed crossed.

N, N '-O-phthalic amido peroxide caproic acid is useful here organic peroxide acid, particularly ought be applied to be formulated into pH less than 10 in the machine-washing tableware composition, preferably less than 9.5 o'clock.Additional enzymes

Other optional member that can be used in the detergent composition is one or more additional enzymes.

Preferred additional enzymes material comprises that routine mixes commercially available lipase, amylase, neutrality and Sumizyme MP, esterase, cellulase, polygalacturonase, Sumylact L and the peroxidase in the detergent composition.Suitable enzyme is at United States Patent (USP) 3,519, comes into question in 570 and 3,533,139.

Preferably the proteolytic enzyme that can commercial buy comprise those by Novo Nordisk A/S (Denmark) with trade name Alcalase, Savinase, Primase ^R, Durazym ^RAnd Esperase ^RThe enzyme of selling, and those by Gist-Brocades with trade name Maxatase ^R, Maxacal ^R, and Maxapem ^RThe enzyme of selling, those enzymes of selling by Genencor International and those by Solvay Enzymes with trade name Opticlean ^RAnd Optimase ^RThe enzyme of selling.Also have the proteolytic enzyme of in our application USSN08/136797 that awaits the reply, describing to be used in the detergent composition of the present invention.Proteolytic enzyme can mix in the present composition with the amount of the 0.0001%-2% organized enzyme of composition weight.

Preferred amylase comprises the α-Dian Fenmei that obtains as by special bacterial strain Bacillus licheniformis, at GB-1, among 269,839 (Novo) detailed description is arranged.Preferred commercially available amylase comprise as those by Gist-Brocades with trade name Rapidase ^RThe enzyme of selling and those by NovoNordisk A/S with trade name Fungamyl ^R, Termamyl ^RAnd BAN ^RThe enzyme of selling.Amylase can mix in the present composition with the amount of the 0.0001%-2% organized enzyme of composition weight.

Lipolytic enzyme (lipase) can be with the 0.0001%-2% of composition weight, preferred 0.001%-1%, and more preferably the amount of 0.001%-0.5% organized enzyme exists.

Lipase can be for example by fungi or bacterium in the source of the Humicola that comprises pseudomonas pseudoalcaligenes or Pseudomonas fluorescens that produces lipase, Thermomyces sp. or pseudomonas strain acquisition.Also can be used for herein from the chemistry of these bacterial strains or the lipase of genetically altered mutant.

A kind of preferred lipase is derived from pseudomonas pseudoalcaligenes, and it is described in the European patent EP-B-0218272 that has authorized.

Here another kind of preferred lipase is to express from the gene of Humicola lauginosa with this gene by the clone to obtain in the aspergillus oryzae host, as described in European patent application EP-A-0258068, it can be by Novo Nordisk A/S, Bagsvaerd, Denmark commerce is buied, and trade mark is called Lipolase.In the people's such as Huge-Jensen that authorize on March 7th, 1989 the United States Patent (USP) 4,810,414 this lipase has been described also.

At (EC3.1.1.50) also is fit to, and it can be considered to a kind of lipase of specific type, does not promptly need the lipase of interface activation.The at of adding in the detergent composition has been disclosed in as among the WO88/09367 (Genencor).

The available cellulase comprises bacterium and fungal cellulase in the present invention.Preferably, they have the pH optimum range of 5-9.5.People's such as Barbesgoard United States Patent (USP) 4,435,307 discloses suitable cellulase, and it discloses the fungal cellulase that is produced by Humicola insolens.GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832 also disclose the plain enzyme of useful fiber.

The example of these cellulases is by Humicola insolens (grey humicola lanuginosa kind thermoidea), particularly the cellulase of detritus bacteria strain DSM1800 generation.The plain enzyme of other useful fiber is that to derive from molecular weight be 5.5 for about 50KDa, iso-electric point and contains the cellulase of 415 amino acid whose Humicola insolens.Particularly suitable cellulase is the cellulase with color provide protection.The example of these cellulases is cellulases of describing in the European Patent Application No. of submitting on November 6th, 1,991 91202879.2 (Novo).

Peroxidase and oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching ", promptly in order to stop in the washing operation dyestuff that falls down from substrate or pigment to be transferred on other substrate the washing soln.Peroxidase is well known in the art, and comprises as horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro-and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in the PCT International Application No. WO of for example submitting on November 6th, 1,991 89/099813 and European patent application EP 91202882.6.

Said cellulase and/or peroxidase are impregnated in the detergent composition with the amount of the 0.0001%-2% organized enzyme of detergent composition weight usually.The enzyme stabilising system

The present invention preferably contains enzyme composition, and can to comprise about 0.001%-about 10%, and preferably about 0.005%-is about 8%, most preferably from about the enzyme stabilising system of about 6% (weight) of 0.01%-.The enzyme stabilising system can be any enzyme stabilising system compatible with the detergency enzyme.These enzyme stabilising systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid and composition thereof.These enzyme stabilising systems also can comprise irreversible enzyme inhibitor such as reversible protease inhibitors.

Composition of the present invention can comprise that also 0-is about 10%, the chlorine bleaching remover of about 6% (weight) of preferably about 0.01%-, and its chlorine bleaching species that are added into to prevent to be present in many sources make enzyme react with and inactivate, particularly under alkaline condition.Although cl content is few in the water, be generally the about 1.75ppm of about 0.5ppm-, the chlorine that exists in the cumulative volume of the water that contacts with enzyme in washing process is normally many, and therefore, the stability of enzyme may be a problem in the practicality.

Suitable chlorine remover negatively charged ion can extensively obtain, and illustrates by following salt, and these salt comprise ammonium cation or sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Also can use oxidation inhibitor such as carbamate, xitix etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and composition thereof.If desired, can use other conventional remover such as hydrosulfate, nitrate, muriate, hydrogen peroxide cource such as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc., and composition thereof.Dye transfer suppresses

The invention still further relates to the dye transfer that is suppressed at the dissolved and suspension dyestuff that runs in the fabric washing operating process that contains colored fabric from a kind of fabric to another kind of fabric.The polymeric dye transfer inhibitor

Detergent composition of the present invention also can comprise 0.01%-10%, 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 combination of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.A) polyamine N-oxide pllymers

Be applicable to that polyamine N-oxide pllymers of the present invention comprises the unit with following structural:

Wherein P is a polymerizable unit, and the R-N-O group can be connected on this unit, or wherein the R-N-O group forms the part of this polymerizable unit or the combination of the two.

A is -O-,-S-,-N-; X is 0 or 1; R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or its arbitrary combination, and the nitrogen of N-O group can be connected on this group, or wherein the nitrogen of N-O group is the part of these groups.

The N-O group can be represented with the following formula general formula: Wherein R1, R2 and R3 are aliphatic group, aromatics, heterocycle or alicyclic group or its combination, x or/and y or/and z be 0 or 1 and wherein the nitrogen of N-O group can be connected on these groups, or wherein the nitrogen of N-O group forms the part of these groups.This N-O group can be that the part of polymerizable unit (P) maybe can be connected on the polymeric skeleton or the combination of the two.

Wherein the N-O group suitable polyamine N-oxide that forms the part of polymerizable unit comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatics, alicyclic ring or heterocyclic group.The polyamine N-oxide of one class declaration comprises a wherein class polyamine N-oxide of the part of the nitrogen formation R-group of N-O group.Preferred polyamine N-oxide compound be those wherein R be the material and the derivative thereof of heterocyclic group such as pyridine, pyrroles, imidazoles, pyridine alkane, piperidines, quinoline, acridine.

Another kind of said polyamine N-oxide comprises that the nitrogen of N-O group wherein is connected to the class polyamine N-oxide on the R-group.

Other suitable polyamine N-oxide is that the N-O base is connected to the polyamine oxide compound on the polymerizable unit.

The preferred classes of these polyamine N-oxide is the polyamine N-oxide with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of said R group.The example of these classifications is that wherein R is the polyamine oxide compound and the derivative thereof of heterogeneous ring compound such as pyridine, pyrroles, imidazoles.

Another kind of preferred polyamine N-oxide compound is the polyamine oxide compound with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is connected on the said R group.The example of these classifications is that wherein the R group can be the polyamine oxide compound as phenyl of aromatic group.

As long as the amine oxide polymers that forms is water miscible, and has the dye transfer rejection, any polymer backbone can use.The example of suitable polymeric skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and composition thereof.

The amine that amine n-oxide polymkeric substance of the present invention generally has: the amine n-oxide ratio is 10: 1-1: 1000000.Yet the amount that is present in the amine oxide group in the polyamine oxide polymer can change along with suitable copolymerization or along with suitable N-oxidisability.Preferred amines: the amine n-oxide ratio is 2: 3-1: 1000000.More preferably 1: 4-1: 1000000, most preferably 1: 7-1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and one of them monomer type is that amine n-oxide and another monomer type are amine n-oxides or are not.The unitary pka of the amine oxide of polyamine N-oxide＜10, preferred pka＜7, more preferably pka＜6.

Can obtain the almost polyamine oxide compound of any polymerization degree.The polymerization degree is not crucial, as long as this material has desirable water-soluble and dye suspension ability.Usually, molecular-weight average is 500-1,000,000; Preferred 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

Be preferred for polymkeric substance of the present invention and can comprise the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, wherein said polymkeric substance has 5,000-50,000, more preferably 8,000-30,000, most preferably 10,000-20,000 molecular-weight average.The N-vinyl imidazole that preferred N-vinyl imidazole N-vinylpyrrolidone copolymer has: N-vinyl pyrrolidone ratio is 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4.C) Polyvinylpyrolidone (PVP)

It is 2 that detergent composition of the present invention also can use molecular-weight average, 500-400, and 000, preferred 5,000-200,000, more preferably 5,000-50,000 and most preferably 5,000-15,000 Polyvinylpyrolidone (PVP) (" PVP ").Suitable Polyvinylpyrolidone (PVP) can be commercial available from ISP Corporation, New York, NY and Montreal, (viscosity molecular weight is 10 to Canada name of product PVP K-15,000), (molecular-weight average is 40 to PVP K-30,000), PVP K-60 (molecular-weight average is 160,000) and PVP K-90 (molecular-weight average is 360,000).PVP K-15 also can be available from ISP Corporation.What other was suitable can comprise Sokalan HP165 and Sokalan HP12 by commercial Polyvinylpyrolidone (PVP) available from BASF Cooperation.

Polyvinylpyrolidone (PVP) can be with the 0.01%-5% of washing composition weight, preferred 0.05%-3% and more preferably the amount of 0.1%-2% mix in the detergent composition of the present invention.Be provided at the preferred 0.5ppm-250ppm of amount of the Polyvinylpyrolidone (PVP) in the washing soln, more preferably 2.5ppm-150ppm, more preferably 5ppm-100ppm.D) Ju Yi Xi oxazolidinone

Detergent composition of the present invention also can use the Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.Said Ju Yi Xi oxazolidinone has 2,500-400, and 000, preferred 5,000-200,000, more preferably 5,000-50,000 and most preferably 5,000-15,000 molecular-weight average.

The amount of mixing the Ju Yi Xi oxazolidinone in the detergent composition can be 0.01%-5% (weight), preferably 0.05%-3% (weight) and more preferably 0.1%-2% (weight).The amount that is provided at the Ju Yi Xi oxazolidinone in the washing soln generally is 0.5ppm-250ppm, preferred 2.5ppm-150ppm, more preferably 5ppm-100ppm.E) polyvinyl imidazol

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

The amount of mixing the polyvinyl imidazol in the detergent composition can be 0.01%-5% (weight), preferably 0.05%-3% (weight) and more preferably 0.1%-2% (weight).The amount that is provided at the polyvinyl imidazol in the washing soln is 0.5ppm-250ppm, preferred 2.5ppm-150ppm, more preferably 5ppm-100ppm.Corrosion inhibitor

The present composition also can comprise corrosion inhibitor.These corrosion inhibitors are components of preferred machine-washing tableware composition of the present invention, and preferred 0.05%-10% with total composition weight, the amount admixture of preferred 0.1%-5%.

Suitable corrosion inhibitor comprise usually be mainly chain aliphatic hydrocarbon, carbonatoms is the paraffin oil of 20-50; Preferred paraffin oil is selected from the C that is mainly side chain _25-45Kind, it has about 32: 68 cyclic hydrocarbon: non-cyclic hydrocarbon ratio; The paraffin oil that satisfies these characteristics is by Wintershall, Salzbergen, and Germany sells with trade name WINOG70.

Other suitable corrosion inhibition immunomodulator compounds comprises benzotriazole and any derivative, mercaptan and glycol, particularly has the mercaptan of 4-20 carbon atom, and it comprises lauryl mercaptan, benzene sulphur, phenol, thionaphthol, thionalid (thionalide) and anthracene thiophenol.C ₁₂-C ₂₀Lipid acid or its salt, particularly Aluminium Tristearate Micronized sterile also is fit to.C ₁₂-C ₂₀Hydroxy fatty acid or its salt also are fit to.The octadecane of phosphorylation and other oxidation inhibitor also are fit to as beta-hydroxy toluene (BHT).The heavy metal ion sequestering agent

Detergent composition of the present invention can be prepared like this to contain heavy metal ion chelating agent.The weight metal ion sequestrant is the preferred ingredient in laundry of the present invention and the machine-washing tableware composition, and it is with the 0.005%-3% of total composition weight, preferred 0.05%-1%, and most preferably the amount of 0.07%-0.4% is by admixture.

The heavy metal ion chelating agent that is applicable to this paper includes organic phosphonates such as amino alkylidenyl polyalkylene phosphonate, basic metal ethane 1-hydroxyl diphosphonate (disphosphonates), nitrilo trimethylene phosphonic salt.

Preferably diethylenetriamine pentamethylenophosphonic acid(DTPP) salt, hexamethylene-diamine tetramethylene phosphonic acid salt and hydroxyl methylene radical 1 in the above-mentioned classification, the 1-diphosphonate.

Phosphonate compounds can its sour form or is existed as the complex form of basic metal or alkaline-earth metal ions, and said metal ion: the molar ratio of said phosphonate compounds is at least 1: 1.US-A-4,259,200 have described these title complexs.Preferably, the organic phospho acid salt compound is its magnesium salts form.

Other is applicable to that heavy metal ion sequestering agent of the present invention comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid such as second diamino tetraacethyl, ethylidene pentaacetic acid, ethylenediamine disuccinic acid or its water-soluble alkali metal salts.Particularly preferably be quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement, or its mixture.Preferred EDDS compound is free acid form and its sodium or magnesium salts or title complex.The example of these preferred EDDS sodium salts comprises Na ₂EDDS and Na ₃EDDS.The example of these preferred EDDS magnesium complexes comprises MgEDDS and Mg ₂EDDS.The present composition most preferably contains magnesium complex.

Other is applicable to that heavy metal ion chelating agent of the present invention also has 2-hydroxyethyl oxalic acid described in iminodiacetic acid derivatives such as EPA317542 and the EPA399133 or glyceryl iminodiethanoic acid.

This paper heavy metal ion chelating agent can be made up of the mixture of mentioned kind.Softening agent

Fabric softener also can be impregnated in the laundry detergent composition of the present invention.These reagent can be inorganic or organic types.Inorganic softening agent is by at GB-A-1, disclosed smectic clays example in 400,898 and USP5,019,292.The organic fabric softening agent comprises as disclosed water-insoluble tertiary amine in GB-A-1514276 and EP-B-0011340 and itself and single C ₁₂-C ₁₄The combination of quaternary ammonium salt is disclosed among the EP-B-0242919.The organic composition of the fabric sofetening system that other is useful comprises as at EP299, disclosed high molecular weight peo material in 575 and EP313,146.

The amount of smectic clays is generally 5%-15%, more preferably 8%-12% (weight), and it is added in the remainder of preparation with the material as the dry mixed component.Organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides material are with 0.5%-5% (weight), usually the amount of 1%-3% (weight) is mixed, and high molecular weight peo material and water-soluble cationic material be with 0.1%-2%, and the amount of 0.15%-1.5% (weight) is mixed usually.These materials are impregnated in the spraying drying part of composition usually, although can with exsiccant composite grain form it be added more easily in some cases, or with the fusing liquid form it is sprayed onto on other solid ingredient of composition.Calcium

0.01%-3%, more preferably the calcium ion of 0.15%-2% can be added in the present invention is used for manually washing tableware by preparation detergent composition.

Calcium ion can be for example muriate, oxyhydroxide, oxide compound, formate or acetate, or nitrate.

If anion surfactant is the form of acid, the form of calcium with calcium oxide or calcium hydroxide slip can be added and neutralizing acid so.The calcium stable agent

Oxysuccinic acid, toxilic acid or acetate or its salt, or some lime soap dispersing agent compound can be added in any calcareous compositions formulated, thereby the product stability that provides particularly stop the precipitation of insoluble calcium phosphate.Magnesium

Preferably with 0.01%-3%, most preferably the magnesium ion of 0.15%-0.9% (weight) adds in the manually washing tableware composition of the present invention to improve whipability.Solvent

Detergent composition of the present invention can comprise organic solvent.Manually washing tableware composition of the present invention preferably comprises the 1%-30% with composition weight, preferred 3%-25%, the more preferably solvent system of the amount of 5%-20% existence.Solvent system can be single or the blended solvent system; But preferred blended solvent system.Preferably, the main ingredient of solvent system is a low volatility at least.

Be applicable to that organic solvent of the present invention has general formula R O (CH ₂C (Me) HO) _nH, wherein R is the integers that alkyl, alkenyl or alkaryl with 1-8 carbon atom and n are 1-4.R preferably contains the alkyl group of 1-4 carbon atom; With n be 1 or 2.Particularly preferred R group is normal-butyl or isobutyl-.Preferred this kind solvent is a 1-n-butoxy propan-2-ol (n=1); With 1 (2-n-butoxy-1-methyl ethoxy) propan-2-ol (n=2) and composition thereof.

Other is used for solvent of the present invention and comprises water-soluble CARBITOL solvent or water-soluble CELLOSOLVE solvent.Water-soluble CARBITOL solvent is 2-(2-alkoxyl group oxyethyl group) alcohol compound, and wherein alkoxy grp is derived from ethyl, propyl group or butyl; Preferred water-soluble diethylene glycol ethyl ether is 2-(2-butoxy oxyethyl group) ethanol, is also referred to as the butyldiglycol ether.Water-soluble CELLOSOLVE solvent is a 2-alkoxyl group ethoxy ethanol compounds, and the 2-bu-toxyethoxy is preferred.

Other appropriate solvent is benzylalcohol and glycol such as 2-ethyl-1,3-hexylene glycol and 2,2,4-trimethylammonium-1,3-pentanediol.

Lower molecular weight, water miscible, liquid macrogol also are to be applicable to solvent of the present invention.

Alkane list and glycol, particularly C ₁-C ₆Alkane list and glycol be suitable for use in of the present invention.C ₁-C ₄Monohydroxy-alcohol (as ethanol, propyl alcohol, Virahol, butanols and composition thereof) is preferred, and special preferred alcohol.C ₁-C ₄Dibasic alcohol comprises that propylene glycol also is preferred.Hydrotropic agent

Hydrotropic agent generally is added in manually washing tableware of the present invention and the rinse aids composition, and generally with 0.5%-20%, the amount of preferred 1%-15% (weight) exists.

Useful hydrotropic agent comprises sodium xylene sulfonate, potassium and ammonium, toluenesulfonic acid sodium salt, potassium and ammonium, and cumene sodium sulfonate, potassium and ammonium, and composition thereof.

The useful compound of other hydrotropic agent of the present invention comprises the multi-carboxylate.Some multi-carboxylates have calcium chelating ability and hydrotropy energy.Useful especially hydrotropic agent is an alkyl polyethoxye poly carboxylic acid salt tensio-active agent as previously described.Other optional member

Other optional ingredients that is suitable for being added in the present composition comprises spices, pigment and filling salt, and sodium sulfate is preferred filling salt.The form of composition

Detergent composition of the present invention can be prepared with form such as powder, particle, mashed prod, liquid, gel and the tablet of any hope.Manually washing tableware composition of the present invention preferably is mixed with liquid or gel form.Liquid composition

Detergent composition of the present invention can be configured to liquid detergent composition.These liquid detergent compositions generally comprise 94%-35% (weight), preferred 90%-40% (weight), the liquid vehicle of 80%-50% (weight) most preferably, water for example, the mixture of preferably water and organic solvent.Gelatinous composition

Detergent composition of the present invention can also be a gel form.The general apparatus of these compositions has an appointment 750, and the polyalkenyl polyethers of about 4,000,000 the molecular weight of 000-is prepared.Solids composition

Detergent composition of the present invention can also be a solid form, such as powder, particle and tablet.

The particle diameter of the granular size of granular composition component of the present invention preferred no more than 5% greater than the particle diameter of 1.4mm and no more than 5% less than 0.15mm.

Granular detergent composition of the present invention generally has at least 450 grams per liters, more generally at least 600 grams per liters and the more preferably tap density of 650 grams per liters-1200 grams per liter.

Tap density is measured by common funnel and cup equipment, and it is embossed in the conical hopper on the base rigidly and plate valve is housed so that the funnel content is placed into the cylindrical cup that places the axial setting below the funnel in its lower end by one.The top and bottom of funnel are respectively 130mm and 40mm.Installing like this makes the lower end at the above 140mm of base upper surface place.The cup total height is 90mm, and internal height is that 87mm and internal diameter are 84mm.Nominal volume is 500ml.

In order to measure, incline by hand powder is filled up funnel, plate valve is opened, the powder cup that overfills.The cup that fills up is taken off from frame, and by straight flange instrument such as knife are removed excessive powder by its upper limb from cup.Then the cup that fills up is weighed, and the value of the powder weight that obtains is doubled with the unit of obtaining is the tap density of grams per liter.Carry out replicate measurement as required.Manufacture method-granular composition

Usually, can make granular detergent composition of the present invention by the whole bag of tricks, it comprises dry mixed, spraying drying, agglomeration and granulating.Washing methods

Composition of the present invention can be used to any washing or purging method basically, and it comprises and has the method that rinse aid composition independently can add rinse step wherein.The method of machine-washing tableware

A kind of preferred machine-washing tableware method comprises with containing dissolving or being suspended in the above-mentioned machine-washing tableware of significant quantity wherein or article that are selected from pottery, glassware, hollow ware and cutlery that the liquid, aqueous processing of rinse composition is stain.The machine-washing tableware composition of significant quantity is meant that 8g-60g is dissolved or dispersed in product in the washing soln that volume is the 3-10 liter, and it is typical products dosage and the washing soln volume that is generally used in the conventional machine-washing tableware method.The manually washing tableware method

According to manually washing tableware method of the present invention, with the plate and the significant quantity of staiing, the about 20g of usually about 0.5g-(per 25 pending plates), the about 10g of preferably about 3g-composition contact of the present invention.The actual amount of the detergent composition that uses relies on user's judgement, and will depend on following factor, as the quantity of the particulate product preparation of composition, composition concentration, the contamination plate that is cleaned and the degree of soiling of plate.

In a preferred manually washing tableware method of the present invention, the concentrated solution of detergent composition is used on the plate surface to be washed.The concentrated solution of composition is meant and is not less than 20% (weight), preferably is not less than the product diluent of 50% (weight), most preferably uses composition with undiluted form.

Another preferred manual washing in the dish method of the present invention, used the diluting soln of a large amount of detergent composition.Preferably plate is soaked for some time in diluting soln, be typically 5 seconds-30 minutes.

In detergent composition, the component of slightly writing represents to have following meaning: LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate XYAS: C _1X-C _1YSodium alkyl sulfate SAS: the C of sodium-salt form ₁₂-C ₁₄Secondary (2,3) alkyl-sulphate APG: formula C ₁₂-(glucosyl) _xThe alkyl polyglycoside tensio-active agent, wherein x is

1.5AEC: formula C ₁₂The alkyl ethoxy carboxylate table of oxyethyl group (2) carboxylate salt

Surface-active agent SS: the secondary soap surfactant 25EY that formula 2-butyl is sad: with the C of average Y moles of ethylene oxide condensation _12-15For main component

Straight chain primary alcohol 45EY: with the C of average Y moles of ethylene oxide condensation ₁₄-C ₁₅Be main one-tenth

The straight chain primary alcohol XYEZS that divides: with the C of average every mole of Z moles of ethylene oxide condensation _1X-C _1YAlkane

Base sodium sulfate nonionogenic tenside: have the propoxylation degree of 3.8 average degree of ethoxylation and 4.5

C ₁₃-C ₁₅The Fatty Alcohol(C12-C14 and C12-C18) of blended ethoxylated/propoxylated, by

BASF Gmbh sells CFAA: C with trade name Plurafax LF404 ₁₂-C ₁₄Alkyl N-methyl glucose amide TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide silicate: amorphous sodium silicate (SiO ₂: Na ₂O ratio=2.0) NaSKS-6: formula δ-Na ₂Si ₂O ₅Crystal stratiform silicate carbonate: Carbon Dioxide na phosphates: tripoly phosphate sodium STPP MA/AA: molecular-weight average about 80,1: 4 toxilic acid/acrylic copolymer polyacrylate of 000: have 8,000 molecular-weight average, by BASF GmbH with trade name

The polyacrylate homopolymer zeolite A that PA30 sells: main particle diameter is the formula Na of 1-10 micron ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O

The hydrated sodium aluminosilicate Citrate trianion: citrate trisodium dihydrate citric acid: citric acid perborate: empirical formula NaBO ₂H ₂O ₂Anhydrous sodium perborate monohydrate bleaching

Agent PB4: anhydrous sodium perborate tetrahydrate percarbonate: empirical formula 2Na ₂CO ₃3H ₂O ₂Anhydrous SPC-D SYNTHETIC OPTICAL WHITNER TAED: tetraacetyl ethylene diamine PAP: N, N '-O-phthalic amido peroxide caproic acid paraffin: the paraffin oil lipoxygenase of selling with trade name Winog 70 by Wintershall: the lipoxygenase proteolytic enzyme of selling by ICN Biochemicals: the egg of selling with trade name Savinase by Novo Nordisk A/S

White enzyme amylase: go out with trade name Termamyl 60T by Novo Nordisk A/S

The amylase polygalacturonase of selling: sell with trade name Pectinex AR by Novo Nordisk A/S

The polygalacturonase Sumylact L: the Sumylact L lipase of selling by Novo Nordisk A/S: the fat of selling with trade name Lipolase by Novo Nordisk A/S

Separate the enzyme peroxidase: the peroxidase cellulase: by the fibre of Novo Nordisk A/S with trade name Carezyme sale

Tie up plain enzyme CMC: Xylo-Mucine HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: by the two inferior second of Monsanto with trade name Dequest 2060 sales

Base triamine pentamethylene phosphonic acids PVP: polyvinylpyrrolidonepolymers polymers EDDS: the quadrol-N of sodium-salt form, N '-disuccinic acid [S, S] isomer suds suppressor: 25%Mpt be 50 ℃ paraffin, 17% water drain silica,

The granular suds suppressor of 58% paraffin oil: 12% polysiloxane of granular form/silicon-dioxide, 18% octadecane

Alcohol, 70% starch SCS: cumene sodium sulfonate vitriol: anhydrous sodium sulphate

In following example, the amount of the enzyme that uses is expressed as the weight percent of composition.Example 1

Prepare following machine-washing dish washing detergent compositions of the present invention (weight part)

A B C D E F citrate 24.0--4.0 24.0 29.0 citric acids---15.0--phosphate-30.0 46.0---MA/AA 6.0--6.0 6.0-silicate 27.5-33.0 13.0 27.5 25.7 carbonate 12.5 23.5-9.0 12.5-perborate 10.4 10.4 10.4 10.4 10.4 1.9 PB4-----8.7 TAED 3.0 3.0 3.0-3.0 4.4 PAP---7.0--BTA-0.3---0.3 paraffin-0.5---0.5 HEDP-----0.5 proteinase-10 .04 0.04 0.04 0.04 0.04 0.04 amylase, 0.02 0.01 0.01 0.02 0.01 0.02 lipase 0.03-0.03 0.03 0.03-LOX, 0.05 0.07 0.04 0.01 0.08 0.05 non-ionic surface active agent-1.5 1.5 1.5 1.5 1.5 sulfate 1.4 2.4 2.4 12.1 12.1 3.0 35AE3S--5.0-5.0-granular foam inhibitor 1.0-----water and micro substance reach 100%

When being used for machine-washing tableware method, the clean effect that said composition provides.1% the composition D aqueous solution has about 9.0 pH.Example 2

Prepare following liquid manually washing tableware composition of the present invention.

Weight percent

I II III IV V 23AE 0.8S 10.0 10.0 6.0 5.0 10.0 23AE 3S 7.0 7.0 10.0 15.0 7.0 C _12/14Alkyl amine oxide 2.0 1.0-1.0 2.0 C _12/14Alkyl dimethyl trimethyl-glycine-1.0 1.5 2.0-C _12/14--1.5--Ampholak (TM) CFAA 12.0 6.0 12.0 11.0 12.0 C ₁₀Alkyl ethoxylates (average 8) 2.0 5.0 5.0 4.6 5.0 magnesium ions-0.6-0.3 0.6 calcium ion--0.3 0.15 0.1 maleic acid--0.2 0.3-LOX 0.05 0.01 0.02 0.03 0.04 proteinase-10 .01,0.02 0.01 0.02 0.03 water and micro substance reach 100%

Prepare composition by mixing all tensio-active agents except glucamide.Then magnesium salts and calcium salt are dissolved in the solution in advance with toxilic acid, and add in the surfactant mixtures with remaining ingredient.At last, pH is decreased to 7.3, and detects viscosity with hydrochloric acid.Example 3

Prepare following liquid manually washing tableware composition of the present invention.The pH of composition is transferred to 7.0-7.4.

Weight percent

I II III IV VLAS----10.023AE 0.8S 10.0 10.0 9.0 5.0 5.023AE 3S 3.0 7.0 8.0 15.0-SS--4.0--C _12/14Alkyl amine oxide 2.0 1.0-1.0 2.0AEC---5.0-C _12/14Alkyl dimethyl trimethyl-glycine-1.0 1.5 2.0-C _12/14--1.5--Ampholak (TM) CFAA 12.0-12.0 11.0-APG-12.0---C ₁₀Alkyl ethoxylates (average 8) 5.0 5.0 5.0 4.6 5.0 magnesium ions-0.6 0.3 0.3 0.6 calcium ion--0.3 0.15 0.1 maleic acid--0.2 0.3-LOX, 0.05 0.1 0.02 0.03 0.04 proteinase-10 .01,0.02 0.01 0.02 0.03 water and micro substance reach 100% example 4

The of the present invention granular fabric cleaning composition that is prepared as follows:

I II III IV

LAS 22.0 22.0 22.0 22.0

Phosphoric acid salt 23.0 23.0 23.0 23.0

Carbonate 23.0 23.0 23.0 23.0

Silicate 14.0 14.0 14.0 14.0

Zeolite A 8.2 8.2 8.2 8.2

DETPMP 0.4 0.4 0.4 0.4

Sodium sulfate 5.5 5.5 5.5 5.5

Proteolytic enzyme--0.02-

Lipoxygenase 0.04 0.06 0.1 0.04

Water and micro substance reach 100% example 5

The of the present invention granular fabric cleaning composition that is prepared as follows:

I II III IV

LAS 12.0 12.0 12.0 12.0

Zeolite A 26.0 26.0 26.0 26.0

SS 4.0 4.0 4.0 4.0

SAS 5.0 5.0 5.0 5.0

Citrate trianion 5.0 5.0 5.0 5.0

Sodium sulfate 17.0 17.0 17.0 17.0

Perborate 16.0 16.0 16.0 16.0

TAED 5.0 5.0 5.0 5.0

Lipoxygenase 0.20 0.01 0.02 0.08

Proteinase-10 .06 0.03 0.02 0.08

Water and micro substance reach 100% example 6

The granular fabric cleaning composition of the present invention of the washing that is particularly useful in colored fabric that is prepared as follows:

LAS 11.4 10.7

TAS 1.8 2.4

45AS 3.0 3.1

45E7 4.0 4.0

68E11 1.8 1.8

Citrate trianion 14.0 15.0

Citric acid 3.0 2.5

Zeolite A 32.5 32.1

MA/AA 5.0 5.0

DETPMP 1.0 0.2

Lipoxygenase 0.01 0.05

Polygalacturonase 0.02 0.01

Sumylact L 0.04 0.03

Proteinase-10 .02 0.02

Lipase 0.03 0.04

Amylase 0.03 0.03

Silicate 20.0 2.5

Vitriol 3.5 5.2

PVP 0.3 0.5

Perborate 0.5 1.0

Peroxidase 0.01 0.01

Phenolsulfonate 0.1 0.2

Water and micro substance reach 100% example 7

The of the present invention granular fabric cleaning composition that is prepared as follows:

LAS 6.5 8.0

Vitriol 15.0 18.0

Zeolite A 26.0 22.0

Sodium nitrilo triacetate 5.0 5.0

PVP 0.5 0.7

TAED 3.0 3.0

Boric acid 4.0-

Perborate 0.5 1.0

Phenolsulfonate 0.1 0.2

Proteinase-10 .06 0.02

Lipoxygenase 0.01 0.02

Silicate 5.0 5.0

Carbonate 15.0 15.0

Peroxidase 0.1 0.1

Water and micro substance reach 100% example 8

Prepared following of the present invention granular fabric cleaning composition:

45AS 8.0

25E3S 2.0

25E3 6.0

Zeolite A 17.0

NaSKS-6 16.0

Carbonate 7.0

MA/AA 5.0

CMC 0.4

N-vinyl imidazole and vinyl pyrrole 0.1

Poly-(the 4-vinylpyridine of alkane ketone

Pyridine)-the N-oxide block copolymer

Lipoxygenase 0.05

Proteinase-10 .01

Lipase 0.02

Cellulase 0.02

TAED 6.0

Percarbonate 22.0

EDDS 0.3

Granular suds suppressor 3.5

Water and micro substance reach 100% example 9

The granular fabric cleaning composition of the present invention that following providing " whole washing is soft " performance has been provided:

LAS 7.6

68AS 1.3

45E7 4.0

Coconut alkyl dimethyl hydroxyethyl ammonium chloride 1.4

Citrate trianion 5.0

Zeolite A 15.0

MA/AA 4.0

DETPMP 0.4

Perborate 15.0

TAED 5.0

Smectic clays 10.0

Proteinase-10 .02

Lipase 0.02

Amylase 0.03

Lipoxygenase 0.03

Cellulase 0.02

Silicate 3.0

Carbonate 10.0

Suds suppressor 1.0

CMC 0.2

Water and micro substance reach 100% example 10

Prepare the following pre-treatment that is applicable to staining fabric and be applicable to the heavy-filth liquid fabric cleaning composition of the present invention of machine-washing method:

I II III IV V

24AS 20.0 20.0 20.0 20.0 20.0

SS 5.0 5.0 5.0 5.0 5.0

Citrate trianion 1.0 1.0 1.0 1.0 1.0

12E ₃ 13.0 13.0 13.0 13.0 13.0

Monoethanolamine 2.5 2.5 2.5 2.5 2.5

Lipoxygenase 0.02 0.01 0.05 0.01 0.03

Proteolytic enzyme--0.02 0.04-

Lipase--0.02--

Water/propylene glycol/ethanol (100: 1: 1) example 11

Prepared following heavy-filth liquid fabric cleaning composition of the present invention:

I II

C _12-14Alkenyl succinic 3.0 8.0

Citric acid 10.0 15.0

25AS 8.0 8.0

25AE2S - 3.0

25AE7 - 8.0

25AE3 8.0 -

DETPMP 0.2 -

Oleic acid 1.8-

Ethanol 4.0 4.0

Propylene glycol 2.0 2.0

Lipoxygenase 0.05 0.01

Proteinase-10 .02 0.02

PVP 1.0 2.0

Perborate 0.5 1

Phenolsulfonate 0.1 0.2

Peroxidase 0.04 0.01

NaOH reaches pH7.5

Water and micro substance reach 100% example 12

Prepared following liquid rinse assistant composition of the present invention (weight part)

A B C D E F citric acid 6.5 6.5 6.5 6.5 6.5 6.5 non-ionic surface active agents 12.0 12.0 12.0 12.0 12.0 12.0 HEDP-2.5 2.5 5.0 5.0 5.0 DETPMP--3.0---EDDS---3.0--polyacrylates---pH 3.3 1.8 1.8 3.3 3.3 3.3 water and the micro substance of-5.0-LOX 0.02 0.06 0.08 0.04 0.06 0.02 SCS 4.8 4.8 4.8 4.8 4.8 4.8 ethanol 6.0 6.0 6.0 6.0 6.0 6.0 ammonia 0.7--0.7 0.7 0.7 1% solution reach 100%

Claims (12)

1. detergent composition, it comprises at least a detergent component that is selected from tensio-active agent and washing-aid compound, it is characterized in that said composition comprises lipoxygenase.

2. detergent composition according to claim 1, the amount that wherein said lipoxygenase exists is counted the heavy 0.0001%-2% of composition by the weight of organized enzyme.

3. detergent composition according to claim 1 or 2, it comprises 0.1%-30% (weight) organic polymer.

4. detergent composition in the machine-washing method of being applicable to according to claim 1-3, it comprises additional one or more and is selected from the detergent component of SYNTHETIC OPTICAL WHITNER, additional enzymes, suds suppressor, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.

5. detergent composition according to claim 4, wherein additional enzyme is selected from amylase, proteolytic enzyme or lipase.

6. detergent composition according to claim 1-5, it comprises the said washing-aid compound of 1%-80% (weight).

7. detergent composition according to claim 1, it comprises the said tensio-active agent of 1%-35% (weight), and wherein tensio-active agent is selected from the tensio-active agent of nonionic, negatively charged ion, positively charged ion, zwitter-ion, both sexes (ampholytic) and both sexes (amphoteric).

8. detergent composition according to claim 4, it comprises and is selected from following SYNTHETIC OPTICAL WHITNER

(a) the inorganic perhydrate salt that exists with the amount of the 1%-40% of composition weight;

(b) before the peroxyacid bleach that exists with the amount of the 1%-20% of composition weight

Body;

(c) organic peroxide acid that exists with the amount of the 1%-15% of composition weight; And

Its mixture.

9. detergent composition according to claim 5, it comprises and is selected from following additional enzymes.

(a) the organized enzyme amount is neutrality and the alkaline egg of the 0.0001%-2% of composition weight

White enzyme;

(b) the organized enzyme amount is the amylase of the 0.0001%-2% of composition weight;

(c) the organized enzyme amount is the lipase of the 0.0001%-2% of composition weight; And mix

Compound.

10. one kind is applicable to detergent composition in the manually washing tableware method according to claim 1, and it comprises one or more and is selected from profoamer, the additional detergent components of II family metal ion and additional enzymes.

11. lipoxygenase is the purposes that reduces filter residue in the rinse aid composition.

12. lipoxygenase is used in the cleaning combination to destroying the purposes of food in the machine at the wash dining set machine.