CN1091803C - Detergent compositions - Google Patents

Abstract

There is provided a detergent composition comprising conventional detergent components characterized in that it contains a pectic enzyme. The pectic enzyme is preferably incorporated into the compositions at a level of from 0.0001 % to 2 % active enzyme by weight of the composition.

Description

Cleaning composition

The present invention relates to cleaning composition, comprise the composition that contains polygalacturonase of washing dish and laundry.

Be used to wash dish and cleaning method, as doing washing and washing the cleaning product of dish method, its performance can be estimated by many parameters, and this comprises that ability of removing dirt and the degradation production that prevents dirt or dirt are deposited to the ability on the substrate again.

Food stain usually is difficult to remove effectively from the substrate of making dirty.Heavy or the dried spot for the look that is produced by fruit and/or vegetables juice, remove them is stern challenges.The specific examples of this spot comprises orange juice, Tomato juice, banana, mango or asparagus broccoli spot.Substrate can be a textiles, also can be crust such as glass or ceramic.

In such as fruit syrup, find to have pectin substance.The effect of pectin substance is that dispersed particle is suspended in this fruit juice, makes the person's character of the fruit juice thickness and opaque that becomes.Polygalacturonase generally is used in fruit juice/vegetables juice processing industry, makes juice clarification (taking off pectin) by the pectin substance that decomposes wherein.

But, never recognized in the past in detergent formulation, particularly in laundry, wash dish and clean the benefit of using polygalacturonase in the prescription that home appliances uses.

The applicant finds now, and it is of great value that polygalacturonase is added in the cleaning composition.This kind enzyme is added the benefit that the removing spot can be provided, can remove food stain, particularly remove the fruit juice and the vegetables juice spot of exsiccation.

The applicant also finds, adds dispersion agent in containing the cleaning composition of polygalacturonase, and particularly the organic polymer dispersion agent is of great value.Dispersion agent helps the dispersion of the spot degradation production of enzyme, prevent its when washing reprecipitation on washes.

A target of the present invention is exactly to propose a kind of cleaning composition that contains polygalacturonase, and when being used for cleaning and washing operation, it can provide the benefit of removing spot.

Specific objective of the present invention is to propose a kind ofly to contain the laundry of polygalacturonase and to wash the dish composition, and this enzyme provides enhanced fruit and or the removal ability of vegetables (juice) spot.

Brief summary of the invention

According to the present invention, a kind of at least a cleaning composition that is selected from the scrubbed component of tensio-active agent and washing-aid compound that contains has been proposed, it is characterized in that described composition contains polygalacturonase.

Of the present invention one preferred aspect, cleaning composition also contains the decentralized compound of dispersion agent, particularly organic polymer.

Polygalacturonase

A key ingredient of cleaning composition of the present invention is a polygalacturonase.According to the present invention add polygalacturonase content in the composition be organized enzyme account for composition weight 0.0001%～2%, preferred 0.0005%～0.5%, more preferably 0.001%～0.05%.

Polygalacturonase one vocabulary shows any material that pectin substance is decomposed in this article, and pectin substance can find in plant tissue, and it is the common ingredients of fruit juice and orange juice, tomato juice and Sucus Vitis viniferae.Pectin substance contains nougat aldehydic acid and/or its derivative.

Pectin substance comprises pectin and pectic acid.The polymkeric substance that the galacturonic acid chain that pectin is generally connected by α-1 → 4 glycosidic link is formed.General about 2/3 carboxyl is by methanol esterification in natural pectin.These methyl esters are carried out the partial hydrolysis meeting obtain low-methoxy pectin, it tends to form gel with calcium ion.The methyl esters complete hydrolysis just obtains pectic acid.

Polygalacturonase comprise hydrolysis of pectin methyl esters key pectin methylesterase, the glycosidic link between the fracture galacturonic acid molecule polygalacturonase and act on the pectic acid, the non-hydrolytic cleavage that causes α-1 → 4 glycosidic link is with the pectin transeliminase of the unsaturated derivative that forms galacturonic acid or be lyase.

Polygalacturonase herein comprises the polygalacturonase and any mutation by obtaining such as genetic engineering technique of natural source.Any such mutation can be used for cleaning composition of the present invention by specialized designs and optimize effectiveness of performance.Such as, can design some mutation, enzyme is increased the stability of the component of often running in this composition.In addition, also can design some mutation allows their optimal ph or temperature performance scope can be suitable for specific washing application.

Can be by plant, fruit particularly, and make polygalacturonase by fungic origin.The bacterial strain of some aspergillus niger family provides common fungic origin.The commodity polygalacturonase tends to the mixture of pectin methylesterase, polygalacturonase and pectin lyase class.

The commodity polygalacturonase comprises that Novo Nordisk A/S company commodity are called the commodity of the commodity Cytolase by name of Pectinex AR, International Bio-Synthetics company (branch of Gist-Brocades BV company) commodity Rapidase by name, Genencor Lnternational company and Solvay company commodity Clarex by name etc.

Scrubbed component

Composition of the present invention contains at least a scrubbed component that is selected from tensio-active agent and washing-aid compound.

Cleaning composition of the present invention also can contain additional scrubbed component.The concrete kind of these additional scrubbed component and adding quantity thereof will depend on the physical form of composition, and will carry out the attribute of cleaning operation with it.

Composition of the present invention can become hand washing and machine is washed dish composition, hand washing and machine laundry composition such as prescription, adds composition and is suitable for being used in the pretreated composition of pollution textiles, rinse aid composition and is applicable to the composition of general home appliances cleaning operation comprising laundry.

When becoming, prescription is suitable for the machine-washing method, when washing the composition that the dish method uses such as machine laundry method and machine, the present composition had preferably both contained tensio-active agent and helped washes compound, contains one or more in addition and preferably is selected from organic polymer, SYNTHETIC OPTICAL WHITNER, additional enzyme, suds suppressor, lime soap dispersing agent, soil-suspending agent, the anti-scrubbed component of sinking agent and corrosion inhibitor etc. again.As additional scrubbed component, laundry composition also can contain softening agent.

When prescription becomes when being used to hand-wash the composition of washing the dish method, the present composition preferably contains tensio-active agent and preferably is selected from other scrubbed component such as organic polymer, suds booster, II family metal-salt, solvent, hydrotropic agent and additional enzyme.

Surfactant system

As main scrubbed component, cleaning composition of the present invention can contain and is selected from negatively charged ion, positively charged ion, nonionic and various types of zwitterionicss and composition thereof.

The weight content of tensio-active agent is washed dish, laundry and rinse aid composition according to machine of the present invention and is generally 0.1～60%.Preferred add-on is 0.5%～35% (wt), and most preferred is 0.5%～0.2% (wt); And be generally 5%～60% according to hand washing dish composition of the present invention, be preferably 15%～45% (wt).

Tensio-active agent preferably fill a prescription become with composition in the enzyme component compatibility.In liquid or gelatinous composition, surfactant formula preferably makes it promote, or is not reduced in the stability of any enzyme in the said composition at least.

USP 3,929, and 678 (Laughhin and Heuring, on December 30th, 1975 issued) have typically listed the dissimilar and kind of positively charged ion, nonionic, zwitterionics; At " Surface Active Agents and Detergents " (Vol I, II; Schwartz, Perry and Berch work) also provided further example in the book.USP 4,259, listed suitable cats product among 217 (Murphy, on March 31st, 1981 issued).

When various amphotericses existed, they generally used with one or more negatively charged ion and/or nonionogenic tenside.

Anion surfactant

In composition, can comprise any anion surfactant that can be used for washing purpose basically.They can comprise that anion sulfate, sulfonate, carboxylate salt and sarcosinate (comprise such as Na, K, NH ₄With the NH that replaces ₄Salt is as Monoethanolamine MEA BASF, diethanolamine, triethanolamine salt etc.) tensio-active agent.

Other anion surfactant comprises isethionate such as acyl isethinate, N-ethanoyl taurate, the fatty acid amide of methyl ox sulphur, alkyl succinate, sulfosuccinate, sulfosuccinate monoesters (particularly saturated and undersaturated C ₁₂～C ₁₈Monoesters), sulfosuccinic acid diesters (particularly saturated and undersaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are suitable for, such as rosin, staybelite be present in or derive from the resinous acid and the hydrogenation resin acid of tallow oil.

The anion sulfate acid salt surfactant

The anion sulfate tensio-active agent of Shi Yonging comprises straight chain and ramose primary alkyl sulphates, alkyl polyoxyethylene ether sulfate, aliphatic oil base glycerol base vitriol, alkylphenol polyoxyethylene vitriol, C in this article ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) glucosamine sulfate and alkyl polysaccharide vitriol are as the vitriol of alkyl polyglucoside (compound of Xu Shu non-ionic type non-sulfuric acidization in this article).

The alkyl polyoxyethylene ether sulfate tensio-active agent preferably in each molecule by about 0.5 C that carries out ethoxylation to about 20 moles ethylene oxide chain link ₆-C ₁₈Alkyl-sulphate.Preferred alkyl polyoxyethylene sulfate surfactant be in each molecule by about 0.5 to about 20 moles, preferred about 0.5 C to about 5 mole ethylene oxide chain link ethoxylations ₆-C ₁₈Alkyl-sulphate.

The anion sulfoacid salt surfactant

The anionic sulphonate tensio-active agent of Shi Yonging comprises C herein ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle's alkane or secondary alkyl sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonation polycarboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol sulfonate and mixture arbitrarily thereof.

The anionic carboxylic acid salt surfactant

The anionic carboxylate tensio-active agent of Shi Yonging comprises alkyl polyoxyethylene carboxylate salt, alkyl polyoxyethylene polycarboxylic acid salt surfactant and soap class (" alkyl carboxylate ") herein, particularly some secondary soap class of narrating at this paper.

The preferred alkyl polyoxyethylene carboxylate salt that uses in this article comprises that general formula is RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Compound, wherein R is C ₆-C ₁₈Alkyl, x is 0-10, polyoxyethylated distribution (based on weight) is such: when x was 0, the polyoxyethylene amount was less than 20%, when x greater than 7 the time, it is less than 25%; When R is C ₁₃Or more hour, the about 2-4 of x average out to, when R greater than C ₁₃The time, the about 3-10 of x average out to; M is a positively charged ion, preferably has basic metal, alkaline-earth metal, ammonium, monoethanolamine, diethanolamine and trolamine; Most preferably Na, K, NH ₄With them and Mg ionic mixture.Preferred alkyl polyoxyethylene carboxylate salt is that R is C ₁₂-C ₁₈The compound of alkyl.

The alkyl polyoxyethylene polycarboxylate of Shi Yonging comprises that having general formula is RO-(CHR in this article ₁-CHR ₂-O)-R ₃Compound, wherein R is C ₆-C ₁₈Alkyl, x are 1-25; R ₁And R ₂Be selected from H, formyloxy, amber acidic group, hydroxy succinic acid base and composition thereof.R wherein ₁Or R ₂In have at least one to be amber acidic group or hydroxy succinic acid base, R ₃Be selected from H, replacement or unsubstituted C ₁-C ₈Alkyl, and their mixture.

The secondary soap surfactant of negatively charged ion

Preferred soap class tensio-active agent is to be connected with the unitary secondary soap surfactant of carboxyl on its secondary carbon.This, carbon can be in ring texture second month in a season, such as in to the octyl group phenylformic acid, and also can be on the cyclohexane carboxylic acid that alkyl replaces.The best ether-containing key not of this of carbon soap class tensio-active agent does not contain ester bond and hydroxyl second month in a season yet.The N atom does not preferably have in its end group group (amphiphilic moieties).Secondary soap class tensio-active agent generally contains 11-15 total carbon atom, though more slightly (as reaching 16) also allow, as to the octyl group phenylformic acid.

Following formula further specifies preferred secondary soap surfactant.

A. the secondary soap of a very preferred class comprises that general formula is R ³CH (R ⁴) COOM contain secondary carboxyl material, wherein R ³Be CH ₃(CH ₂) _x, R ⁴Be CH ₃(CH ₂) _y, y can be 0 or the integer of 1-4 here, and x is the integer of 4-10, and the x+y sum is 6-10, preferred 7-9, most preferably 8.

B. another kind of preferred secondary soap class comprises such class carboxylic compound, and wherein carboxyl substituent is on cyclic hydrocarbon group, and promptly general formula is R ⁵-R ⁶-COOM, wherein R ⁵Be C ₇-C ₁₀, preferred C ₈-C ₉Alkyl or alkenyl, R ⁶Be a ring texture, such as benzene, pentamethylene and hexanaphthene.Note that R ⁵The ring on can and carboxyl be in ortho position, a position or contraposition position.

C. also have the preferred secondary soap of a class to comprise that general formula is

CH ₃(CHR) _K-(CH ₂) _m-(CHR) _n-CH (COOM) (CHR) _o-(CH ₂) _p-(CHR) _q-CH ₃, wherein each R is C ₁-C ₄Alkyl, wherein, k, n, o, q are the integers of 0-8, require to comprise that the total number of carbon atoms of carboxyl is 10-18.

Among A, B, the C, each M can be suitable particularly water miscible counter ion in the above.

Particularly preferred secondary soap surfactant used herein be selected from 2-methyl isophthalic acid-hendecoic 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

Another kind of suitable anion surfactant is that general formula is RCON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇Straight chain or branch's alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ions.Preferred example is myristyl and the oil base methyl sarcosinate that is sodium-salt form.

Nonionogenic tenside

In composition, can comprise any nonionogenic tenside that can be used for washing purpose basically.List the indefiniteness example of useful nonionogenic tenside below.

The nonionic polyhydroxy fatty acid amide surfactant

The polyhydroxy fatty acid amide surfactant of Shi Yonging is to have formula R in this article ²The compound of CONR ' Z, wherein: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or their mixture; Z has the hydrocarbyl chain of straight chain and at least 3 hydroxyls continuous polyhydroxy alkyl of chain is therewith arranged, perhaps its polyoxygenated alkyl derivative (preferred ethoxylation or propoxylated derivative).Z preferably derives from the reducing sugar in reductive amination process; Preferred Z is sugar alcohol base (glycityl).

Alkylphenol nonionic condenses

The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide polycondensate are suitable for application in this article.The polycondensate of general preferred polyethylene oxide.This compounds has comprised straight chain or the alkylphenol of branch's alkyl and the condensation product of alkylidene oxide with about 18 carbon atoms of about 6-.

Non-ionic polyoxyethylene alcohol tensio-active agent

Fatty Alcohol(C12-C14 and C12-C18) alkyl polyoxyethylene polycondensate with the about 25mole oxyethane of about 1-is applicable to purposes herein.The alkyl chain of this Fatty Alcohol(C12-C14 and C12-C18) can be a straight chain, or ramose; Can be primary alconol or secondary alcohol, generally contain 6-22 carbon atom.Particularly preferably be alcohol and every mole alcohol about 2 condensation products of alkyl with 8-20 carbon atom to about 10mole oxyethane.

Non-ionic polyoxyethylene/polyoxypropylene fatty alcohol surfactant

Polyoxyethylene C ₆-C ₁₈Fatty Alcohol(C12-C14 and C12-C18) and C ₆-C ₁₈Mixed polyoxyethylene/polyoxypropylene Fatty Alcohol(C12-C14 and C12-C18) is the tensio-active agent that is suitable for herein, particularly water miscible compound.Preferred polyoxyethylene Fatty Alcohol(C12-C14 and C12-C18) is that ethoxylation degree is the C of 3-50 ₁₀-C ₁₈The polyoxyethylene Fatty Alcohol(C12-C14 and C12-C18); More preferably ethoxylation degree is the C of 3-40 ₁₂-C ₁₈The polyoxyethylene Fatty Alcohol(C12-C14 and C12-C18).Preferred polyoxyethylene/polyoxypropylene Fatty Alcohol(C12-C14 and C12-C18) has the alkyl chain length of 10-18 carbon atom, and ethoxylation degree is 3-30, and the propoxylation degree is 1-10.

The condenses of nonionic EO/PO and propylene glycol

Oxyethane is suitable in this article with the product that the hydrophobic group that is formed by propylene oxide and propylene glycol condensation carries out condensation.The hydrophobic part of this compound preferably has the molecular weight of about 1500-about 1800, and water-fast performance is arranged.The example of this compounds comprises some trade(brand)name Pluronic by BASF AG ^TMThe tensio-active agent of selling.

The condensation product of nonionic (ED) and PO/ ethylenediamine adduct

Oxyethane is suitable for using in this article with the product that the product that is obtained by propylene oxide and reacting ethylenediamine carries out condensation.Hydrophobic part in this product has comprised the reaction product of quadrol and excessive propylene oxide, and its molecular weight is generally about 2500 to about 3000.The example of this class nonionogenic tenside comprises the trade(brand)name Tetronic of BASF AG ^TMCompound.

The nonionic alkyl polysaccharide surfactant

The alkyl polysaccharide surfactant of Shi Yonging is disclosed in USP 4 herein, 565,647 (Llenado, on January 21st, 1986 issued) among, it have comprise about 6 to about 30 carbon atoms, preferred about 10 to the hydrophobic group of about 16 carbon atoms and saccharides more than polysaccharide glycosides for example, it is about 1.3 to about 10, preferred about 1.3 to about 3,1.3 hydrophilic radicals to about 2.7 sugar units most preferably from about.Can use any reducing sugar that contains 5 carbon or 6 carbon atoms,, and can replace glucosyl with galactosyl such as glucose, semi-lactosi.(in case of necessity, have on the positions such as 2-, 3-, 4-to connect hydrophobic group, so just obtain and glucoside or corresponding glucose of galactoside or semi-lactosi).Key can be between a sugar unit that increases and a position in 2-, 3-, 4-and/or the 6-position of original sugar unit between sugar.

Preferred APG has following general formula:

R ²O (C _nH _2n) _t(glucosyl) _x

Wherein, R ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein alkyl comprise 10 to 18, preferred 10 to 14 carbon atoms; N is 2 or 3; T is 0 to 10, is preferably 0; X is 1.3 to 8, and is preferred 1.3 to 3, more preferably 1.3 to 2.7.Glucosyl preferably comes from glucose.

The nonionic fatty acid amide surfactant

The fatty acid amide surfactant of Shi Yonging has general formula R herein ⁶CON (R ⁷) ₂, R in the formula ⁶Be to contain 7-21, the alkyl of preferred 9-17 carbon atom, each R ⁷All be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, x is in the scope of 1-3.

Two property (amphoteric) tensio-active agent

Two surfacants of Shi Yonging comprise amine oxide tensio-active agent and the two property carboxylic acids (alkyl amphocarboxylic acid) of alkyl herein.

The two property dicarboxylic acid of the alkyl of Shi Yonging are New Yorks herein, the dense Miranol that the Miranol company in Dayton city makes ^TMC2M.

The amine oxide tensio-active agent

The amine oxide of Shi Yonging has R herein ³(OR ⁴) _xN ⁰(R ⁵) ₂General formula, R in the formula ³Be selected from alkyl, hydroxyalkyl, amidopropyl, alkyl phenyl or their mixture, they contain 8-26, preferred 8-18 carbon atom; R ⁴Be alkylidene group or hydroxy alkylidene, they contain 2-3, preferred 2 carbon atoms, or their mixture; X is 0-5, preferred 0-3; Each R ⁵Be to contain 1-3 carbon atom, the alkyl or the hydroxyalkyl of preferred 1-2 carbon atom perhaps contain 1-3, the polyethylene oxide group of preferred 1 ethylene oxide group.R ⁵Group can form a ring texture such as being connected to each other by Sauerstoffatom or nitrogen-atoms.

This class amine oxide tensio-active agent specifically comprises C ₁₀-C ₁₈Alkyl-dimethyl amine oxide and C ₈-C ₁₈Alkoxyethyl dihydroxy ethyl amine oxide.This class examples of substances comprises dimethyl-octa amine oxide, diethyl decyl amine oxide compound, two (2-hydroxyethyl) dodecyl amine oxide, dimethyl dodecyl amine oxide, dipropyl tetradecyl amine oxide, methylethyl hexadecyl amine oxide, laurylamide base propyl group dimethylamine oxide compound, hexadecyl dimethylamine oxide compound, stearyl dimethylamine oxide compound, tallow dimethylamine oxide compound and dimethyl 2-hydroxyl octadecyl amine oxide.C preferably ₁₆-C ₁₈Alkyl-dimethyl amine oxide and C ₁₀-C ₁₈Amido alkyl dimethylamine oxide compound.

Zwitterion (Zwitterionic) tensio-active agent

Cationic and anionic surfactant also can be included in this paper cleaning composition.This type of tensio-active agent extensively can be described as secondary amine and tertiary amines derived thing, heterocyclic secondary and tertiary amines derived thing or quaternary ammonium, quaternary phosphonium or uncle's sulfonium compound derivative.Trimethyl-glycine and sulfonation beet alkali surface activator are the examples of the zwitterionics that is suitable for herein.

Beet alkali surface activator

Betaines used herein is that general formula is R (R ¹) ₂N ⁺R ²COO ^-Compound, R is C in the formula ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl or C ₁₀-C ₁₆Amido alkyl, each R ¹Be C ₁-C ₃Alkyl, preferable methyl; R ²Be C ₁-C ₅Alkyl, preferred C ₁-C ₃Alkylidene group, more preferably C ₁-C ₂Alkylidene group.The example of the betaines compound that is fit to comprises coconut monoethanolamide base propyl-dimethyl trimethyl-glycine, hexadecyldimethyl benzyl ammonium trimethyl-glycine, C ₁₂-C ₁₄Amido propyl betaine, C ₈-C ₁₄Acid amides hexyl diethyl betaines, 4-[C ₁₄-C ₁₆Acyl methyl nitrosourea base diethyl ammonium]-1-carboxyl butane, C ₁₆-C ₁₈Amide group dimethyl betaine, C ₁₂-C ₁₆Amide group amyl group dimethyl betaine, C ₁₂-C ₁₆Acyl group methyl nitrosourea base dimethyl betaine.Preferred trimethyl-glycine is C ₁₂-C ₁₈Alkyl dimethyl ammonium hexanoate and C ₁₀-C ₁₈Amidopropyl (or ethyl) dimethyl (or diethyl) trimethyl-glycine.The title complex beet alkali surface activator also is applicable to the present invention.

The sulfonation beet alkali surface activator

The sulfonation trimethyl-glycine of Shi Yonging is that general formula is R (R herein ¹) ₂N ⁺R ²SO ₃ ^-Compound, R is C in the formula ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl, more preferably C ₁₂-C ₁₃Alkyl, each R ¹Be generally C ₁-C ₃Alkyl, preferable methyl; R ²Be C ₁-C ₆Alkyl, preferred C ₁-C ₃Alkylidene group, preferably hydroxy alkylidene.

Both sexes (ampholytic) tensio-active agent

Amphoterics can be included in the cleaning composition of this paper.This class tensio-active agent is stated as the aliphatic derivatives of secondary amine or tertiary amine widely, the perhaps aliphatic derivatives of heterocyclic secondary and tertiary amine, and fatty group wherein can be straight chain or ramose.

Cats product

Cats product also can be used in the composition of this paper.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, all the other positions of N are replaced by methyl, hydroxyethyl or hydroxypropyl in the formula.

Washing-aid compound

Cleaning composition of the present invention can contain to help washes compound as main scrubbed component.Helping and washing compound is the preferred ingredient of washing dish and laundry composition according to machine of the present invention, is generally 1%-80% with its consumption of composition weight meter, preferred 10%-70%, most preferably 20%-60%.

Being used for the manual composition of washing the dish method at most only contains low levels and helps and wash compound.Help the content of washing compound preferably to be no more than 1.5% of composition weight in the dish composition manual washing.

It can be water miscible helping and wash compound, but great majority are non-water-soluble.When composition is that the preferably water dissolubility helps and washes compound when washing dish composition, particularly machine and washing dish composition and rinse aid composition.

Helping of being fit to washed compound and comprised water-soluble monomer polycarboxylate or its sour form, homopolymerization or copolymerization polycarboxylic acid or its salt, the polycarboxylic acid here comprises at least 2 two carboxyls being opened by no more than 2 carbon atoms separate each other, any mixture of some in carbonate, supercarbonate, borate, phosphoric acid salt, silicate and aforementioned each compound.

Carboxylate salt or polycarboxylate washing assistant can be also oligopolymer of monomer on type, though since price and performance, the polycarboxylate of general preferred monomers.

The carboxylate salt that contains a carboxyl that is fit to comprises the water-soluble salt of lactic acid, oxyacetic acid and their ether derivant.The polycarboxylate that contains two carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of succsinic acid, oxysuccinic acid, ethylene oxybisacetic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The polycarboxylate that contains three carboxyls is particularly including water-soluble citrate, equisetic acid-1,2,3-propane trisalt (aconitate) and citraconate, and succinate derivative, such as at BP 1,379, the carboxy methoxy-succinic acid salt of narration in 241, at BP 1,389, the aminosuccinic acid of the newborn oxygen base succinate of narration and narration in Netherlands patent applications 7205873 in 732, also has the oxo bridge polycarboxylate, such as at BP 1,387, the 2-oxa--1 of narration in 947,1,3-tricarboxylic acid alkali propane.

The polycarboxylate that contains four carboxyls is included in BP 1,261, oxo bridge disuccinate, 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2, the 3-propane tetracarboxylic acid salt of narration in 829.Contain the substituent polycarboxylate of sulphonyl and be included in BP 1,398, disclosed sulphonyl succinic acid derivative and at BP1 in 421 and 1,398,422 and at USP 3,936,488, the sulfonylation cracking Citrate trianion of narration in 439,000.

Alicyclic ring and heterocycle polycarboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene 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 polyhydroxy-alcohol such as sorbyl alcohol, N.F,USP MANNITOL and Xylitol.Polycarboxylic aromatic acids comprises mellitic acid, 1,2,4,5 pyromellitic acids and at BP 1,425, disclosed naphthoic acid derivative in 343.

In above-claimed cpd, preferred polycarboxylic acid is the hydroxycarboxylate that each molecule contains no more than 3 carboxyls, more particularly Citrate trianion.

The mixture of female acid of monomer or oligomeric polycarboxylate sequestrant or itself and its salt also can be regarded useful helping as citric acid or citric acid/citrate mixture and wash compound.

The borate washing assistant and contain washing composition store and wash conditions under can produce boratory one-tenth borate thing washing assistant and also can use, be not lower than about 50 ℃ but be not recommended in wash conditions, use when particularly being lower than 40 ℃.

The example of carbonate builders is basic metal and alkaline earth metal carbonate, comprises Na ₂CO ₃, and sesquicarbonate, and they are at German patent application 2,321, the ultra-fine CaCO of narration in 001 (announcement on November 15th, 1973) ₃Mixture.

The object lesson of phosphate builders is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and sodium orthophosphate, potassium and ammonium, partially poly-/sodium phosphate, wherein the polymerization degree is 6-21, and phytate.

The silicate that is fit to comprises SiO ₂: Na ₂O is than being 1.0-2.8, preferred 1.6-2.4, most preferably being 2.0 water-soluble metasilicate.This silicate can be the form of anhydrous salt or salt hydrate.SiO ₂: Na ₂O than equal 2.0 be most preferred silicate.

The silicate preferred content of washing in the dish composition at machine of the present invention is the 5%-50% of composition weight, more preferably 10%-40%.

The example that is difficult for water-soluble washing assistant comprises the crystal layered silicate and extremely is difficult for molten sodium silicoaluminate.

The crystal layered silicate has following general formula:

NaMSi _xO _x+1·yH ₂O

M is Na or H in the formula; X is 1.9-4; Y is 0-20.In EP-A-0164514, disclose this crystalloid layered silicate, in DE-A-3417649 and DE-A-3742043, disclose its preparation method.Be used for purpose of the present invention, x generally has 2,3 or 4 value in the general formula, is preferably 2.Most preferably Hoechst company is with the δ-Na of trade(brand)name NaSKS-6 sale ₂Si ₂O ₅

Crystalline layered sodium silicate preferably is present in the particulate state cleaning composition, exists with the intimately mixed particulate state of ion stabilizedization of solid, water soluble material as a kind of.This ion stabilizedization of solid, water soluble thing is selected from organic acid, organic and inorganic acid salt and their mixture.

The aluminosilicate zeolite that is suitable for has Na _z[(AlO ₂) _z(SiO ₂) _y] XH ₂The structure cell general formula of O, z and y are at least 6 in the formula, and the mol ratio of z/y is 1.0-0.5, and x is at least 5, is preferably 7.5-276, more preferably 10-264.This silico-aluminate is the hydrate type, is preferably to contain 10%-28%, more preferably contains the crystallization of 18%-22% combination water.

The silico-aluminate ion exchange material can be naturally occurring material, but synthetic preferably.Synthetic crystalline silica-aluminate ion exchange material is sold with trade mark Zeolite A.Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and composition thereof, and Zeolite A has following structural formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂]·xH ₂O

Here x is 20-30, particularly 27.The structural formula of Zeolite X is Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂O.

Organic polyhydroxyl compound

Organic polyhydroxyl compound is the special preferred ingredient of cleaning composition of the present invention.The antifouling enzyme liberating degradation production of this polymerizable compound is deposited on the washes.

Organic polyhydroxyl compound one speech is intended to general polymerizable organic compound as dispersion agent and anti-resedimentation agent and soil-suspending agent in the cleaning composition.

The content of organic polyhydroxyl compound is generally the 0.1%-30% of composition weight in cleaning composition of the present invention; Preferred 0.5%-15%, most preferably 1%-10%.The example of organic polyhydroxyl compound comprises polycarboxylic acid or its salt of water-soluble organic homopolymerization or copolymerization, and polycarboxylic acid wherein comprises at least two each other by no more than 2 carboxyls that carbon atom separates.Back one base polymer is disclosed in GB-A-1, in 596,756.The example of this salt is that molecular weight is the multipolymer of the polyacrylate of 2000-5000 and it and maleic anhydride, and the molecular weight of this multipolymer is 20,000-100,000, particularly 40,000 to 80,000.

Other organic polyhydroxyl compound that is suitable for comprises that molecular weight is 3,000-100, and 000 acrylamide and acrylate polymer, and molecular weight is 2,000-80,000 acrylate/fumarate multipolymer.

Polyamino compound used herein comprises as the disclosed compound that those are obtained by aspartic acid among EP-A-305282, EP-A-305283 and the EP-A-351629.

Other organic polyhydroxyl compound that is suitable in this paper cleaning composition comprises derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose and Natvosol.

Some useful organic polyhydroxyl compounds are polyoxyethylene glycol again, and its molecular weight is 1,000-10, and 000, preferred 2,000-8,000, more preferably 4,000.

Lime soap dispersing agent

Composition of the present invention can contain lime soap dispersing agent, and it is not more than 8 as defined lime soap dispersing power (LSDP) hereinafter, preferably is not more than 7, more preferably no more than 6.The content of lime soap dispersing agent is generally the 0.1%-40% of composition weight, is preferably 1%-20%, more preferably 2%-10%.

Lime soap dispersing agent is that a kind of can preventing owing to calcium, magnesium ion make basic metal, ammonium or the amine salt of lipid acid sedimentary material takes place.Provide the quantitative measurement of lime soap dispersing agent efficient with LSDP, its measuring method is to use at H.C.Borghetty and C.A.Bergman at J.Am.Oil.Chem, Soc., and Volume 27, the calcium soap dispersion measurement method of being narrated among the p88-90 (1950).This calcium soap dispersion measurement method is extensive use of for those skilled in the art, sees also such as following survey article: W.H.Linfield at Surfactant Science Series, and Vol 7, p3; W.N.Linfield is at Tenside Surf.Det.Vol 27.p159-161 (1990) and M.K.Nagarajan, W.F.Masler, and at Cosmetics andToiletries, Vol.104, p71-73 (1989).LSDP is the weight of dispersion agent and will will be 333ppm CaCO in 30ml equivalence hardness ₃(Ca: Mg=3: in the water 2) by the scatter per-cent of weight of needed sodium oleate of the formed calcium soap precipitates of 0.025g sodium oleate.

Tensio-active agent with good L SDP will comprise some amine oxide, trimethyl-glycine, sulfonation trimethyl-glycine, alkyl polyoxyethylene vitriol and polyoxyethylene groups alcohol.

The L SDP that the present invention uses is not more than 8 tensio-active agent, and its example comprises C ₁₆-C ₁₈Alkyl-dimethyl amine oxide, C ₁₂-C ₁₈Alkyl polyoxyethylene vitriol, its average degree of ethoxylation are that 1-5, particularly ethoxylation degree are about 3 C ₁₂-C ₁₅Alkyl polyoxyethylene vitriol (LSDP=4) and average degree of ethoxylation are the C of 12 (L SDP=6) or 30 ₁₃-C ₁₅Alkyl polyoxyethylene base alcohol, their trade(brand)name are respectively the Lutensol A012 and the Lutensol A 030 of BASF AG.

The polymerization lime soap dispersing agent of Shi Yonging has narration in the article of M.K.Na-garajan and W.F.Masler herein, asks for an interview Cosmetics and Toiletries, Vol.104, p71-73 (1989).The example of this polymerization lime soap dispersing agent comprises the water-soluble salt of vinylformic acid, methacrylic acid or their mixtures and acrylamide or substituted acrylamide multipolymer, and the molecular weight of these polymkeric substance is generally 5,000-20,000.

Press down foam system

When cleaning composition prescription of the present invention becomes the machine-washing composition, preferably contain and press down foam system, its consumption is the 0.01-15% of composition weight, preferred 0.05-10%, more preferably 0.1-5%.

The foam owner that presses down who is fit to wants to comprise any known anti-alveolation compound, comprises such as the anti-alveolation compound of polysiloxane, the anti-alveolation compound of 2-alkyl alkanol and the anti-alveolation compound of liquid wax.

Anti-in this article alveolation compound one speech meaning is that its effect can be lowered the solution owing to cleaning composition, foam or any compound of bubble or the mixture of compound that produces especially when stirring this solution.

Certain preferred anti-alveolation compound used herein is included in the polysiloxane compound that is defined as the anti-alveolation compound that comprises the polysiloxane component herein.The anti-alveolation compound of such polysiloxane generally also contains silica component.Polysiloxane one speech used herein and in this industry refers to the various relative high polymkeric substance of molecular weight that contain siloxane unit and various alkyl emphatically.The preferred anti-alveolation compound of polysiloxane is a kind of polysiloxane, particularly has the end capped polydimethylsiloxane of three silyls.

Other anti-alveolation compound that is fit to comprises fatty monocarboxylic acid and water-soluble salt thereof.At USP2, narrated this type of material among 954,347 (the Wayne St.John, issue September 27 nineteen sixty).Fatty monocarboxylic acid and salt thereof as suds suppressor generally have about 24 carbon atoms of 10-, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is suitable for comprises basic metal (as Na, K and Li) salt, ammonium salt and alkanol ammonium salt.

Other anti-alveolation compound that is suitable for comprises such as high-molecular-weight hydrocarbons, as paraffin, fatty acid ester (as the fatty acid triglycercide ester), the fatty acid ester of monovalent alcohol, aliphatics C ₁₈-C ₄₀The aminotriazine that ketone (as stearone), N-alkyl replace, as trialkyl to six alkyl melamine, perhaps as the primary amine that contains 1-24 carbon atom of cyanuric chloride and 2 or 3 moles and secondary amine reaction product and the dialkyl group or tetraalkyl diammonium chloride triazine, propylene oxide, two stearic amide and a stearyl two basic metal (as Na, K, Li) phosphoric acid salt and the phosphoric acid ester that form.Can use liquid hydro carbons, as paraffinic hydrocarbon and halo paraffinic hydrocarbon.This liquid hydrocarbon is liquid under room temperature and barometric point, and its pour point is-40 ℃-Yue 5 ℃ approximately, and under atmospheric pressure minimum boiling point is not less than 110 ℃.Also know and can use wax shape hydrocarbon, preferably its fusing point is lower than 100 ℃.In for example USP 4,265,779 (Gandolfo, on May 5th, 1981 issued), narrated the hydro carbons suds suppressor.The hydrocarbon here comprises the saturated or unsaturated hydrocarbons of aliphatics with about 70 carbon atoms of about 12-, alicyclic, aromatic series and heterocycle family." paraffin " speech that uses in the discussion of this suds suppressor is used for comprising the mixture of real paraffin and cyclic hydrocarbon.

The multipolymer of oxyethane and propylene oxide, particularly blended polyoxyethylene/polyoxypropylene Fatty Alcohol(C12-C14 and C12-C18) (its chain length is a 10-16 carbon atom, and ethoxylation degree is 3-30, and the propoxylation degree is 1-10) also are suitable in this article as kilfoam.

In DE 40 21 265, narrated the anti-alveolation compound of 2-alkyl alkanols that is suitable in this article.The 2-alkyl alkanol of Shi Yonging comprises hydroxy-end capped C in this article ₆-C ₁₆Alkyl chain, described alkyl chain have a C on the 2-position ₁-C ₁₀The alkyl chain substituting group.In composition of the present invention, can use blended 2-alkyl alkanol.

The preferred foam system that presses down comprises:

(a) anti-alveolation compound, the preferred anti-alveolation compound of polysiloxane most preferably comprises following two components

The anti-alveolation compound of polysiloxane.

(i) account for poly-two of the anti-alveolation compound of polysiloxane gross weight 50-99%, preferred 75-95%

Methylsiloxane; And

(ii) account for the anti-alveolation compound of polysiloxane/silicon-dioxide gross weight 1-50%, preferred 5-25

The silicon-dioxide of %;

Wherein said silicon-dioxide/polysiloxane kilfoam consumption is 5-50%, preferred 10-40% (wt).

(b) a kind of compound dispersing agent most preferably comprises polysiloxane/glycol rake shape multipolymer,

Its polyoxyalkylene content is 72-78%, and the ethylene oxide/propylene oxide ratio is 1: 0.9

-1: 1.1, the weight content of compound dispersing agent is 0.5-10%, preferred 1-10%;

Particularly preferred this class polysiloxane/glycol rake shape multipolymer is a Dow Corning company

The commodity of commodity DCO 544 by name;

(c) inert support fluid compound comprises that most preferably ethoxylation degree is 5-50, preferred 8

-15 C ₁₆-C ₁₈Alkyl polyoxyethylene alcohols, its weight content are 5-80%,

Preferred 10-70%.

The particulate state of Shi Yonging presses down the mixture that the bubble system comprises top disclosed alkylation siloxanes and solid silica in this article.

Solid silica can be the silicon-dioxide that thermal silica, precipitated silica or gel formation technology are made.The mean particle size of the silicon-dioxide that is fit to is 0.1-50 μ m, preferred 1-20 μ m, and specific surface area is at least 50m ²/ g can handle to make it directly to be connected on the silicon-dioxide or by means of silicone resin making this silicon dioxide granule have hydrophobicity with dialkyl silicon group and/or trialkyl silyl.The preferred use by dimethyl and/or trimethyl silicon based and obtain hydrophobic silicon dioxide granule.Should to make the weight ratio of silicon-dioxide and polysiloxane be 1 to the silica containing amount that is fit to of contained preferred granular anti-alveolation compound in cleaning composition of the present invention: 100-3: 10, and preferably 1: 50-1: 7.

The representative that the another kind of particulate state that is fit to presses down foam system is that granularity is that 10nm-20nm, specific surface area are greater than 50m ²/ g and with the titanium dioxide silicon of molecular weight for the tight blended of the dimethyl silicone oil hydrophobic silaneization (most preferably trimethyl silicone hydride) of about 500-about 200,000, the weight ratio of polysiloxane and silanized silica is about 1: about 1: 2 of 1-.

In EP-A-0210731, narrate highly preferred particulate state and pressed down foam system, it comprises the anti-alveolation compound of a kind of polysiloxane and a kind of fusing point at 50-85 ℃ organic support material, and organic carrier wherein contains glycerine and the monoesters of the lipid acid of 12-20 carbon atom carbochain is arranged.The another kind of preferred particulate state that discloses EP-A-0210721 presses down foam system, and wherein organic carrier is lipid acid or the alcohol that 12-20 carbon atom carbochain is arranged, or their fusing point is 45-80 ℃ a mixture.

In the co-pending European application 91870007.1 of Procter and Gamble company, narrate another kind of particulate state very preferably and pressed down foam system, it comprises the anti-alveolation compound of polysiloxane, solid support material, a kind of organic-containing materials and glycerine, and the weight ratio of the anti-alveolation compound of glycerine and polysiloxane is 1: 2-3: 1.Co-pending European application 91201342.0 also discloses a kind of particulate state very preferably and has pressed down foam system, it includes the anti-alveolation compound of polysiloxane, a kind of solid support material, a kind of organic-containing materials and crystalline or unbodied silico-aluminate, and the weight ratio of this silico-aluminate and the anti-foam material of polysiloxane is 1: 2-3: 1.Preferred carrier materials in above-mentioned two particulate state Foam Controls very preferably all is a starch.

The example that particulate state used herein presses down foam system is the particulate state agglomeration component of being made by agglomeration process by following each composition.

(i) account for the anti-alveolation compound of the polysiloxane component of gross weight 5%-30%, preferred 8-15%,

The preferably combination of polysiloxane and silicon-dioxide;

(ii) account for the support material component of gross weight 50-90%, preferred 60-80%, preferred starch;

(iii) account for the agglomeration binder ingredients of gross weight 5-30%, preferred 10-20%, wherein should group

Dividing compound can be any compound or its mixture that is used as the agglomeration tackiness agent usually,

Described agglomeration adhesive component comprises that most preferably ethoxylation degree is the C of 50-100 ₁₆-C ₁₈

The alcohol of alkyl polyoxyethylene base; And

The (iv) C of 2-15%, preferred 3-10% (weight) ₁₂-C ₂₂Hydrogenated fatty acid.

SYNTHETIC OPTICAL WHITNER

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

SYNTHETIC OPTICAL WHITNER is that laundry of the present invention and machine are washed the preferred ingredient in the dish composition.Dish is washed in craft of the present invention and the rinse aid composition does not preferably contain SYNTHETIC OPTICAL WHITNER.

Chlorine bleach comprises alkaline metal hypochlorite and chlorination cyanurate.In the present composition, use chlorine bleach will be as far as possible usefulness less, preferably do not contain chlorine bleach in the composition.

The inorganic peracid salt SYNTHETIC OPTICAL WHITNER

Dish washed by machine of the present invention and laundry composition preferably includes the inorganic peracid salt that generally exists with sodium-salt form, and its content accounts for the 1-40% of composition weight, preferred 2-30%, more preferably 5-25%.

The example of inorganic peracid salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic peracid salt is generally an alkali metal salt.Inorganic peracid salt with the crystalline solid forms of supplementary protection not is includable.Yet to some peracid salt, its granular composition preferably uses and can offer peracid salt has the material of better stability in storage in particulate product coated form.

Sodium peroxoborate can be with one hydration standard molecule formula NaBO ₂H ₂O ₂Or four hydrated form NaBO ₂H ₂O ₂3H ₂O exists.

SPC-D is the preferred peracid salt that joins in the cleaning composition of the present invention, and this is to have the 2Na of being equivalent to ₂CO ₃3H ₂O ₂Adducts, its commercial form is a crystalline solid.SPC-D preferably joins in this composition with the form that applies.Preferred coating materials comprises the mixture of alkali metal sulfates and carbonate.GB 1,466, narrated among 799 (Interox, on March 9th, 1977 issued) this coating with and coating process.The weight ratio of mixing salt coating material and percarbonate is 1: 200-1: 4; Preferred 1: 99-1: 9, more preferably 1: 49-1: 19.Mixing salt is Na preferably ₂SO ₄And Na ₂CO ₃Mixture, its general formula is Na ₂SO ₄NNa ₂CO ₃, wherein n is 0.1-3, preferred 0.3-1.0, more preferably 0.2-0.5.

The another kind of coating material that is suitable for is SiO ₂: Na ₂The O ratio is 1: 6-3.4: 1, preferred 2.8: 1 water glass, provide with the form of the aqueous solution, and the content of sodium silicate solid is the 2-10% of percarbonate weight, (being generally 3-5%).In coating, also can comprise Magnesium Silicate q-agent.Suitable coating material in addition comprises basic metal and alkaline earth metal sulphate and carbonate.

Peroxide one vitriolate of tartar is the another kind of peracid salt that can be used in this cleaning composition.

Peroxyacid bleach precursor

Dish washed by machine of the present invention and the laundry cleaning composition preferably also comprises peroxyacid bleach precursor (bleach-activating agent).The add-on of peroxy acid bleach precursor is generally the 1-20% of composition weight, preferred 1-10%, more preferably 1-7%.

Join machine of the present invention and wash the peroxyacid bleach precursor that dishwashing washs in the composition and generally contain one or more N-acyl groups or O-acyl group, this precursor can be selected from all kinds of very widely materials.The classification that is fit to comprises the acyl derivative of acid anhydrides, ester, imide and imidazoles and oxime, and GB-A-1586789 has narrated useful example in these compounds.Most preferred class is at GB-A-836988,864798,1147871 and 2143231 disclosed esters and disclosed imide in GB-A-855735 and 1246388.Particularly preferred bleach precursor compound is that general formula is (CH ₃CO) ₂-N-(CH ₂) _x-N-(CH ₃CO) ₂N, N, N ', N ' tetrem acylated compounds, wherein x can be 0 or the integer of 1-6.

Example comprises the wherein tetra-acetylated methylene diamine (TAMD) of x=1; The tetra-acetylated hexanediamine (TAHD) of the tetra acetyl ethylene diamine of x=2 (TAED) and x=6.These and similar compounds have been narrated among the GB-A-907356.Most preferred peroxyacid bleach precursor is TAED.

Another kind of peroxy acid bleach activating compounds is the acid amides substitution compound of narrating in EP-A-0170386.

Other peroxyacid bleach precursor compound comprises acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems, trimethylammonium acyloxy benzene sulfonic acid sodium salt, acetoxyl group benzene sulfonic acid sodium salt and benzoyloxy benzene sulfonic acid sodium salt, such as disclosed in EP-A-0341947.

Organic peroxide acid

Dish washed by machine and the laundry cleaning composition also can contain organic peroxide acid, and content is the 1-15% of composition weight, preferred 1-10%.

Useful organic peroxide acid is included in the acid amides of narrating among the EP-A-0170386 and replaces peroxy acid.

Other organic peroxide acid, as described in the EP-A-0341947, comprise diperoxy dodecandioic acid, diperoxy dodecane dicarboxylic acid, diperoxy tetradecane dicarboxylic acid, list and diperoxy n-nonanoic acid, the basic sharp acid of list and diperoxy Brazil, single peroxide phthalic acid, this formic acid of peroxide and their salt.

Additional enzymes

The optional component of another that uses in this cleaning composition is one or more additional enzymes.

Preferred additional enzymes comprises commodity lipase, amylase, neutrality and Sumizyme MP, esterase, cellulase and the peroxidase in the common adding cleaning composition.At USP 3,519, suitable enzyme has been discussed in 570 and 3,533,139.

Preferred commercially available protein enzyme comprises that Denmark Novo Nordisk A/S company commodity are called Alcalase ^, Salvinase ^, Primase ^, Durazym ^And Esperase ^Gist-Brocades company commodity are called Maxatase ^, Maxacal ^And Maxapem ^The commodity of GenencorInternational company and the trade(brand)name Opticlean of Solvay Enzymes company ^And Optimase ^Deng commodity.The proteolytic enzyme of narration also can be included in the cleaning composition of the present invention in our common pending application USSN 08/136797.The amount that joins proteolytic enzyme in the present composition can be the 0.0001-2% (in organized enzyme) of composition weight.

Preferred amylase comprises such as at GB-1, the α-Dian Fenmei that is obtained by the specific bacterial strain of B lichens that is described in detail among 269,839 (Novo).Preferred commodity starch enzyme comprises such as Gist-Brocadses company commodity Rapidase by name ^, Novo NordiskA/S company commodity Fungamyl by name ^, Teramyl ^And BAN ^Commodity.The diastatic amount that joins among the present invention is the 0.0001-2% organized enzyme of composition weight.

The add-on of lipolytic enzyme (lipase) is the active lipolytic enzyme of the 0.0001-2% of composition weight, preferred 0.001-1%, more preferably 0.001-0.5%.

Lipase can be from fungi or bacterium on the source, such as planting bacterium, high temperature mould or pseudomonas from the corruption of making lipase, the bacterial strain that comprises pseudomonas pseudoalcaligenes or Pseudomonas fluorescens, the lipase that also uses these bacterial strain chemistry or gene modification dissociant to obtain in this article.

A kind of preferred lipase derives from the pseudomonas pseudoalcaligenes of narrating in the European patent EP-B-0218272 of approval.

Another kind of preferred enzyme is herein planted the gene of bacterium and is carried out vegetative propagation by deriving from the pubescence corruption, and be injected into as in host's the Oryza aspergillus and obtain, in European patent application EP-A-0258068, this there is narration, its commodity are from the Novo Nordisk A/S company of Denmark Bagsvaerd, and commodity are called Lipolase ^USP 4,810, also narrated this lipase in 414 (people such as Huge-Jensen, on March 7th, 1989).

That another kind is suitable for is at [EC.3.1.1.50], and it also can be regarded as a kind of special lipase, promptly a kind of enzyme that need not interface activation.The at that joins in the cleaning composition is disclosed in such as WO 88/09367 (Genencor).

Operable in the present invention cellulase had both comprised that the bacteria cellulose enzyme also comprised fungal cellulase.They preferably will have the optimization pH value of 5-9.5.The cellulase that is fit to is disclosed in the USP 4,435,307 of Barbesgoard etc.It discloses by corruption plants the fungal cellulase that bacterium Insolens makes.At GB-A-2, the cellulase that is fit to is also disclosed in 075,028, GB-A-2,095,275 and DE-OS-2,247,832.

The example of this cellulase is to plant bacterium insolens (Humicola grisca var.thermoidea) by corruption, particularly rotten cellulase of planting the manufacturing of bacterium DSM 1800 bacterial strains.The plain enzyme of other useful fiber is to derive from corruption to plant bacterium insolens, the about 50KDa of molecular weight, and iso-electric point is 5.5, contains 415 amino acid whose cellulases.The cellulase of particularly suitable is to have to be of value to the cellulase of protecting color characteristics.The example of this cellulase is the cellulase of narration in european patent application No91202879.2 (Novo company, on November 6th, 1991 submitted to).

Peroxidase and oxygen source use together such as percarbonate, perborate, persulphate, hydrogen peroxide etc.They are as " solution bleaching ", prevent that promptly in washing operation dyestuff under substrate or pigment from transferring on other substrate the washing soln.Peroxidase is known in prior art, comprises such as horseradish peroxidase, lignoenzyme and halo peroxidase (such as chloro and bromo peroxidase).The cleaning composition that contains peroxidase is being disclosed such as PCT International Application No. WO 89/099813 with in the European patent application EP No.91202882.6 that submitted on November 6th, 1991.

Described cellulase that adds in cleaning composition and/or peroxidase consumption are the 0.0001-2% that organized enzyme accounts for cleaning composition weight.

The enzyme stabilising system

Preferably containing enzyme composition and can contain about 10%, preferred about 8%, the enzyme stabilising system of about 6% (weight) of 0.1-more preferably from about of about 0.005-of the 0.001-that has an appointment herein.This enzyme stabilising system can be any stabilising system compatible with detergent enzyme.Such stabilising system can contain Ca ion, boric acid, propylene glycol, short chain carboxy acid, organic boronic and their mixture.Such stabilising system also can comprise the possibility of reversal enzyme inhibitors, as the possibility of reversal proteinase inhibitor.

The composition of this paper also can comprise about 10%, the preferred chlorine bleaching scavenging agent of about 6% (weight) of about 0.01-of 0-, adds it and be used for preventing that the chlorine bleaching thing that exists from attacking and make enzyme deactivation in many tap water, particularly under alkaline condition.Though the water containing chlorine amount may be very low, be generally the about 1.75ppm of about 0.5-, chlorine is more than general in the total amount of the water that contact with enzyme in washing process, and therefore, in use the stability of enzyme also may be problematic.

The chlorine scavenger negatively charged ion that is fit to can extensively obtain, can be by containing NH ₄ ⁺Cationic salt or sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide wait and illustrate.Antioxidant such as carbaminate, xitix etc.Organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and their mixture also can use.Also can use other conventional scavenging agent such as hydrosulfate, nitrate, muriate, hydrogen peroxide cource such as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D if desired, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate and their mixture etc.

The inhibition of dye transfer

The inhibition method that the dyestuff that the dissolved that the present invention also relates to be run in the washing operation of colored fabric suspends shifts to another kind of fabric from a kind of fabric.

The polymeric dye transfer inhibitor

The cleaning composition of this paper also can contain the polymeric dye transfer inhibitor of 0.01-10%, preferred 0.05-0.5% (weight).

This polymeric dye transfer inhibitor preferably is selected from multipolymer, Polyvinylpyrolidone (PVP) or their combination of polyamine N-oxypolymer, N-vinyl pyrrolidone and N-vinyl imidazole.

A) polyamine N-oxypolymer

The polyamine N-oxypolymer of Shi Yonging contains the unit of following structural formula herein:

P is a polymerizable unit in the formula, can be connected with the R-N-O group in the above, and perhaps R-N-O group wherein constitutes the part of polymerizable unit, and perhaps both all are.A is -O-,-S-,-N-; X is 0 or 1;

R be aliphatic, polyoxyethyleneization is aliphatic, aromatic, heterocycle or alicyclic group, or any combination between them, the N of the N-O base of can ining succession thereon, perhaps the N in the N-O base is the part in these groups.

Can use as shown in the formula structure represent the N-O group:

R in the formula ₁, R ₂And R ₃Be that aliphatics, aromatic series, heterocycle or alicyclic group or they are used in combination, x and/or y and/or z are 0 or 1, and the N on N-O base of ining succession on it, and perhaps the N on the N-O base forms the part of these groups.This N-O base can be the part of polymerizable unit (P), perhaps can link to each other with polymeric skeleton, and perhaps the both is.

The polyamine N-oxide that is fit to that N-O base constitutes a polymerizable unit part in formula comprises that R in the formula is selected from the polyamine N-oxide of aliphatics, aromatic series, alicyclic or heterocyclic group group.The described polyamine N-oxide of one class has comprised the group of the polyamine N-oxide of the N formation R base part of N-O base in the formula.Preferred polyamine N-oxide compound is that R is a heterocyclic radical in the formula, as the compound of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, bifurcation pyridine and their derivatives.

Another kind of described polyamine N-oxide comprises the polyamine N-oxide that the N in the N-O base links to each other with the R base in the formula.

Other suitable polyamine N-oxide is the polyamine N-oxide that the N-O base links to each other with polymerizable unit.

Preferred these polyamine N-oxide of a class are to have general formula (I), and R is aromatic series, heterocycle family or alicyclic group, and N-O functional group's N is the polyamine N-oxide of a described R base part.The example of this class is that R is a heterogeneous ring compound in the formula, as the polyamine N-oxide of pyridine, pyrroles, imidazoles and their derivative.

Another kind of preferred polyamine N-oxide compound is to have general formula (I), and R is aromatic series, heterocycle or alicyclic radical, wherein N-O functional group's N and the basic polyamine oxide compound that links to each other of described R.The example of this class is the polyamine oxide compound that the R base can be aryl such as phenyl in the formula.

As long as the amine oxide polymkeric substance that forms is water miscible and has the dye transfer inhibition, can use any polymer backbone.The polymeric skeleton example that is fit to is polyethylene base class, polyalkylene class, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.

Amine is 10 with the ratio of amine n-oxide in amine N-oxypolymer of the present invention: 1-1: 1,000,000.Yet,, can change the amount of the amine oxide base that in polyamine N-oxypolymer, exists by suitable copolymerization or suitable N-oxidisability.This amine is preferably 2 with the ratio of amine oxide: 3-1: 1,000,000, more preferably 1: 4-1: 1,000,000, most preferably 1: 7-1: 1,000,000.In fact polymkeric substance of the present invention has comprised random or segmented copolymer, and wherein a class monomer is an amine n-oxide, and another kind of monomer can be an amine n-oxide, also can not be.The unitary PKa of amine oxide＜10 in this polyamine N-oxide, preferred PKa＜7, more preferably PKa＜6.

Can obtain polyamine N-oxide with any polymerization degree almost.As long as this material has required water-soluble and dye suspension ability, the polymerization degree is not crucial.Molecular-weight average is generally 500-1, and 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

Preferred polymers used herein can comprise a kind of polymkeric substance that is selected from N-vinyl imidazole-N-vinylpyrrolidone copolymer, and the molecular-weight average of wherein said polymkeric substance is 5,000-50, and 000, preferred 8,000-30,000, more preferably 10,000-20,000.The mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1-0.2 in preferred N-vinyl imidazole-N-vinylpyrrolidone copolymer, preferred 0.8-0.3, more preferably 0.6-0.4.

C) Polyvinylpyrolidone (PVP)

The cleaning composition of this paper also can use Polyvinylpyrolidone (PVP) (PVP), and its molecular-weight average is 2,500-400, and 000, preferred 5,000-200,000, more preferably 5,000-50,000, most preferably 5,000-15,000.The PVP that is fit to is the commodity of buying from New York, New York and Montreal, CAN city ISP company, commodity are called PVP K-15, and (molecular-weight average is 10,000), PVP K30 (molecular-weight average 40,000), PVP K-60 (molecular-weight average 160,000) and PVPK-90 (molecular-weight average 360,000).ISP company also supplies PVP K-15.Other PVP by BASF AG's supply of commodities comprises Sokalan HP165 and Sokalan HP 12.

The add-on of PVP is the 0.01-5% of washing composition weight in this paper cleaning composition, preferred 0.05-3%, more preferably 0.1-2%.The PVP amount that occurs in washing soln is 0.5-250ppm, preferred 2.5-150ppm, more preferably 5-100ppm.

D) Ju Yi Xi oxazolidinone

Cleaning composition herein also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidinone is 2,500-400, and 000, preferred 5,000-200,000, more preferably 5,000-50,000, most preferably 5,000-15,000.

The amount of the Ju Yi Xi oxazolidinone that adds in cleaning composition is 0.01-5% (weight), preferred 0.05-3%, more preferably 0.1-2%.The amount of the Ju Yi Xi oxazolidinone that occurs in washing soln is generally 0.5-250ppm, is preferably 2.5-150ppm, more preferably 5-100ppm.

E) polyvinyl imidazol

The cleaning composition of this paper also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazol is 2,500-400, and 000, preferred 5,000-50,000, more preferably 5,000-15,000.

The amount of the polyvinyl imidazol that adds in cleaning composition is 0.01-5% (wt), preferred 0.05-3%, more preferably 0.1-2%.The amount that appears at the polyvinyl imidazol in the washing soln is 0.5-250ppm, preferred 2.5-150ppm, more preferably 5-100ppm.

Corrosion inhibitor

This composition also can contain corrosion inhibitor.This corrosion inhibitor is the preferred ingredient that machine of the present invention is washed the dish composition, and its add-on is the 0.05-10% of composition total weight, preferred 0.1-5%.

The corrosion inhibitor that is fit to comprises paraffin oil, and general main is the aliphatic hydrocarbon of the branching of carbonatoms 20-50; Preferred paraffin oil is selected from cyclic hydrocarbon and is about 32: 68 the C that is mainly branching with non-cyclic hydrocarbon ratio ₂₅-C ₄₅Hydrocarbon; The Wintershall company of Germany Salzbergen is exactly the paraffin oil that satisfies this performance with the commodity that trade(brand)name WINOG 70 sells.

Other corrosion inhibition immunomodulator compounds that is fit to comprises benzotriazole and derivative arbitrarily thereof, and mercaptan and dibasic alcohol particularly have the mercaptan of 4-20 carbon atom, comprise lauryl mercaptan, thiophenols, thionaphthol, thionalid, sulfo-anthrol.C ₁₂-C ₂₀Lipid acid or its salt, particularly Aluminium Tristearate Micronized sterile also is suitable for.C ₁₂-C ₂₀Hydroxy fatty acid or its salt also are suitable for, and the octane of Phosphation is to decane and other oxidation inhibitor, and (BHT) also is suitable for such as beta-hydroxy toluene.

Heavy metal ion chelating agent

Can contain heavy metal ion chelating agent in the prescription of cleaning composition of the present invention.Heavy metal ion chelating agent is the preferred ingredient that laundry of the present invention and machine are washed the dish composition, and its content is the 0.005-3% of composition total weight, preferred 0.05-1%, more preferably 0.07-0.4%.

Suitable heavy metal ion chelating agent used herein comprises organophosphate, as amino alkylidenyl poly-(alkylidene group phosphoric acid salt), ethane 1-hydroxyl bisphosphate an alkali metal salt, nitrilo trimethylene phosphonic salt.

Above-mentioned all kinds of in the middle of, preferably diethylenetriamine five (methylene radical phosphoric acid salt), hexamethylene-diamine four (methylene radical phosphoric acid salt) and hydroxy ethylene-1,1-diphosphate.

Phosphate compounds can exist with its sour form, also can be used as basic metal or alkaline-earth metal ions title complex and exists, and the mol ratio of described metal ion and described phosphate compounds was at least 1: 1.At US-A-4, narrated this title complex in 259,200, the organic phosphoric acid salt compound preferably exists with the form of its magnesium salts.

The heavy metal ion chelating agent that other is suitable for used herein comprises nitrilotriacetic acid(NTA) and polynary aminocarboxylic acid, such as ethylene diaminetetraacetic acid, ethylidene pentaacetic acid, ethylene diamine disuccinic acid or their water-soluble alkali metal salts.Particularly preferably be ethylene diamine-N, the salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement ammonium, or their mixture.Preferred EDDS is free acid or sodium or magnesium salts or its complex form.The example of preferred sodium salt comprises Na ₂EDDS and Na ₃EDDS.The example of preferred magnesium complex comprises MgEDDS and Mg ₂EDDS.Magnesium complex is most preferred.

At other heavy metal example sequestrants used herein are imine oxalic acid derivatives, as the 2-hydroxyethyl oxalic acid and the glyceryl imido oxalic acid of narration in EPA 317 542 and 399,133.

Heavy metal ion chelating agent used herein can be by above-mentioned all kinds of composition mixtures.

Softening agent

In laundry cleaning composition of the present invention, also can comprise fabric softener.This softening agent can be inorganic or organic.GB-A-1,400,898 and USP 5,019,292 in to disclose smectic clays be the example of inorganic softening agent.As at GB-A-1,514,276 and EP-B-0 011 340 described in, the organic fabric softening agent comprises water-soluble tertiary amine, discloses tertiary amine and single C in EP-B-0 242 919 ₁₂-C ₁₄The combination of alkyl quaternary ammonium salts.The organic constituent of the fabric softener that other is suitable for comprises as disclosed high molecular weight polyethylene glycol in EP 299,575 and 313,146.

Be added in the rest part of prescription as doing mixed component, the add-on of smectic clays is generally 5-15%, preferred 8-12% (weight).The add-on of organic fabric softening agent such as water-soluble tertiary amine or two long-chain acid amides is generally 0.5-5% (weight), preferred 1-3%, and the add-on of high molecular weight polyethylene glycol and water-soluble cationic material is 0.1-2%, preferred 0.15-1.5% (weight).These materials generally are the spray-dired parts that is added to composition, though more more convenient to do mixed particle adding in some cases, also can be used as melt liquid they are sprayed on other solid ingredient of composition.

Calcium

In the cleaning composition prescription of washing dish by hand, can add 0.01-3%, the calcium ion of preferred 0.15-1%.

Such as adding calcium ion with the form of muriate, oxyhydroxide, oxide compound, formate, acetate or nitrate.If anion surfactant is the form of acid, calcium can add with this acid that neutralizes with the water slurry form of calcium oxide or calcium hydroxide.

The calcium stable agent

In any composition that contains calcium, can add oxysuccinic acid, toxilic acid or acetate or their salt, or add some lime soap dispersing agent compound,, particularly prevent insoluble calcium precipitation so that good product stability to be provided.

Magnesium

Wash in craft of the present invention and preferably to add 0.01-3% in the dish composition, the magnesium ion of preferred 0.15-2% (weight) is to improve foam performance.

Solvent

Cleaning composition of the present invention can contain organic solvent.Wash the 1-30% that amount that the dish composition contains solvent system is preferably composition weight, preferred 3-25%, more preferably 5-20% according to craft of the present invention.This solvent system can be single solvent or mixed solvent system, but mixed solvent system preferably.Preferably the main component of solvent system is a low volatility at least.

Suitable organic solvent used herein has following general formula:

RO(CH ₂C(Me)HO) _nH，

R is alkyl, thiazolinyl or alkylaryl in the formula, and they have 1-8 carbon atom; N is the integer of 1-4.R is preferably the alkyl that contains 1-4 carbon atom, and n is 1 or 2.Particularly preferred R agent is normal-butyl or isobutyl-.Preferred this kind solvent is 1-n-butoxy propan-2-ol (n=1) and 1-(2-n-butoxy-1-methyl ethoxy) propan-2-ol (n=2) and their mixture.

Other solvent used herein comprises water-soluble CARBITOL (Trivalin SF) solvent or water-soluble CELLOSOLVE (cellosolve) solvent.Water-soluble Trivalin SF is 2-(2-alkoxyl group oxyethyl group) alcohol compound, and wherein alkoxyl group derives from ethyl, propyl group or butyl; Preferred water-soluble Trivalin SF is 2-(2-butoxyethyl group) ethanol, also claims diethylene glycol monobutyl ether.Water-soluble cellosolve is a 2-alkoxyl group ethoxy ethanol compounds, preferred 2-bu-toxyethoxy.

Other solvent that is suitable for is phenylcarbinol and glycols, as 2-ethyl-1, and 3-hexylene glycol and 2,2,4-trimethylammonium-1,3-pentanediol.

The low-molecular weight water-soluble liquid macrogol also is the solvent that this paper is suitable for.

Alkyl list pure and mild glycol, particularly C ₁-C ₆The pure and mild glycol of alkane list is adapted at using herein.Preferred C ₁-C ₄Single hydroxyl alcohol (as ethanol, propyl alcohol, Virahol, butanols and their mixture), especially preferably ethanol; C ₁-C ₄Dihydroxy alcohol, (comprising propylene glycol) also is particularly preferred.

Hydrotropic agent

Hydrotropic agent generally is added to craft of the present invention and washes in dish and the rinse aid composition, and add-on is generally 0.5-20%, preferred 1-15% (weight).

Useful hydrotropic agent comprises xylene monosulfonic acid Na, K and NH ₄Salt, toluenesulphonic acids Na, K and NH ₄Salt, isopropyl sulfonic acid Na, K and NH ₄Salt and their mixture.

Can be used as hydrotropic other compound herein and comprise polycarboxylate.Some polycarboxylate has the calcium chelating and the hydrotropy.Useful especially hydrotropic agent is an alkyl polyethoxye polycarboxylic acid salt tensio-active agent, those that narrated as this paper front.

The component that other is optional

Other the optional component that is suitable for joining in the present composition comprises essence, pigment and filling salt; Sodium sulfate is preferred filling salt.

The composition shape

Cleaning composition of the present invention can be filled a prescription becomes arbitrarily required shape, such as powdery, particulate state, paste, liquid, gel and sheet.The composition fits best that the present invention washes dish by hand becomes liquid or gel.

Liquid composition

Cleaning composition of the present invention can fit in liquid detergent compositions.This liquid detergent compositions generally contains 94-35% (weight), preferred 90-40%, and the more preferably liquid vehicle of 80-50% is such as water.The mixture of water and organic solvent is preferential the selection.

Gelatinous composition

Cleaning composition of the present invention also can be gel.Generally about 750 with molecular weight, the polyalkenyl polyethers of 000-about 4,000,000 is prepared such composition.

Solids composition

Cleaning composition of the present invention also can be solid state, such as powder.Particle and sheet.

The granularity of particulate composition component of the present invention should be to make in this particle no more than 5% diameter greater than 1.4mm, and no more than 5% diameter is less than 0.15mm.

The tap density of particulate state cleaning composition of the present invention generally is at least 450g/l, preferably 600g/l, more preferably 650-1200g/l at least.

The mensuration of tap density is with simple funnel agar diffusion method, is included in and fixes a conical hopper on the matrix, in its underpart one flap valve is housed, and can allow the funnel content be vented to be arranged in the cylindrical cup of alignment with it of funnel below.The funnel upper and lower ends is respectively 130mm and 40mm, and its installation method is to make 140mm place above chassis surface, its lower end.Cup height overall 90mm, interior high 87mm, internal diameter 84mm, its nominal volume are 500ml.

When measuring with hand with powder impouring funnel, open flap valve and fill cup by powder and overflow.From framework, shift out the cup of filling, scraped from the cup upper edge, scrape off unnecessary powder with the instrument such as the knife of a straight flange.Then the cup of filling is weighed, the powder weight that obtains is on duty with 2, just obtain the tap density value of representing with g/l.Replicate measurement if necessary.

Manufacture method-granular composition

General by various different methods, comprise do mix, spraying drying, agglomeration and granulation make granular detergent compositions of the present invention.

Washing methods

Basically can use the present composition with any washing or purging method, comprise having rinse step and adding the rinse aid method for compositions respectively.Preferred machine and the manual dish method of washing will be narrated in the back.

Machine is washed the dish method

Preferred machine is washed the dish method and is comprised with the aqueous solution that wherein dissolves or disperseed the above-mentioned machine of significant quantity to wash dish or rinse composition and handle dirty article, as pottery, glassware, hollow vessel, cutter and mixed sundries ware." machine of significant quantity is washed the dish composition " meaning is promptly dissolved in the washing soln that 3-10 rises or is dispersed with the 8-60g product, and this is typical doses and a washings volume commonly used in conventional machine washes the dishes method.

Wash the dish method by hand

The dish method is washed in craft of the present invention, and dirty dish will contact with the present composition of significant quantity; 25 plates of general every processing are about the about 20g of 0.5-, the about 10g of preferably about 3-.The amount of the actual cleaning composition that uses will depend on user's judgement, depend on that also specific product prescription, composition concentration, the plate number that will clean and the pollution level of plate etc. as composition are all multifactor.

Preferred manual washing in the dish method of the present invention, the strong solution of scrubbed component is put on the plate surface to be washed, " strong solution " speech meaning is that the dilution of product is not less than 20% (weight), preferably is not less than 50% (weight), and most preferably composition uses with undiluted form.

Another preferred manual washing in the dish method of the present invention is used the dilute solution of a large amount of these cleaning composition.Preferably plate being placed in the dilute solution and soaking for some time, generally is 5 seconds-30 minutes.

In cleaning composition, the component implication of abbreviation is as follows:

LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

XYAS:C _1X-C _1YSodium alkyl sulfate SAS: the C that is sodium-salt form ₁₂-C ₁₄Secondary (2,3) alkyl-sulphate APG: alkyl gathers the glycoside tensio-active agent, and general formula is C ₁₂(glucosyl) _x, x=1.5AEC: alkyl polyoxyethylene carboxylate surface active agent, general formula are C ₁₂(CH ₂CH ₂O) ₂-

Carboxylate salt SS: the sad secondary soap surfactant 25EY of formula 2-butyl: be mainly C ₁₂-C ₁₅Linear primary alconol produce with the condensation of average Y moles of ethylene oxide

Thing 45EY: be mainly C ₁₄-C ₁₅Straight chain primary alcohol produce with the condensation of average Y moles of ethylene oxide

Thing XYEZS:C _1X-C _1YThe sodium alkyl sulfate and the condensation of the average Z moles of ethylene oxide of per molecule produce

Thing nonionic: C ₁₃-C ₁₅Mixed polyoxyethylene/polyoxypropylene Fatty Alcohol(C12-C14 and C12-C18), average ethoxylation

Degree 3.8, average propoxylation degree 4.5, BASF AG's vending articles name

Plurafax LF 404, CFAA:C ₁₂-C ₁₄Alkyl N-methyl glucose amide TFAA:C ₁₆-C ₁₈Alkyl N-methyl glucose amide silicate: amorphous sodium silicate (SiO ₂: Na ₂O=2.0) NaSKS-6: crystalline layered silicate, structural formula δ-Na ₂Si ₂O ₅Carbonate: Carbon Dioxide na phosphates: tripoly phosphate sodium STPP MA/AA:1: 4 toxilic acids/acrylic copolymer, about 80,000 polyacrylates of molecular-weight average: the polyacrylate homopolymer, molecular-weight average 8,000, BASF AG goes out

Sell trade(brand)name PA30 zeolite A: hydrated sodium aluminosilicate, molecular formula are Na ₁₂(AlO ₂SiO ₂) _n27H ₂O, elementary grain

Degree 1-10 μ m Citrate trianion: citric acid (dihydrate) trisodium citric acid: the citric acid perborate: the anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER of a hydration, empirical formula are NaBO ₂H ₂O ₂PB ₄: anhydrous sodium perborate tetrahydrate percarbonate: anhydrous SPC-D SYNTHETIC OPTICAL WHITNER, empirical formula are 2Na ₂CO ₃3H ₂O ₂TAED: tetra acetyl ethylene diamine paraffin: Wintershall company sells, the paraffin oil polygalacturonase of trade(brand)name Winog 70: the pectin that Novo Nordisk A/S company sells with trade(brand)name Pectinex AR

Lytic enzyme proteolytic enzyme: the proteolysis that Novo Nordisk A/S company sells with trade(brand)name Savinase

Enzyme amylase: the shallow lake that Novo Nordisk A/S company sells with trade(brand)name Termamyl 60T

Powder lytic enzyme lipase: the steatolysis that Novo Nordisk A/S company sells with trade(brand)name Lipolase

Enzyme peroxidase: peroxidase cellulase: the Mierocrystalline cellulose that Novo Nordisk A/S company sells with trade(brand)name Carezyme

Lytic enzyme CMC: Xylo-Mucine HEDP:1, the diethylidene three that 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP:Monsanto company sells with trade(brand)name Dequest 2060

Amine five (methylene phosphonic acid) PVP: Polyvinylpyrolidone (PVP) EDDS: quadrol N, N '-disuccinic acid, [S, S] the isomer suds suppressor that is sodium-salt form: 25% whiteruss (50 ℃ of Mpt), 17% hydrophobicity white carbon black and

58% paraffin oil granular suds suppressing agent: 12% polysiloxane/white carbon black, 18% stearyl alcohol and 70% particulate state are formed sediment

Powder SCS: cumene sodium sulfonate vitriol: anhydrous sodium sulphate

All enzyme dosages are the % number that organized enzyme accounts for composition weight in the following example.

Embodiment 1 is prepared as follows machine according to the present invention and washes dishwashing and wash composition (weight part)

	A	B	C	D	E	F
							Citrate trianion	24.0	-	-	24.0	24.0	29.0
Phosphoric acid salt	-	30.0	46.0	-	-	-
							MA/AA	6.0	-	-	6.0	6.0	-
Silicate	27.5	-	33.0	27.5	27.5	25.7
							Carbonate	12.5	23.5	-	12.5	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	3.0	4.4
							Benzotriazole	-	0.3	-	-	-	0.3
Paraffin	-	0.5	-	-	-	0.5
							HEDP	-	-	-	-	-	0.5
Proteolytic enzyme	0.04	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	-
							Polygalacturonase	0.05	0.07	0.04	0.01	0.08	0.05
Nonionic	-	1.5	1.5	1.5	1.5	1.5
							Vitriol	1.4	2.4	2.4	12.1	12.1	3.0
35AE3S	-	-	5.0	-	5.0	-
							Granular suds suppressor	1.0	-	-	-	-	-
Water and less important thing	To 100%

When being used in machine and washing the dish method, said composition provides good dirt ability.

Embodiment 2

According to the manual dish composition of washing of the following liquid of the present invention's preparation

Weight %

	I	II	III	IV	V
						23AE0.8S	10.0	10.0	6.0	5.0	10.0
23AE3S	7.0	7.0	10.0	15.0	7.0
						The C12/14 alkyl amine oxide	2.0	1.0	-	1.0	2.0
C12/14 alkyl dimethyl trimethyl-glycine	-	1.0	1.5	2.0	-
						C12/14 Ampholak(TM)	-	-	1.5	-	-
CFAA	12.0	6.0	12.0	11.0	12.0
						C10 alkyl polyoxyethylene thing (average 8)	2.0	5.0	5.0	4.6	5.0
Mg ++	-	0.6	-	0.3	0.6
						Ca ++	-	-	0.3	0.15	0.1
Toxilic acid	-	-	0.2	0.3	-
						Polygalacturonase	0.05	0.01	0.02	0.03	0.04
Proteolytic enzyme	0.01	0.02	0.01	0.02	0.03
						Water and less important thing	To 100%

The all surface promoting agent that mixes except that glucamide prepares composition.Then magnesium salts and calcium salt are dissolved in solution in advance with toxilic acid, and are added in the surfactant mixture of other component.With hydrochloric acid pH is adjusted to 7.3 at last, check viscosity.

Embodiment 3

The manual dish composition of washing of the liquid of the present invention that is prepared as follows.The pH value of composition is transferred to 7.0-7.4.

Weight %

	I	II	III	IV	V
						LAS	-	-	-	-	10.0
23AE0.8S	10.0	10.0	6.0	5.0	5.0
						23AE3S	3.0	7.0	10.0	15.0	-
SS	-	-	4.0	-	-
						The C12/14 alkyl amine oxide	2.0	1.0	-	1.0	2.0
AEC	-	-	-	5.0	-
						C12/14 alkyl dimethyl trimethyl-glycine	-	1.0	1.5	2.0	-
C12/14 Ampholak(TM)	-	-	1.5	-	-
						CFAA	12.0	-	12.0	11.0	-
APG	-	12.0	-	-	-
						C10 alkyl polyoxyethylene thing (average 8)	5.0	5.0	5.0	4.6	5.0
Mg ++	-	0.6	0.3	0.3	0.6
						Ca ++	-	-	0.3	0.15	0.1
Toxilic acid	-	-	0.2	0.3	-
						Polygalacturonase	0.05	0.1	0.02	0.03	0.04
Proteolytic enzyme	0.01	0.02	0.01	0.02	0.03
						Water and less important thing	To 100%

Embodiment 4

It is as follows to have prepared particulate state fabric cleaning composition of the present invention:

	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	-
					Polygalacturonase	0.04	0.06	0.1	0.04
Water and a small amount of component	To 100%

Embodiment 5 is as follows by the particulate state fabric cleaning composition of the present invention's preparation:

	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
					Polygalacturonase	0.20	0.01	0.02	0.08
Proteolytic enzyme	0.06	0.03	0.02	0.08
					Water and less important thing	To 100%

Embodiment 6

It is as follows to have prepared the particulate state fabric cleaning composition of the present invention that is particularly useful in washing colored fabric:

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
Polygalacturonase	0.01	0.05
			Proteolytic enzyme	0.02	0.02
Lipase	0.03	0.04
			Amylase	0.03	0.03
Silicate	2.0	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 less important thing	To 100%

Embodiment 7

Prepared following particulate state fabric cleaning composition of the present invention:

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
			Proteolytic enzyme	0.06	0.02
Polygalacturonase	0.01	0.02
			Silicate	5.0	5.0
Carbonate	15.0	15.0
			Peroxidase	0.1	0.1
Water and less important thing	To 100%

Embodiment 8

Prepared following particulate state fabric cleaning composition of the present invention:

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
Poly 4 vinyl pyridine N-oxide compound vinyl imidazole and vinylpyrrolidone copolymer	0.1
		Polygalacturonase	0.05
Proteolytic enzyme	0.01
		Lipase	0.02
Cellulase	0.02
		TAED	6.0
Percarbonate	22.0
		EDDS	0.3
The particulate state suds suppressor	3.5
		Water and less important thing	To 100%

Embodiment 9

Prepared the particulate state fabric cleaning composition following of the present invention that " softnessization by washing " ability is 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
		Proteolytic enzyme	0.02
Lipase	0.02
		Amylase	0.03
Polygalacturonase	0.03
		Cellulase	0.02
Silicate	3.0
		Carbonate	10.0
Suds suppressor	1.0
		CMC	0.2
Water and less important thing	To 100%

Embodiment 10

Prepared the heavy-filth liquid fabric cleaning composition following of the present invention that is used for pre-treatment spot fabric and is used for machine laundry 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
12E3	13.0	13.0	13.0	13.0	13.0
						Monoethanolamine MEA BASF	2.5	2.5	2.5	2.5	2.5
Polygalacturonase	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)

Embodiment 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
			Polygalacturonase	0.05	0.01
Proteolytic enzyme	0.02	0.02
			PVP	1.0	2.0
Perborate	0.5	1
			Phenolsulfonate	0.1	0.2
Peroxidase	0.04	0.01
			NaOH	To pH7.5
Water and less important thing	To 100%

Embodiment 12

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

	A	B	C	D	E	F
							Citric acid	6.5	6.5	6.5	6.5	6.5	6.5
Nonionic	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	-	-
Polyacrylate	-	-	-	-	5.0	-
							Polygalacturonase	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
							PH 1% solution	3.3	1.8	1.8	3.3	3.3	3.3
Water and less important thing	To 100%

Embodiment 13

Prepared the heavy-filth liquid fabric cleaning composition following of the present invention that is used for pre-treatment spot fabric and is used for machine laundry method:

C 12-14Alkenyl succinic acid	6.0
		Citric acid	5.0
24AS	20.0
		45AE7	10.0
C 12-C 14Lipid acid	11.0
		DETPMP	0.2
Ethanol	1.5
		Propylene glycol	11.5
Polygalacturonase	0.05
		NaOH	To pH7.5
Water and less important thing	To 100%

When being used in the cotton goods that spot is arranged are carried out pre-treatment and when doing washing test method, above-mentioned each composition all shows the performance of good removal spot.

Pollute two tissue substance samples and allow spot dry with mango, banana and coffee spot respectively.Allow them carry out following washing procedure separately: with the cleaning composition pre-treatment of about 0.3ml the fabric of spot is arranged, allows it soak about 15 minutes, then in the washing soln that contains 1% (weight) cleaning composition 20 ℃ of washings down.The 1st group of sample washs with above-mentioned composition I.Second group of sample is with same but do not contain the cleaning compositions of polygalacturonase.For the composition that contains polygalacturonase the evaluation group of banana spot being marked is 2.0 units (Scheff é stagings).

Embodiment 14

Machine testing

Broken Caulis et Folium Brassicae capitatae and spinach (40g)

	Caulis et Folium Brassicae capitatae		Spinach
						Polygalacturonase	No polygalacturonase	Polygalacturonase	No polygalacturonase
The amount of on strainer, being left after main the washing	16g	35g	4.3g	27g
					Percentage ratio on the strainer	40	87	11	80
Index	218	100	727	100

Condition:

Pre-rinsing: about 55 ℃ 30 minutes; 10 ° of German hardness, pH4.5, the Caulis et Folium Brassicae capitatae/spinach of 40g chopping, 40FDU/ml polygalacturonase X3L

Embodiment 15

Polygalacturonase heating pre-wash, main cycles of washing under 55 ℃ then

Broken Caulis et Folium Brassicae capitatae (40g)

	The W/ polygalacturonase	No polygalacturonase
			The amount of on strainer, being left after main the washing	0g	35.8g
Percentage ratio on the strainer	0	89
			Index	952	100

Condition:

Pre-rinsing: about 55 ℃ following 30 minutes; 10 ° of German hardness, pH4.5; The Caulis et Folium Brassicae capitatae of 40g chopping; 40FDU/ml polygalacturonase X3L

Main washing: 55 ℃ (15 minutes), 4,000ppm washing composition

Embodiment 16

Polygalacturonase then is that 55 ℃ of masters wash circulation in the post rinsing of heating.

Broken Caulis et Folium Brassicae capitatae (40g)

	The W/ polygalacturonase	No polygalacturonase
			Main residual content of washing in the after filter	15.5g	31.5
Percentage ratio on the strainer	39	78
			Index	25.8	100

Condition:

Main washing: 55 ℃ of circulations (15 minutes), the Caulis et Folium Brassicae capitatae of 40g chopping, 40FDU/ml polygalacturonase X3L, 4,000ppm washing composition.

Post rinsing: about 55 ℃ following 30 minutes, 10 ° of German hardness, pH4.5

Claims (21)

1, contains at least a cleaning composition that is selected from the detergent component of tensio-active agent and washing-aid compound, it is characterized in that, described composition contains polygalacturonase, and its amount is that the active pectin enzyme accounts for the 0.0001-2% of composition weight and the organic polyhydroxyl compound of 0.5-15 weight %.

2, be applicable to the cleaning composition of the claim 1 of machine-washing method, it contains one or more additional scrubbed component that are selected from SYNTHETIC OPTICAL WHITNER, additional enzymes, suds suppressor, lime soap dispersing agent, dirt suspension and anti-precipitation agent again and corrosion inhibitor.

3, according to the cleaning composition of claim 2, wherein additional enzymes is selected from amylase, proteolytic enzyme and lipase.

4, according to the cleaning composition of claim 2, it contains a tenderizer.

5, according to the cleaning composition of claim 1, described the helping that it contains 1-80% (weight) washed compound.

6, contain the cleaning composition of claim 1 of the described tensio-active agent of 1-35% (weight), wherein tensio-active agent is selected from nonionic, negatively charged ion, positively charged ion, zwitterion, two property and amphoterics.

7, the cleaning composition that contains a kind of claim 2 of SYNTHETIC OPTICAL WHITNER, this SYNTHETIC OPTICAL WHITNER is selected from following compound and composition thereof: (a) inorganic peracid salt, its content are the 1-40% of composition weight; (b) peroxyacid bleach precursor, its content are the 1-20% of composition weight; (c) organic peroxy carboxylic acid, its content are the 1-15% of composition weight.

8, the cleaning composition that contains the claim 3 of additional enzymes, this additional enzymes are selected from following enzyme and their mixture: (a) neutrality and Sumizyme MP, its amount are that the organized enzyme consumption is the 0.0001-2% of composition weight; (b) amylase, its amount are that organized enzyme content is the 0.0001-2% of composition weight; (c) lipase, its amount are that organized enzyme content is the 0.0001-2% of composition weight.

9, according to the cleaning composition of claim 2, the foam that presses down that it mixes 0.01-15% (weight) is.

10, be applicable to and manual wash the cleaning composition of the claim 1 of dish method that it contains one or more additional detergent components that is selected from suds booster, II family metal ion and additional enzymes.

11, according to the cleaning composition of claim 1, wherein said composition is the height bubble.

12, according to the cleaning composition of claim 10, wherein said composition is liquid or gel form.

13, according to the cleaning composition of claim 10, wherein said composition contains helping of no more than 1.5% (weight) washes compound.

14, according to the cleaning composition of claim 10, wherein said composition does not contain SYNTHETIC OPTICAL WHITNER.

15, according to the cleaning composition of claim 10, it contains the described tensio-active agent of 5%-60% (weight).

16, according to the cleaning composition of claim 10, it contains the calcium ion of 0.01%-3% (weight).

17, according to the cleaning composition of claim 10, it contains the magnesium ion of 0.01%-3% (weight).

18, according to the cleaning composition of claim 10, it contains the suds booster of 0.01%-20%.

19, according to the cleaning composition of claim 10, it contains the hydrotropic agent of 0.5%-25% (weight).

20, polygalacturonase is used for the rinse aid composition to reduce the strainer residue.

21, polygalacturonase is used for the dishwasher cleaning combination to decompose the food in the dishwasher.