CN1373180A - Washing method - Google Patents

Abstract

The invention relates to a washing method. There is a provided a detergent composition containing: (a) 0.005-1 wt.% a heavy metal ion sequestrant selected from ethylenediamine-N,N'-disuccinic acid, its salts or their mixture; and (b) a wash solution free of bleach is supplied to a base with dirt. The wash solution contacts with the base with dirt. The base with dirt then is cleaned by detergent composition containing bleach.

Description

Washing methods

The application is dividing an application of the PCT/US95/04085 application for a patent for invention that being entitled as of submitting to April 3 nineteen ninety-five " contains heavy metal chelant and the washing composition of the peroxyacid bleach system that postpones to discharge ", original application enters the China national stage on December 11st, 1996, and obtains Chinese patent application 95193547.X.

Technical field

The present invention relates to a kind of washing methods, the solution that comprises the no SYNTHETIC OPTICAL WHITNER that will contain heavy metal ion chelating agent is supplied with the basic thing of being with dirt, the basic thing of this solution and said band dirt is kept in touch, and the basic thing that washs said band dirt then with the detergent composition that contains SYNTHETIC OPTICAL WHITNER.

Background technology

The plant dirt of removing the dirt/spot that can bleach such as tea, fruit juice and band look on dirt/spot base thing satisfactorily from band has challenge for the prescription teacher who is used for for example doing washing or the wash up machine washing is washed this detergent composition of method.

Remove the traditional method of this dirt/spot of bleaching and to use bleaching components such as oxygen bleaching agent, comprise hydrogen peroxide and organic peroxide acid.This organic peroxide acid normally obtains on the spot by the hydrolysis reaction excessively between hydrogen peroxide and organic peroxide acid bleach precursor.

The problem of using some organic peroxide acid SYNTHETIC OPTICAL WHITNER to run in the laundry washing methods is that these peroxyacid bleachs tend to influence the color stability of fabric of being in the suds.Can comprise fabric enamel fading of dyestuff or partial irregular colored bleached area for the types of damage of fabric.

Therefore, the detergent formulation teacher is faced with the double challenge of the following said product of preparation, this product should be able to farthest be removed the dirt/spot that can bleach, but should make this SYNTHETIC OPTICAL WHITNER minimum for reducing to of any unwelcome influence of fabric color stability.

The applicant find by use in washing methods that peroxyacid bleach causes to any unwelcome influence of fabric color stability be relevant with the rate of release of peroxyacid bleach in washing soln, also relevant with the absolute magnitude of the peroxy acid that in washing soln, exists.

Peroxyacid bleach in washing soln fast rate of release trend towards increasing following possibility, that is: will observe the unwelcome influence of fabric color stability, the high absolute magnitude of SYNTHETIC OPTICAL WHITNER in washing soln also is like this.

Reduce the be in the suds absolute magnitude of the SYNTHETIC OPTICAL WHITNER used of the rate of release of peroxyacid bleach or reduction and can tend to improve this problem, this can a kind ofly reach influence and realize mutually by what the stain that can bleach is removed ability.

Yet existing applicant has found to use the composition that contains heavy metal ion chelating agent and peroxyacid bleach source, the release of the peroxyacid bleach that wherein provides in washing soln is with respect to the release of heavy metal ion chelating agent, the method that postpones can be enhanced to the removal of the stain that can bleach.In addition, use said composition in the washing methods, the tendency to the disadvantageous effect of fabric color stability that will be observed is reduced in laundry.

In addition, the applicant found before the basic thing of band dirt is being used the washing methods washing of the Betengent product that contains SYNTHETIC OPTICAL WHITNER, with containing heavy metal ion chelating agent and the optionally solution pre-treatment of water soluble detergency promoter, can obtain the benefit that the stain that can bleach is removed.

Summary of the invention

Therefore, but the purpose of this invention is to provide and be applicable to that laundry and wash up machine washing wash and have the composition of enhancing to the bleach spot removal in the method.

Another object of the present invention provides the composition of the washing methods that is used for doing washing, and wherein said composition is for causing that the otherwise impact to the fabric color stability shows lower tendency.

The purpose that the present invention is correlated with provides the stain pretreatment process, is included in before the Betengent product washing that contains SYNTHETIC OPTICAL WHITNER, with containing the heavy metal ion chelating agent and the basic thing of the solution pre-treatment band dirt of water soluble detergency promoter optionally.

Summary of the invention

According to an aspect of the present invention, provide a kind of detergent composition, it contains: (a) heavy metal ion chelating agent; (b) organic peroxide acid bleach systems, release with respect to said heavy metal ion chelating agent wherein is provided, make said organic peroxide acid in washing soln, postpone the method that discharges, so that in T50 test method described herein, the concentration that obtains heavy metal ion chelating agent is less than 120 seconds for the time of its ultimate density 50%, and the concentration that obtains organic peroxide acid is that time of its ultimate density 50% was greater than 180 seconds.

According to a further aspect in the invention, provide a kind of detergent composition, it contains: (a) heavy metal ion chelating agent; (b) organic peroxide acid bleach system, release with respect to said heavy metal ion chelating agent wherein is provided, make said organic peroxide acid in washing soln, postpone the method that discharges, so that in T50 test method described herein, the concentration that obtains said heavy metal ion chelating agent obtains said organic peroxide acid for the time ratio of its ultimate density 50% concentration is short 100 seconds at least required time of its ultimate density 50%, preferably lacked 120 seconds at least, more preferably lacked 150 seconds at least.

Said organic peroxide acid bleach system preferably includes following combination: (i) hydrogen peroxide cource body; (ii) organic peroxide acid bleach precursor compound.

The preferred aspect according to the present invention, said composition also contains: (c) water soluble detergency promoter wherein provides the release with respect to said water soluble detergency promoter, make said organic peroxide acid in washing soln, postpone the method that discharges, so that in T50 test method described herein, the concentration that obtains said water soluble detergency promoter is for the time of its ultimate density 50% is less than 120 seconds, the concentration that obtains said organic peroxide acid for time of its ultimate density 50% greater than 180 seconds.

According to a further aspect in the invention, provide a kind of washing methods, the step that comprises is:

(1) composition solution that will contain the no SYNTHETIC OPTICAL WHITNER of heavy metal ion chelating agent is supplied with the basic thing of being with dirt;

(2) make the basic thing of said solution and said band dirt keep in touch the effective timed interval;

(3) with comprising the washing methods that uses the detergent composition that contains SYNTHETIC OPTICAL WHITNER, wash the basic thing of said band dirt.Heavy metal ion chelating agent

Detergent composition of the present invention contains heavy metal ion chelating agent.The heavy metal ion chelating agent meaning in this article has been the component of chelating heavy metal ion effect.These components also can have calcium and magnesium sequestering power, but preferably they to showing selectivity in conjunction with heavy metal ion such as iron, magnesium and copper.

Heavy metal ion chelating agent content is generally 0.005% to 20% of composition, and is preferred 0.1% to 10%, and more preferably 0.25% to 7.5%, 0.5% to 5% (weight) most preferably.

Heavy metal ion chelating agent, it is a tart in nature, have for example phosphonic acids or carboxylic functionality, its existence form can be their acid form or as with the form of the title complex/salt of the counter cation that is fit to such as basic metal or alkaline-earth metal ions, ammonium or the ammonium that replaces or its any mixture.Preferred any salt/title complex is water miscible.The mol ratio of said counter cation and heavy metal ion chelating agent preferably was at least 1: 1.

Be applicable to that heavy metal ion chelating agent of the present invention includes organic phosphonates, for example poly-(alkylene phosphonic acids salt), ethane of amino alkylidenyl-1-hydroxyl di 2 ethylhexyl phosphonic acid an alkali metal salt and nitrilo trimethylene phosphonic salt.

Preferably diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1,1 diphosphonate in the above material.

Other is applicable to that heavy metal ion chelating agent of the present invention comprises nitrilotriacetic acid(NTA) and polyaminocarboxylic acid, for example ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two L-glutamic acid, 2-hydroxy propylidene diamines disuccinic acid or its any salt.

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

As at EP-A-317,542 and EP-A-399, be applicable to that heavy metal ion chelating agents that other are fit to of the present invention are iminodiacetic acid derivatives described in 133, for example 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid.

At EP-A-516, iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and the aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant described in 102 also are applicable to the present invention.At EP-A-509, the β-An Jibingsuan-N that describes in 382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also suit.

EP-A-476,257 to have described suitable be the sequestrant of base with amino.EP-A-510,331 have described the sequestrant that is obtained by collagen protein, Keratin sulfate or casein.EP-A-528,859 have described suitable alkyl imino oxalic acid sequestrant, pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, and the 4-tricarboxylic acid also suits.G-NH2-N, N '-disuccinic acid (GADS) also suits.The organic peroxide acid bleach systems

Essential features of the present invention is the organic peroxide acid bleach systems.In a kind of preferred enforcement, this bleach system contains hydrogen peroxide cource body and organic peroxide acid bleach precursor compound.The preparation of organic peroxide acid is undertaken by its precursor and hydrogen peroxide cource body situ reaction.Preferred hydrogen peroxide cource body comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In another kind is preferably implemented, the ready-formed organic peroxide acid is directly mixed in the composition.The composition that contains the mixture of hydrogen peroxide cource body and organic peroxy acid precursor and ready-formed organic peroxide acid also is suggested.Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

Inorganic perhydrate salt is preferred hydrogen peroxide cource body.These salt are normally with basic metal, and the form of particular certain cancers is mixed, and its amount is the 1%-40% of composition weight (weight), more preferably 2%-30% (weight), most preferably 5%-25% (weight).

The example of suitable inorganic perhydrate salt comprises borate, percarbonate, superphosphate, persulphate and persilicate and its any mixture.This inorganic hydrate salt is an alkali metal salt normally.What can comprise not other protection is the inorganic perhydrate salt of crystalloid solid.Yet for some perhydrate salt, this granular component preferred embodiment is to use the coating form of this material, and this provides stability in storage preferably for the perhydrate salt in the granulated product.

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

Alkali metal percarbonate, especially SPC-D are the preferred perhydrate that is included in the present composition.Found that the composition that contains percarbonate has the trend that forms undesirable gel under tensio-active agent and the water existence that is reduced in than the analogous composition that contains perborate.It is believed that this is because percarbonate generally has less surface-area and less porosity than perborate monohydrate.This few surface-area and few porosity work the fine particle agglomerative effect altogether that suppresses with surfactant agglomerates, so it is favourable to disperseing.

SPC-D is to have corresponding to formula 2Na ₂CO ₃3H ₂O ₂Addition compound, it is commercial that what buy is crystalline solid, SPC-D is most preferably mixed in this based composition with the form that is coated, this provides its stability in product.

The suitable coating material that is provided at stability in the product comprises the mixing salt of water-soluble alkali vitriol and carbonate.This coating material and method for coating are described in the GB-1 that on March 9th, 1977 licensed to Interox, in 466,799.The coating material mixing salt with the weight ratio of percarbonate 1: 200 to 1: 4 scope, more preferably 1: 99 to 1: 9, most preferably 1: 49 to 1: 19.Preferred this mixing salt is the mixing salt of sodium sulfate and yellow soda ash, has general formula: Na ₂SO ₄NNa ₂CO ₃, wherein n is 0.1 to 3, and preferred n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5.

The present invention also can preferably use other coating material that contains silicate (independent or with borate or boric acid or other inorganics), paraffin, oils, fatty soap.

Peroxide one Potassium Persulphate is an another kind of inorganic perhydrate salt useful in the detergent composition of the present invention.Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that generates peroxy acid in crossing hydrolysis reaction with hydroperoxidation.General peroxyacid bleach precursor can be expressed from the next: Wherein L is a leavings group, and X is necessary any functionality, so that in the structure of the peroxy acid that passed through the hydrolysis generation is:

The peroxyacid bleach precursor compound preferably with the 0.5%-20% (weight) of detergent composition weight, more preferably 1%-15% (weight), most preferably 1.5%-10% (weight) amount is mixed.

Suitable peroxyacid bleach precursor compound generally contains one or more N-or O-carboxyl groups, and this precursor can be selected from multiclass, and suitable type comprises the acyl derivative of acid anhydride, ester, imide, lactan and imidazoles and oxime.The example of useful material is disclosed among the GB-A-1586789 in these types.Suitable ester be disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.

The applicant finds that the damage of " irregular " is especially relevant with the peroxyacid bleach precursor compound that peroxy acid is provided through hydrolysis, and wherein said peroxy acid is: (i) derivative of peroxybenzoic acid or its non-cationic replacement; Or (ii) positively charged ion peroxy acid.

Find that also the benzoxazine precursor is responsive especially to this problem.Leavings group

Leavings group, promptly L group hereinafter must have enough reactive behavioies for the hydrolysis reaction excessively that occurs in the Best Times scope (for example cycles of washing).Yet, if the L reactive behavior too by force this activator be used for bleaching composition and be difficult to stablize.

Preferred L group is selected from:

With its mixture, wherein R ¹Be alkyl, aryl or the alkaryl that contains 1 to 14 carbon atom, R ³Be alkyl chain, the R that contains 1 to 8 carbon atom ⁴Be H or R ³, and Y be H or solubilization group.Any R ¹, R ³And R ⁴Can be replaced by any functional group of necessity, these functional groups comprise, for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.

Preferred solubilization group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³It is the alkyl chain that contains 1-4 carbon atom, M provides deliquescent positively charged ion to bleach-activating agent, X provides deliquescent negatively charged ion to bleach-activating agent, M is basic metal, ammonium or replacement ammonium cation preferably, sodium and potassium are most preferred, and X is halogenide, oxyhydroxide, Methylsulfate or acetate negatively charged ion.Peroxybenzoic acid precursors and its derivative

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.

The peroxybenzoic acid precursors compound of suitable O-acylations comprises and replacing and unsubstituted benzoyl oxygen benzene sulfonate, comprises for example benzoyl oxygen benzene sulfonate:

The suitable benzoylation product that also has Sorbitol Powder, glucose and all saccharidess and benzoylation reagent for example comprises: AC=COCH ₃The Bz=benzoyl

Imide type peroxybenzoic acid precursors compound comprises the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises that the useful peroxybenzoic acid precursors that contains the N-acyl group of N-benzoyl imidazoles and N-benzoyl benzoglyoxaline and its comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

Other peroxybenzoic acid precursors comprises benzoyl diacyl peroxide, benzoyl four acyl peroxides and has the compound of following formula.

Phthalate anhydride is another suitable peroxybenzoic acid precursors compound herein:

Suitable N-acylated lactams peroxybenzoic acid precursors has formula:

Wherein n is 0 to 8, and is preferred 0 to 2, R ⁶Be aryl, alkoxy aromatic yl or alkaryl that contains 1 to 12 carbon atom or the phenyl that contains the replacement of 6 to 18 carbon atoms, preferred benzoyl.Peroxybenzoic acid derivative precursor

Peroxybenzoic acid derivative precursor provides the peroxybenzoic acid that replaces through hydrolysis.

The suitable peroxybenzoic acid derivative precursor that replaces comprises any peroxybenzoic acid precursors disclosed herein; wherein benzoyl is replaced by (being non-cationic) functional group of any non-positive charge of necessity; these functional groups comprise, for example alkyl, hydroxyl, alkoxyl group, halogen atom, amine, nitrosyl radical and amide group.

The peroxybenzoic acid precursors compound that a preferred class replaces is the compound that the acid amides of following general formula replaces:

R wherein ¹Be aryl or alkaryl with 1-14 carbon atom, R ²Be arylidene or the alkyl arylene that contains 1-14 carbon atom, R ⁵Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom, any leavings group that L is necessary.R ¹Preferably contain 6-12 carbon atom.R ²Preferably contain 4-8 carbon atom, R ¹Can be aryl, contain the aryl of replacement of substitution in side chain base or alkaryl or the two, and can derive from synthetics or natural goods, comprise for example butter fat.The mutation of similar structures also is applicable to R ²Substituent can comprise alkyl, aryl, halogen atom, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Be preferably H or methyl.R ¹And R ⁵Should not contain more than 18 carbon atoms altogether.The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0170386.The positively charged ion peroxyacid precursor

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

Generally, the positively charged ion peroxyacid precursor is by the functional group with positive charge, and as ammonium or alkyl ammonium group, the peroxy acid of preferred ethyl or the suitable peroxyacid precursor compound of methyl amido replacement partly forms.The positively charged ion peroxyacid precursor generally is present in the solid detergent composition with the form that has suitable negatively charged ion such as halogen ion salt.

The peroxyacid precursor compound that is replaced by positively charged ion can be the derivative of peroxybenzoic acid or its replacement, precursor compound as described above.In addition, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound described below or acid amides replace.

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

The example of preferred cation peroxyacid precursor is described in UK patent application 94 07944.9 and US patent application 08/298903,08/298650,08/298904 and 08/298906.

Suitable positively charged ion peroxyacid precursor comprises the hexanolactam and a benzoyl tetrem acyl glucose benzoyl peroxide of alkyl that any amine or alkylamine replace or benzoyl oxygen benzene sulfonate, N-acidylate.

The benzoyl oxygen benzene sulfonate that preferred cation replaces is 4-(trimethyl ammonium) methyl-derivatives of benzoyl oxygen benzene sulfonate

The alkoxy benzene sulfonate that preferred cation replaces has formula:

The positively charged ion peroxyacid precursor of the hexanolactam class of preferred N-acidylate comprises trialkyl ammonium methylene radical benzoyl caprolactam, especially trimethyl ammonium methylene radical benzoyl caprolactam.

The positively charged ion peroxyacid precursor of the hexanolactam class of other preferred N-acidylate comprises trialkyl ammonium methylene radical alkyl hexanolactam:

Wherein n is 0 to 12.

The preferred cation peroxyacid precursor is 2-(N, N, a N-trimethyl ammonium) ethyl 4-sulfo group phenyl-carbonic acid na chloride in addition.Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids through hydrolysis.The preferred precursor of this class comprises through hydrolysis provides peracetic acid.

Preferred acid imide alkyl peroxycarboxylic acid precursors compound comprises N, N, and N ', N ' tetrem acidylate Alkylenediamine, wherein alkylidene group contains 1-6 carbon atom, and especially wherein alkylidene group contains those compounds of 1,2 and 6 carbon atom.Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen benzene sulfonic acid sodium salt (different-NOBS), nonanoyl oxygen benzene sulfonic acid sodium salt (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.The alkyl peroxy acids precursor that acid amides replaces

The alkyl peroxy acids precursor compound that acid amides replaces also suits, and comprises those compounds with following general formula:

R wherein ¹Be alkyl with 1-14 carbon atom, R ²Be the alkylidene group that contains 1-14 carbon atom, R ⁵Be H or the alkyl that contains 1-10 carbon atom, any leavings group that L is necessary.R ¹Preferably contain 6-12 carbon atom.R ²Preferably contain 4-8 carbon atom.R ¹Can be straight chained alkyl or the branched-chain alkyl that contains the substitution in side chain base or the two, and can derive from synthetics or natural goods, comprise for example butter fat.The mutation of similar structures also is applicable to R ²Substituent can comprise alkyl, halogen atom, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Be preferably H or methyl.R ¹And R ⁵Should not contain more than 18 carbon atoms altogether.The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0170386.Benzoxazine organic peroxy acid precursor

In addition, suitable is benzoxazine type precursor compound, and it is disclosed in for example EP-A-332, in 294 and EP-A-482,807, particularly has those compounds of following formula: Comprise the benzoxazine that this class replaces:

R wherein ₁Be H, alkyl, alkaryl, aryl or aralkyl, wherein R ₂, R ₃, R ₄And R ₅Can be identical or different substituting group, be selected from H, halogen atom, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, COOR ₆(R wherein ₆Be hydrogen or alkyl) and the carbonyl functional group.

Particularly preferred benzoxazine type precursor:

The ready-formed organic peroxide acid

The organic peroxide acid bleach system is except containing organic peroxide acid bleach precursor compound, also can contain (or as this compound surrogate) ready-formed organic peroxide acid, its amount is generally the 1%-15% (weight) of composition, more preferably 1%-10% (weight).

A preferred class organic peroxy acid compound is the compound with acid amides replacement of following general formula:

R wherein ¹Be alkyl, aryl or alkaryl with 1-14 carbon atom, R ²Be alkylidene group, arylidene or the alkyl arylene that contains 1-14 carbon atom, R ⁵Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom.R ¹Preferably contain 6-12 carbon atom.R ²Preferably contain 4-8 carbon atom.R ¹Can be the straight or branched alkyl, contain the aryl of replacement of substitution in side chain base or alkaryl or the two, and can derive from synthetics or natural goods, comprise for example butter fat.The mutation of similar structures also is applicable to R ²Substituent can comprise alkyl, aryl, halogen atom, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Be preferably H or methyl.R ¹And R ⁵Should not contain more than 18 carbon atoms altogether.The organic peroxy acid compound that this class acid amides replaces is described among the EP-A-0170386.

Other organic peroxide acid comprises diacyl and four acyl peroxides, especially diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.List and two is crossed nonane diacid, brassylic acid crossed by list and two and N-O-phthalic amido peroxide caproic acid also is applicable to the present invention.Chlorine bleach

The present composition does not preferably contain chlorine bleach.Bleaching catalyst

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

This bleaching catalyst is used for composition of the present invention with catalytically effective amount, and " catalytically effective amount " no matter the meaning is to use which type of simultaneous test condition, this amount advantageously bleaches and remove spot for enhancing from the target base thing or dirt all is enough.And in the laundering of textile fabrics operation, target base thing generally is to have for example fabric of various food stains, and for automatic wash dining set, target base thing can be porcelain cup or the dish that for example has the tea stain, perhaps stains the polyethylene dish of tomato soup.The variation of test conditions will be depended on the type of washing plant of use and user's custom.The front-loading washing machine that uses in Europe is than common less water and the higher detergent concentration of using of the roof-mounted washing machine of the U.S..Some washing machines have quite long cycles of washing than other washing machine.Some users select to use awfully hot water in laundry operations; Other user uses temperature or even cold water.Nature, the catalytic performance of bleaching catalyst will be subjected to these condition effect, can suitably be adjusted in the content of the bleaching catalyst that uses in the washing composition of full preparation and the bleaching composition.In practice, bound by theory not, adjustable joint the compositions and methods of the invention preferably provide about 1ppm to about 200ppm catalyst substance in wash water solution to be provided in the wash water solution approximately 1/10,000,000 active bleaching catalyst material.In order to further specify this point, specifically under the European condition of using perborate and bleach precursor (for example benzoyl caprolactam), be that about 3 micromole's Mg catalysts are effective under 10 the condition at 40 ℃, pH.Under American condition, need to increase 3-5 times of concentration to obtain identical result.On the contrary, compare with the product that does not have the magnesium salts catalyzer, bleach precursor and Mg catalyst and boratory use under lower perborate consumption condition, can make the prescription teacher obtain the bleaching power of equivalence.

Bleach catalysts material herein can comprise the form of free acid or any suitable salt.

One type bleaching catalyst is to comprise the catalyst system with the active heavy metal cation of definite bleach catalyst, wherein the example of heavy metal cation is copper, iron or magnesium cation, has few or do not have the active assistant metal positively charged ion of bleach catalyst such as zinc or aluminium cations, with definite stability constant of sequestrant, especially ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt have to(for) catalysis and assistant metal positively charged ion.This catalyzer is disclosed in U.S.4, in 430,243.

Other type bleaching catalyst comprises with magnesium being the title complex of base, and it is disclosed in U.S.5, in 246,621 and U.S.5,244,594.The preferred example of these catalyzer comprises Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃With its mixture.Other is described in the european patent application 549,272.Be applicable to that other ligand of the present invention comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.

The example of suitable bleaching catalyst is referring to U.S.4, and 246,612 and U.S.5,227,084 also referring to U.S.5, and 194,416, it discloses monokaryon magnesium (IV) title complex, as Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃-(PF ₆).

Also have another kind of bleaching catalyst, it is disclosed in U.S.5, and in 114,606, it is magnesium (II), (III) and/or (IV) and the water-soluble complexes with non-carboxylate salt polyol ligand of at least three adjacent C-OH groups.Preferred ligand comprises sorbyl alcohol, iditol, dulsitol, mannitol, Xylitol, arabitol, adonitol, the red bright alcohol of meso, meso-inositol, lactose and its mixture.

U.S.5,114,611 disclose and have comprised transition metal, comprise Mn, Co, Fe or Cu, with the bleach catalysts of the title complex of the ligand of non-(greatly) ring.Said ligand has formula:

R wherein ¹, R ², R ³And R ⁴All be selected from the alkyl and the aryl of H, replacement, so that R ¹-N=C-R ²And R ³-C=N-R ⁴Each formation five or six membered ring.This ring can further be substituted.B is an abutment, is selected from O, S, CR ⁵R ⁶, NR ⁷And C=O, wherein R ⁵, R ⁶And R ⁷Be H, alkyl or aryl, comprise replacement or unsubstituted group.Preferred ligand comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrroles and triazole ring.This ring can randomly be substituted base and replace as alkyl, aryl, alkoxyl group, halogenide and nitro.Particularly preferably be 2,2 '-dipyridyl amine ligand.Preferred bleaching catalyst comprises Co, Cu, Mn, Fe-dipyridyl methane and dipyridyl amine complex.Most preferred catalyzer comprises Co (2,2 '-dipyridyl amine) Cl ₂, two (isothiocyanato) dipyridyl amine-cobalt (II), terpyridyl amine-cobalt (II) perchlorate, Co (2,2-dipyridyl amine) ₂O ₂ClO ₄, two (2,2 '-dipyridyl amine) copper (II) perchlorate, three (connection-2-pyridine amine) iron (II) perchlorate and its mixture.

Other example comprises manganese gluconate, Mn (CF ₃SO ₃) ₂, Co (NH ₃) ₅Cl and have four-N-dentate and the double-core Mn title complex of two-N-dentate ligand comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄ ⁺[2,2 '-dipyridyl ₂Mn ^III(u-O) ₂Mn ^IV2,2 '-dipyridyl ₂]-(ClO ₄) ₃

Bleach catalysts of the present invention can prepare with following method: water-soluble ligand and water-soluble manganese salt are mixed in water-bearing media, and the mixture that obtains through evaporation concentration prepares bleach catalysts.The present invention can use any water-soluble salt easily of manganese.Manganese (II), (III), (IV) and/or (V) buy commercial being easy to.In some cases, in washing soln, can there be the manganese of capacity, exists catalysis effectively to measure to guarantee it but in composition, add the Mn positively charged ion usually.The sodium salt of ligand and be selected from MnSO ₄, Mn (ClO ₄) ₂Or MnCl ₂The manganese salt of (seldom preferred) is with ligand: Mn salt mol ratio is to be dissolved in neutrality in about 1: 4 to 4: 1 or slightly in the water of alkaline pH.Water at first is by boiling deoxidation, cooling off with nitrogen purging then.With the solution evaporation that obtains (at N ₂Down, if need), the solid that obtains does not need further refining being used in bleaching of the present invention and the detergent composition.

In another embodiment, water miscible manganese source body such as MnSO ₄Be added in the bleaching/cleaning combination or aqueous bleaching/cleaning body lotion that contains ligand.The title complex of some types generates significantly on the spot, and the performance of this improved SYNTHETIC OPTICAL WHITNER is reliable.In this method that generates on the spot, the ligand of the big excessive mole number that suits to use than manganese, the mol ratio of ligand and Mn was generally 3: 1 to 15: 1.Other ligand also can be removed unsettled metal ion such as iron and copper, has suppressed the SYNTHETIC OPTICAL WHITNER decomposition thus.This system that one class is possible is described in the european patent application 549,271.

The structure of the manganese complex of some catalytically bleaching agent that the present invention describes is illustrated, can infer the coordination compound that it comprises inner complex or other hydration, and they are by the generation that interacts of the carboxyl of ligand and nitrogen-atoms and manganese positively charged ion.In addition, the cationic, oxidized attitude of manganese is not known really in catalytic process, its can be (+II), (+III), (+IV) or (+V) valence state.Because ligand and manganese positively charged ion have six point of contact, therefore can have reason to infer in the aqueous bleaching medium, may have multinuclear material and/or cage structure.The active manganese ligand material of what form of physical presence no matter, it all has obvious catalysis so that the improved bleachability to the spot of stubbornness such as tea stain, tomato-sauce, coffee, bloodstain etc. to be provided.

Other bleach catalysts is described in for example european patent application 408,131 (cobalt complex catalyzer), european patent application 384,503 and 306,089 (catalysis of metalloporphyrin agent), U.S.4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), U.S.4,711,748 and european patent application 224,952 (Mn catalyst that on silico-aluminate, is adsorbed), U.S.4,601,845 (being loaded with the silico-aluminate of manganese and zinc or manganese salt), U.S.4,626,373 (manganese/ligand catalyzer), U.S.4,119,557 (iron complex catalyzer), German patent specification 2,054,019 (cobalt sequestrant catalyzer), Canada's 866,191 (salt that contain transition metal), U.S.4,430,243 (sequestrant that has manganese positively charged ion and non-catalytic metallic cation) and U.S.4,728,455 (gluconic acid Mn catalysts).The relative kinetics that discharges

A main aspect of the present invention provides the release of the release of organic peroxide acid SYNTHETIC OPTICAL WHITNER in washing soln with respect to heavy metal ion chelating agent, the method for delay.

Said method can comprise the method that delay organic peroxide acid SYNTHETIC OPTICAL WHITNER discharges in washing soln.

Said in addition method can comprise the method that increases the rate of release of heavy metal ion chelating agent in solution.Postpone the rate of release method

This method can provide organic peroxyacid bleach source itself to postpone to discharge in washing soln.In addition, when peroxide acid source body was the organic peroxide acid precursor compound, the method that this delay discharges can comprise the method for crossing hydrolysis reaction on the spot that suppresses or prevent to discharge organic peroxide acid in solution.This method can comprise and for example postpone the release of hydrogen peroxide cource body in washing soln, and this is by for example postponing as the release to washing soln of any inorganic perhydrate salt of hydrogen peroxide cource body.

The method that postpone to discharge can comprise with the appointed coating material that postpones release or the mixture of coating material of providing and coats any suitable component.This coating material can comprise the material of poorly water-soluble for example or the coating material of adequate thickness is arranged that the dissolution kinetics of this thick coating material provides controlled rate of release.

Can make ins all sorts of ways provides coating material.The general consumption of any coating material is: the weight ratio of coating material and SYNTHETIC OPTICAL WHITNER is 1: 99 to 1: 2, preferred 1: 49 to 1: 9.

Suitable coating material comprises triglyceride level (for example, partially hydrogenated vegetables oil, soya-bean oil, oleum gossypii seminis), glycerine list or diester, crystallite shape paraffin, gel, Mierocrystalline cellulose, lipid acid and its any mixture.

Other suitable coating material can comprise basic metal and alkaline earth metal sulphate, silicate and carbonate, comprises lime carbonate.

Preferred coating material is to have SiO ₂: Na ₂The O ratio is 1.6: 1 to 3.4: 1, preferred 2.8: 1 water glass, and it provides as the aqueous solution, with 2%-10% (normally 3%-5%) silicate solid that is provided as percarbonate weight.Also can comprise Magnesium Silicate q-agent in the coating material.

Any inorganic salt coating material can be used in combination with the organic binder bond material, so that complex inorganic salt catalyst/organic binder bond coating material to be provided.Suitable tackiness agent comprises C ₁₀-C ₂₀Alcohol ethoxylate, its every mol of alcohol contains the 5-100 moles of ethylene oxide; C more preferably ₁₅-C ₂₀Primary alcohol ethoxylate, its every mol of alcohol contains the 20-100 moles of ethylene oxide.

Other preferred adhesive comprises some polymeric material.The example of this polymeric material is polyvinylpyrrolidone with molecular-weight average 12,000 to 700,000 and the polyoxyethylene glycol (PEG) with molecular-weight average 600 to 10,000.The multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, wherein maleic anhydride is at least 20% (mole) of this polymkeric substance composition, this multipolymer is the other example as the tackiness agent polymeric material.These polymeric materials can contain the C of 5-100 moles of ethylene oxide with itself or with solvent such as water, propylene glycol and above-mentioned every mol of alcohol ₁₀-C ₂₀Alcohol ethoxylate is used in combination.The other example of tackiness agent comprises C ₁₀-C ₂₀List and Glycerol dimer ether also have C ₁₀-C ₂₀Lipid acid.

Derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, Type 3U and Natvosol and all or the poly carboxylic acid of copolymerization or their salt be the other example that is applicable to tackiness agent of the present invention.

A kind of method that applies coating material comprises agglomeration technique.Preferred agglomeration method comprises the above-mentioned any organic binder bond material of use this paper.Agglomeration machine/the mixing machine of any routine can use, and comprises, but is not restricted to disc type, rotary drum and vertical blending machine type.Fusion coating material composition also can be by being poured into or atomizing spray applies on the moving-bed SYNTHETIC OPTICAL WHITNER.

Other method that provides required delay to discharge comprises mechanical means, and this method is the physical properties that changes SYNTHETIC OPTICAL WHITNER, to control its solvability and rate of release.Suitable scheme comprises that compacting, machinery inject, manually inject and by the selection of the granularity of any grain fraction of bleaching compounds being adjusted the solvability of bleaching compounds.

To depend on the composition of grain fraction and need satisfy the kinetics that required delay discharges for the selection of granularity.It is desirable to granularity should be greater than 500 micron, and preferably having average particulate diameter is 800 to 1200 microns.

Provide the other scheme that postpones method for releasing to comprise suitable selection to any other component in the detergent composition matrix, so that when composition is added in the washing soln, the feasible delay release dynamics that can obtain needs of the ionic strength environment that wherein provides.Increase the rate of release method

Increasing heavy metal ion chelating agent all is conceived to all proper method of the speed of solution release.

Strengthen the method that discharges and to comprise that usefulness is designed to strengthen the coating material that discharges and coats any suitable component.That this coating material can comprise highly water-soluble for example or even the material of whipability.

Other method that provides required delay to discharge comprises mechanical means, and this method is to change the physical property of heavy metal ion chelating agent to strengthen its solvability and rate of release.

Suitable scheme can comprise any granularity that contains the heavy metal ion chelating agent component of careful selection.To the selection of granularity will depend on the composition of grain fraction and need satisfy kinetics that required enhancing discharges the two.It is desirable to granularity and should be less than 1200 microns, preferably having average particulate diameter is 1100 to 500 microns.

Provide the other scheme that postpones method for releasing to comprise suitable selection to any other component in the detergent composition matrix, or to the suitable selection of any grain fraction of containing heavy metal ion chelating agent, so that when composition was added in the washing soln, the ionic strength environment that wherein provides can make and obtain required enhancing release dynamics.Relative release rate-kinetic parameter

The release that derives from the organic peroxide acid bleaching components of peroxyacid bleaching system is such with respect to the release of heavy metal ion chelating agent component: in this article in the T50 test method of Miao Shuing, the concentration that obtains said heavy metal ion chelating agent is less than 120 seconds for its ultimate density 50% required time, preferably be less than 90 seconds, more preferably be less than 60 seconds, the concentration that obtains said organic peroxide acid SYNTHETIC OPTICAL WHITNER is that its ultimate density 50% required time was greater than 180 seconds, preferred 180-480 second, more preferably 240-360 second, they there are differences between the time.

In aspect the present invention is most preferred, the release of SYNTHETIC OPTICAL WHITNER is such: in T50 test method described herein, the total amount that acquisition can get oxygen (AVO) for its final quantity 50% required time greater than 180 seconds, preferred 180-480 second, more preferably 240-360 second.The method of measuring AVO content is disclosed in the european patent application 93870004.4.

The present invention another preferred aspect in, wherein peroxyacid bleach source is a peroxyacid bleach precursor, it is used in combination with the hydrogen peroxide cource body, the kinetics that hydrogen peroxide discharges in washing soln is such with respect to the kinetics that the heavy metal ion chelating agent component discharges: in T50 test method described herein, the concentration that obtains said heavy metal ion chelating agent is less than 120 seconds for its ultimate density 50% required time, preferably be less than 90 seconds, more preferably be less than 60 seconds, obtaining said concentration of hydrogen peroxide is that its ultimate density 50% required time was greater than 180 seconds, preferred 180 to 480 seconds, more preferably 240 to 360 seconds.

The final wash concentration of heavy metal ion chelating agent is generally 0.0001%-0.05%, is preferably greater than 0.001%, more preferably greater than 0.002%.

The final wash concentration of any inorganic perhydrate SYNTHETIC OPTICAL WHITNER is generally 0.005%-0.25% (weight), but is preferably greater than 0.05%, more preferably greater than 0.075%.

The final wash concentration of any peroxyacid precursor is generally 0.001% to 0.08% (weight), but preferred 0.005%-0.05%, most preferably 0.015%-0.05%.Postpone the release test method

This paper postpones release dynamics with " TA test method " definition, what should " TA test method " measure is the standard conditions that provide according to this paper when the composition that contains determined component when dissolved, and the amount that obtains this component is the required time of A% of its ultimate density/content.

This standard conditions comprise adding 10g composition in 1 liter of glass cylinder that 20 ℃ of distilled water of 1000ml are housed.Use magnetic stirrer with the material in the 100rpm speed stirred glass cup, this magnetic stirrer is beans/cobble shape, and overall dimension is 1.5cm, and minimum size is 0.5cm.Reach concentration/content and be used as ultimate density/content composition being added in the beaker that water is housed back 10 minutes institutes.

Select suitable analytical procedure with can be determined at accurately add composition in the beaker of water after, burst and the ultimate density of related component in solution.

This analytical procedure can comprise those methods of monitoring the component concentrations amount continuously, comprises for example flash ranging and electric conductance determination (conductrimetric) method.

In addition, can use these methods, it is included in the following at interval titration resultant (titres) of removing of regular time from solution, use proper method, as temperature by quick reduction titration resultant, stop its dissolution process, use the tested component concentrations in any method such as the chemical titration titration resultant then.

Can use suitable method of drawing, comprise curve fitting method, this suitable method can be calculated the TA value by the feedstock analysis result.

The selecteed specific analytical method of measuring concentration of component will depend on the character and the character that contains the composition of this component of component.Water-soluble washing-aid compound

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

The most preferred aspect of the present invention also provides the release of SYNTHETIC OPTICAL WHITNER in washing soln, with respect to the release of preferred water soluble detergency promoter component, and the method for delay.This method can comprise that the bleaching components above-mentioned with obtaining this paper postpones to discharge suitable described herein any delay method for releasing.

Preferred selected said delay method for releasing should make in test method described herein, and the concentration that obtains said water-soluble washing assistant is less than 120 seconds for its 50% time of ultimate density, preferably is less than 90 seconds, more preferably is lower than 60 seconds.

The final wash concentration of water soluble detergency promoter is generally 0.005%-0.4%, preferred 0.05%-0.35%, more preferably 0.1%-0.3%.

Suitable water soluble detergency promoter compound comprises the form of water-soluble mono polymeric polycarboxylate or their acid, all or the poly carboxylic acid of copolymerization or their salt.Wherein poly carboxylic acid comprises at least two carboxyls that are separated from each other, carbonate, supercarbonate, borate, phosphoric acid salt, silicate and aforesaid any mixture of no more than 2 carbon atoms.

Carboxylate salt or polycarboxylate washing assistant can be single polymeric or oligomerization type, but because Time, Cost And Performance, single polymeric polycarboxylate generally is preferred.

The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt of following acid: lactic acid, oxyacetic acid and its derivative.The polycarboxylate that contains two carboxyls comprises the water-soluble salt of following acid: succsinic acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, Diethylene Glycol acid, tartrate, tartronic acid and fumaric acid, and ether carboxylate and thionyl carboxylate salt.The polycarboxylate that contains three carboxyls comprises, especially water miscible Citrate trianion, aconitate and citraconate and succinate derivative.As in English Patent 1,379.241 the carboxyl methoxy succinate of middle description, in English Patent 1, newborn oxygen base (lactoxy) succinate of describing in 389,732 and aminosuccinic acid salt and the oxo polycarboxylate material in Holland's application 7205873, described, as 2-oxa--1,1,3-tricarballylic acid salt, it is described in English Patent 1, in 387,447.

The polycarboxylate that contains four carboxyls comprises the oxygen disuccinate, and it is disclosed in English Patent 1,261, in 829, and 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent polycarboxylate of sulfo group and be included in English Patent 1,398, disclosed sulfo-succinic acid salt derivative and in English Patent 1,439 in 421 and 1,398,422 and U.S.3,936,448, the sulfonated pyrolytic Citrate trianion of describing in 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 polyvalent alcohol, these polyvalent alcohols are sorbyl alcohol, mannitol and Xylitol for example.The aromatics polycarboxylate comprises mellitic acid, 1,2,4, disclosed phthalic acid derivative in 5-pyromellitic acid and the English Patent 1,425,343.

In above-mentioned polycarboxylate, preferably per molecule contains the hydroxycarboxylate of 3 carboxyls of as many as, particularly Citrate trianion.

Parent acid or its mixture and their salt of the polycarboxylate sequestrant of single polymeric or oligomerization, for example citric acid or Citrate trianion/citric acid mixture also are considered as useful builder component.

Also can use the borate washing assistant and contain the washing assistant that can generate borate substance, it can generate borate under washing composition storage or wash conditions, but is lower than about 50 ℃ in the wash conditions temperature, especially is lower than under about 40 ℃, and they are not preferred.

The example of carbonate builders is alkaline-earth metal and alkaline carbonate, is included in German patent application 2,321, disclosed yellow soda ash and concentrated crystal soda and its mixture and calcium carbonate superfine powder in 001 (on November 15th, 1973 is disclosed).

The specific examples of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, poly-partially/sodium phosphate wherein the polymerization degree be about 6 to 21 and the salt of phytinic acid.

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

The amount of the preferred silicate that exists is the 5%-50% (weight) of said composition, more preferably 10%-40% (weight) in detergent composition of the present invention.Additional detergent components

Detergent composition of the present invention also can contain additional detergent component.The accurate feature of these annexing ingredients and its incorporation will depend on the physical form of composition and the character of its washing operation that is used for.

The present composition can for example be configured to hand washing and laundry detergent composition, comprises laundry additive composition and the composition and the wash up machine composition that are applicable to pre-treatment band spot fabric.

When composition of the present invention is configured to the machine-washing method that is applicable to, when for example washing machine and wash up machine washing is washed the composition of method, the present composition preferably contains one or more additional detergent components, it is selected from tensio-active agent, water-insoluble washing assistant, organic polyhydroxyl compound, additional enzymes, suds suppressor, lime soap dispersing agent, dirt suspension and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain the softening agent as additional detergent components.Tensio-active agent

Detergent composition of the present invention can contain the tensio-active agent as additional detergent components, and it is selected from negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics and its mixture.

The general content of tensio-active agent is 0.1%-60% (weight).Tensio-active agent more preferably incorporation is 1%-35% (weight), most preferably 1%-20% (weight).

The tensio-active agent of preferred preparation be with composition in any enzyme component of existing be compatible.In liquid or gelatinous composition, most preferably Pei Zhi tensio-active agent can promote or these compositions of not degrading at least in the stability of any enzyme.

The generality of the species of negatively charged ion, nonionic, both sexes and zwitterionic classes tensio-active agent and these tensio-active agents is disclosed in the U.S.P.3 that authorized Laughlin and Heuring on December 30th, 1975 for example, in 929,678. Other example is disclosed in " Surface Active Agentsand Detergents " (I and II volume, Schwartz.Perry and Berch show).The example of suitable cats product is disclosed in the U.S.P.4 that authorized Murphy on March 31st, 1981, in 259,217.

When having amphoteric, both sexes and zwitterionics, they generally are to be used in combination with one or more negatively charged ion and/or nonionogenic tenside.Anion surfactant

Any anion surfactant useful substantially to the decontamination purpose all can be included in the present composition.These can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant salt (comprise, for example sodium, potassium, ammonium and the ammonium salt that replaces such as list, two and triethanolamine salt).

Other anion surfactant comprises fatty acid amide, alkyl succinate and the sulfosuccinate of isethionate such as acyl isethinate, N-acyl taurine salt, methylamino esilate, the monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂-C ₁₈Monoesters), the diester of sulfosuccinate (especially saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Be present in butter or also suit, as rosin, staybelite and resinous acid and hydrogenated resin acid by resinous acid and hydrogenated resin acid that butter obtain.The anion sulfate acid salt surfactant

Be applicable to that anion sulfate tensio-active agent of the present invention comprises the primary alkyl sulphates of straight chain and side chain, alkyl ethoxy sulfate, fatty oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) glucosamine sulfate and C ₅-C ₁₇Acyl group-N-(C ₁-C ₂Hydroxyalkyl) glucosamine sulfate and alkyl polysaccharide thing vitriol, for example vitriol of alkyl polyglucoside (this paper has also described the non-ionic compound of non-sulfuric acidization).

Alkyl ethoxy sulfate surfactant is preferably selected from C ₆-C ₁₈Its every mole of alkyl-sulphate by about 0.5 to about 20 moles of ethylene oxide ethoxylations.More preferably alkyl ethoxy sulfate surfactant is C ₆-C ₁₈Its every mole of alkyl-sulphate is by about 0.5 to about 20 moles, and preferred about 0.5 to about 5 moles of ethylene oxide ethoxylations.The anion sulfoacid salt surfactant

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

Be applicable to that anionic carboxylate tensio-active agent of the present invention comprises alkyl ethoxy carboxylate, alkyl polyethoxye polycarboxylate tensio-active agent and soap (alkyl carboxylate), secondary soaps especially described herein.

Alkyl ethoxy carboxylate preferred for the present invention comprises having formula RO (CH ₂CH ₂O) _xCH ₃COO ^-M ⁺Those, wherein R is C ₆To C ₁₈Alkyl, x are 0 to 10, and it is such that this ethoxylate distributes: calculate by weight, x is that this amount of substance of 0 o'clock is lower than about 20%; X is lower than about 25% greater than 7 o'clock amount of substance, when average R is C ₁₃Or when lower, average x is about 2 to 4; When average R greater than C ₁₃The time, average x is about 3 to 10, M is a positively charged ion, is preferably selected from basic metal, alkaline-earth metal, ammonium, list, two and triethanol ammonium, most preferably the mixture of sodium, potassium, ammonium and itself and magnesium ion.Preferred alkyl ethoxy carboxylate be those wherein R be C ₁₂-C ₁₈The compound of alkyl.

Be applicable to that alkyl polyethoxye polycarboxylate tensio-active agent of the present invention comprises having formula RO-(CHR ₁-CHR ₂-O)-R ₃Those, wherein R is C ₆-C ₁₈Alkyl, x are 1 to 25, R ₁And R ₂Be selected from hydrogen, formyloxy (methyl acid radical), amber acidic group, hydroxy succinic acid base and its mixture, wherein at least one R ₁Or R ₂Be amber acidic group or hydroxy succinic acid base, R ₃Be selected from hydrogen, replacement or unsubstituted hydrocarbon and its mixture with 1 to 8 carbon atom.The secondary soap surfactant of negatively charged ion

Preferred soap surfactant is to contain the unitary secondary soap surfactant of the carboxyl that is connected on the secondary carbon.This, carbon can be in the ring structure second month in a season, for example to the octyl group phenylformic acid or in the cyclohexane carboxylic acid salt that alkyl replaces.Secondary soap surfactant should preferably not contain ehter bond, ester bond and hydroxyl.Preferably in headgroup (amphiphilic moieties), should not contain nitrogen-atoms.Secondary soap surfactant contains 11-15 carbon atom altogether usually, but slightly many (for example as many as is 16) carbon atom also can be accepted, for example to the octyl group phenylformic acid.

Following general works further illustrates some preferred secondary soap surfactants:

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

B. the preferred secondary soap of other class comprises that carboxyl substituent wherein is those carboxylic compounds on the cyclic hydrocarbon radical unit, i.e. formula R ⁵-R ⁶The secondary soap of-COOM, wherein R ⁵Be C ₇-C ₁₀, preferred C ₈-C ₉Alkyl or alkenyl, R ⁶Be ring structure, (note: R as benzene, pentamethylene and hexanaphthene ⁵With respect to the ring on carboxyl can be in the neighbour, or contraposition).

C. also have another kind of preferred secondary soap to comprise formula CH ₃(CHR) _k-(CH ₂) _m-(CHR) _n-CH (COOM) (CHR) _o-(CH ₂) _p-(CHR) _q-CH ₃Secondary carboxylic compound, wherein R is C ₁-C ₄Alkyl, wherein k.n.o.q. is the integer of 0-8, condition be carbon atom (carbon atom that comprises carboxylate salt) add up to 10 to 18.

In above each formula A.B and C, M can be any suitable, especially water solubilization counter ion.

Being used for especially preferred secondary soap surfactant of the present invention is the water-soluble salt that is selected from following acid: 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and 2-amyl group-1-enanthic acid.The basic metal sarcosinate

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

Any nonionogenic tenside useful substantially to the decontamination purpose all can be included in the composition.Below listed the typical case of useful unrestricted type nonionogenic tenside.The nonionic polyhydroxy fatty acid amide surfactant

Be applicable to that polyhydroxy fatty acid amide of the present invention is to have formula R ²CONR ¹Those compounds of Z, wherein R ₁Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ₂Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is the polyhydroxy alkyl with straight-chain alkyl chain, directly is connected with at least 3 hydroxyls on its hydrocarbyl chain, or its alkoxylate (preferred ethoxylation or propoxylation) derivative.Z preferably reducing sugar from reductive amination process obtains; More preferably Z is a glycosyl.The alkylphenol condensation nonionogenic tenside

The condenses of the polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide is applicable to the present invention.Generally, polyethylene oxide condensation compound is preferred.These compounds comprise having for having an appointment 6 containing of straight or branched structure to the alkylphenol of the alkyl of about 18 carbon atoms and the condensation product of alkylene oxide.Ethoxylated alcohol nonionic surfactant

Fatty Alcohol(C12-C14 and C12-C18) and the about 1 alkyl ethoxylated condensation product to about 25 moles of ethylene oxide are applicable to the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, uncle or secondary alcohol, and generally contain 6 to 22 carbon atoms.Particularly preferably be every mol of alcohol and about 2 condensation products to about 10 moles of ethylene oxide with the alcohol that contains 8 to 20 carbon atom alkyls.The ethoxylated/propoxylated fatty alcohol nonionogenic tenside

Ethoxylation C ₆-C ₁₈Fatty Alcohol(C12-C14 and C12-C18) and C ₆-C ₁₈The blended ethoxylated/propoxylated fatty alcohol, particularly water miscible, be to be applicable to tensio-active agent of the present invention.Preferred ethoxylized fatty alcohol is to have the C that ethoxylation degree is 3-50 ₁₀-C ₁₈Ethoxylized fatty alcohol most preferably has the C that ethoxylation degree is 3-40 ₁₂-C ₁₈Ethoxylized fatty alcohol.It is 10 to 18 carbon atoms that preferred blended ethoxylated/propoxylated fatty alcohol has alkyl chain length, and ethoxylation degree is 3 to 30, and the propoxylation degree is 1 to 10.Nonionic EO/PO condenses with propylene glycol

Oxyethane and condensation product by the hydrophobic group thing of the condensation of propylene oxide and propylene glycol generation be applicable to of the present invention.The hydrophobic part of these compounds preferably has molecular weight about 1500 to about 1800, and shows water-insoluble.The example of this compounds comprises the Pluronic that some commerce of being sold by BASF can be buied ^TMTensio-active agent.Nonionic EO condensation product with propylene oxide/quadrol affixture

The product that is obtained by propylene oxide and reacting ethylenediamine and the condensation product of oxyethane are applicable to the present invention.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, generally its to have molecular weight be about 2500 to about 3000.The example of this class nonionogenic tenside comprises the Tetronic that some commerce of being sold by BASF can be buied ^TMCompound.Alkyl polysaccharide thing nonionogenic tenside

Be applicable to that alkyl polysaccharide thing of the present invention is disclosed in the U.S.4 of the Llenado that authorized on January 21st, 1986,565, in 647, it has and contains about 6 to about 30 carbon atoms, preferred about 10 to the hydrophobic part of about 16 carbon atoms with contain about 1.3 to about 10, preferred about 1.3 to about 3, most preferably from about 1.3 to the unitary poly-saccharides hydrophilic group of about 2.7 saccharidess, for example poly-glycosides.Can use any reducing sugar that contains 5 or 6 carbon atoms, glucose for example, available semi-lactosi and galactosyl partly replace the glucosyl part.(hydrophobic group is connected 2-by selectivity, 3-, and positions such as 4-have obtained glucose or semi-lactosi with respect to glucoside or galactoside like this.) key between the saccharides can be positioned at the 2-on a kind of position and formerly the saccharides unit on the additional saccharides unit, between the 3-, 4-and/or 6.

Preferred alkylpolyglycosides has formula

R ²O (C _nH _2nO) _t(glycosyl) _xR wherein ₂Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains 10-18, preferred 12-14 carbon atom; N is 2 or 3; T is 0 to 10, and is preferred 0, and x is 1.3 to 8, preferred 1.3 to 3, most preferably 1.3 to 2.7.This glycosyl is preferably obtained by glucose.The fatty acid amide nonionic tensio-active agent

Be applicable to that fatty acid amide surfactant of the present invention is to have formula R ⁶CON (R ⁷) ₂Those, R wherein ⁶For containing 7 to 21, the alkyl of preferred 9 to 17 carbon atoms, R ⁷All be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein x is 1 to 3.Amphoterics

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

The example that is applicable to alkyl apho dicarboxylic acid of the present invention is by Miranol, Inc., Dayton, Miranol (TM) the C2M Conc. amine oxide surfactant that NJ produces

The useful amine oxide of the present invention is to have formula R ³(OR ⁴) _xNO (R ⁵) ₂Those compounds, R wherein ³Be selected from and contain 8 to 26 carbon atoms, the alkyl of preferred 8 to 18 carbon atoms, hydroxyalkyl, acyl group amido propyl group and alkyl phenyl or its mixture; R ⁴For containing 2 to 3 carbon atoms, the alkylidene group of preferred 2 carbon atoms or hydroxyl alkylidene group or its mixture; X is 0 to 5, preferred 0 to 3; R ⁵Be and contain 1 to 3, the alkyl or the hydroxyalkyl of preferred 1 to 2 carbon atom, or contain 1 to 3, the polyethylene oxide group of preferred 1 ethylene oxide group.R ⁵Group can be connected to each other, and for example by oxygen or nitrogen-atoms, forms ring structure.

Amine oxide surfactant especially comprises C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₈Alkoxyethyl dihydroxy amine oxides.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, dodecyl amido propyl-dimethyl amine oxide, hexadecyl dimethyl amine oxide compound, stearyl dimethylamine oxide compound, tallow dimethylamine oxide compound and dimethyl-2-hydroxyl octadecyl amine oxide.C preferably ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈Acyl group amidoalkyl dimethyl amine oxide compound.Zwitterionics

Zwitterionics also can mix in the detergent composition of the present invention.These tensio-active agents can be described as the derivative of secondary and tertiary amines derived thing, the heterocycle second month in a season and tertiary amines derived thing or quaternary ammonium, quaternary phosphine or uncle's sulfonium compound widely.Trimethyl-glycine and sultaine are to be used for the typical zwitterionics of the present invention.Beet alkali surface activator

Useful in the present invention trimethyl-glycine is to have formula R (R ¹) ₂N ⁺R ²COO ^-Those compounds, wherein R is C ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl or C ₁₀-C ₁₆The acyl group amidoalkyl, each R ¹Be generally 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 suitable trimethyl-glycine comprises coconut acyl group amido propyl-dimethyl trimethyl-glycine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C _12-14The acyl group amido propyl betaine; C _8-14Acyl group amido hexyl diethyl betaines; 4[C _14-16Acyl group methyl amido diethyl ammonium (ammonio)]-1-carboxyl butane; C _16-18Acyl group amido dimethyl betaine; C _12-16Acyl group amido pentane diethyl betaines; (C _12-16Acyl group methyl amido dimethyl betaine.Preferred trimethyl-glycine is C _12-18Dimethyl Ammonium (ammonio) hexanoate and C _10-18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound betaine tensio-active agent also is applicable to the present invention.Sultaine (sultaine) tensio-active agent

The useful sultaine of the present invention is to have formula R (R ¹) ₂N ⁺R ²SO ₃ ^-Those compounds, wherein R is C 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, preferred hydroxyl alkylidene group.Amphoterics

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

Cats product also can be used in the detergent composition of the present invention, and suitable cats product comprises quaternary ammonium surfactant, and it is selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.Be partly dissolved or insoluble washing-aid compound

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

The example of the water-soluble washing assistant of part comprises crystalline layered silicate.The example of basic water-insoluble washing assistant comprises sodium silicoaluminate.

Crystalline layered sodium silicate has general formula:

NaMSi _xO _2x+1.yH ₂O wherein M is sodium or hydrogen, and x is 1.9 to 4 number, and y is 0 to 20 number.Such crystalline layered sodium silicate is disclosed among the EP-A-0164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.For the object of the invention.X in the above general formula is 2,3 or 4, is preferably 2.Most preferred such material is δ-Na ₂Si ₂O ₅, can buy by Hoechst, be NaSK S-6.

The crystalline layered sodium silicate material is preferably as existing in the seed shape detergent composition with the tight blended particle of solid, water soluble ionizable species.This solid, water soluble ionizable species is selected from organic acid, organic and inorganic acid salt and its mixture.

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

The silico-aluminate ion exchange material can be naturally occurring material, but preferably synthetic obtaining.What synthetic crystallization silico-aluminate ion exchange material can be buied is Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and its mixture of registration.Zeolite A has formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein x is 20 to 30, especially 27.Zeolite X has formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂O.Enzyme

Other useful in detergent composition selection component is one or more additional enzymes.

Preferred additional enzymes material comprises lipase, amylase, neutrality and Sumizyme MP, ester (separating) enzyme, cellulase, polygalacturonase and the peroxidase that commerce can be buied, and they are impregnated in the detergent composition usually.Suitable enzyme is disclosed in U.S.3, in 519,570 and 3,533,139.

The proteolytic enzyme that preferred commerce can be purchased comprises that the trade mark of being sold by Novo Industries A/S (Denmark) is those of Alcalase, Savinase, Primase, Durazym and Esperase, the trade mark of being sold by Gist-Brocades is those of Maxatase, Maxacal and Maxapem, those that sell by Genencor International and be those of Opticlean and Optimase by the trade mark that Solvay Enzymes sells.Proteolytic enzyme can be by mixing according in the composition of the present invention for the 0.0001%-4% organized enzyme amount of composition weight.

Preferred amylase comprises, for example is the α-Dian Fenmei that the special bacterial strain by bacillus licheniformis obtains, and it is described in greater detail in GB-1, among 269,839 (Novo).The amylase that preferred commerce can be buied comprise the trade mark of for example selling by Gist-Brocades be Rapidase those and be those of Termamyl and BAN by the trade mark that Novo Industries A/S sells.Amylase can be by mixing according in the composition of the present invention for the 0.0001%-2% organized enzyme amount of composition weight.

The content of lipolytic enzyme (lipase) is 0.0001% to 2% (weight) of composition weight, preferred 0.001% to 1% (weight), the most preferably active lipolytic enzyme of 0.001% to 0.5% (weight).

Lipase can derive from fungi or bacterium, for example is to plant bacterial classification, tea toadstool kind or pseudomonas kind by corruption, comprises the lipase of the bacterial strain generation of Rhodopseudomonas false pain alkali bacillus or Pseudomonas fluorescens.Lipase chemical or that genetically altered mutation obtains by these bacterial strains also can be used for the present invention.

Preferred lipase is obtained by Rhodopseudomonas false pain alkali bacillus, and it is described among the European patent EP-B-0218272 of mandate.

Other preferred lipase of this paper is by being planted Pseudomonas fetal hair bacterium clone gene and obtaining as this gene of host expresses with aspergillus oryzae by corruption, it is described among European patent application EP-A-0258068, commercial can be by Novo Industri A/S, Bagsvaerd, (Denmark) buys, and trade mark is Lipolase.This lipase also is described in the people's such as Huge-Jensen that authorized on March 7th, 1989 U.S.4, in 810,414.The enzyme stabilising system

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

The present composition also can comprise 0 to about 10%, preferred about 0.01% chlorine bleach scavenging agent to about 6% (weight), and it is added into is in order to be suppressed at the chlorine bleach material damage enzyme that exists in many water supply and to make enzyme deactivation, especially under alkaline condition.Cl content may be a spot of in water, generally at about 0.5ppm to about 1.75ppm scope, but in washing process, the got chlorine in the overall ponding that contact with enzyme is normally a large amount of, so in use enzyme stability is an individual problem.

Suitable chlorine scavenger negatively charged ion wide material sources for example contain the salt, sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide of ammonium cation etc.Also can use antioxidant such as carbaminate, xitix etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and its mixture.Can make other conventional scavenging agent such as hydrosulfate if necessary.Nitrate, muriate, hydrogen peroxide cource body such as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc. and its mixture.Organic polyhydroxyl compound

Organic polyhydroxyl compound is the particularly preferred component of detergent composition of the present invention.The organic polyhydroxyl compound meaning is any polymerizable organic compound that is used as necessity of powder and antiredeposition and soil suspension agent usually in detergent composition.

The amount of the general organic polyhydroxyl compound that mixes in detergent composition of the present invention is 0.1% to 30% of a composition weight, and is preferred 0.5% to 15%, most preferably 1% to 10%.

The example of organic polyhydroxyl compound comprises water miscible all organic or the carboxylic acid of copolymerization or their salt, and wherein poly carboxylic acid comprises the carboxyl of at least two no more than two carbon atoms that are separated from each other.The polymkeric substance of latter's type 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 they and maleic anhydride, and it is 20,000 to 100,000 that this multipolymer has molecular weight, especially 40,000 to 80,000.

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

The polyamino compounds useful in the present invention comprises those that are obtained by aspartic acid, as at EP-A-305282, and those disclosed among EP-A-305283 and the EP-A-351629.

The present invention suits contains the ter-polymers that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol monomeric unit in addition, particularly has molecular-weight average and be those of 5000 to 10000.

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

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

The present composition can contain the lime soap dispersing agent compound, and it has by defined dispersion of calcium soap (LSDP) hereinafter and is not more than 8, preferably is not more than 7, most preferably is not more than 6.Lime soap dispersing agent compound preferred content is the 0.1%-40% (weight) of composition, more preferably 1%-20% (weight), most preferably 2%-10% (weight).

Lime soap dispersing agent is the sedimentary class material of basic metal, ammonium or amine salt that suppresses lipid acid with calcium or magnesium ion.The numerical value of lime soap dispersing agent validity is weighed and is provided by dispersion of calcium soap (LSDP), dispersion of calcium soap is to use by being rolled up by the article Oil.Chem.Soc.27 that H.C.Borghetty and C.A.Bergman.J.Am. showed, and the calcium soap distributed test of describing in the 88-90 page or leaf (1950) is measured.This calcium soap distributed test method is used widely by the professional in present technique field, and this refers to for example in following comment: W.N.Linfield, SurfactantScience Series, 7 volumes, p3; W.N.Linfield, Tenside Surf.Det., 27 volumes, p159-161 (1990); And M.K.Nagarajan, W.F.Masler, Cosmeticsand Toiletries, 104 volumes, p71-73, (1989).Need to disperse by the 0.025g sodium oleate at 30ml 333ppm CaCO ₃(Ca: Mg=3: 2) weight of the sedimental dispersion agent of calcium soap that forms in the water of equivalent hardness is LSDP with the ratio % of sodium oleate weight.

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

Be used for the example that the LSDP of having of the present invention is not more than 8 tensio-active agent and comprise C ₁₆-C ₁₈Dimethyl oxidation amine has the C that average degree of ethoxylation is 1-5 ₁₂-C ₁₈Alkyl ethoxy sulfate particularly has the C of ethoxylation degree about 3 ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant (LSDP=4) and have the C that average degree of ethoxylation is 12 (LSDP=6) or 30 ₁₃-C ₁₅Ethoxylated alcohol, it is to be respectively LutensolA012 and Lutensol A030 by the trade mark that BASF GmbH sells.

Be applicable to that polymerization lime soap dispersing agent of the present invention is described in article Cosmetics and the Toiletries that is shown by M.K.Nagarajan and W.F.Masler, 104 volumes, p71-73 is in (1989).The example of this polymerization lime soap dispersing agent comprises the water-soluble salt of some multipolymer of the acrylamide of vinylformic acid, methacrylic acid or its mixture and acrylamide or replacement, and it is 5,000 to 20,000 that this polymkeric substance generally has molecular weight.Press down foam system

When detergent composition preparation of the present invention was used for the use in washing machine composition, it preferably included and presses down foam system, and its content is the 0.01%-15% of composition, preferred 0.05%-10%, most preferably 0.1%-5% (weight).

Be applicable to that the foam system that presses down of the present invention can comprise any known anti-alveolation compound substantially, comprises for example anti-alveolation compound of polysiloxane, the anti-alveolation compound of 2-alkyl and alcanol.

The anti-herein alveolation compound meaning is to have the solution of inhibition by detergent composition, the especially foaming that produces under this solution situation of stirring or any compound or its mixture of forming process.

The particularly preferred anti-alveolation compound that uses in the present invention is the anti-alveolation compound of polysiloxane defined herein, as comprises any anti-alveolation compound of polysiloxane component.The anti-alveolation compound of this polysiloxane generally also contains silica component.Term used herein " polysiloxane " is industrial general, comprises that multiple relative high-molecular weight contains the polymkeric substance of siloxane unit and all kinds alkyl.The preferred anti-alveolation compound of polysiloxane is a siloxanes, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocks.

Other suitable anti-alveolation compound comprises monocarboxylic acid lipid acid and its water-soluble salt.These materials are described in to be authorized in the United States Patent (USP) 2,954,347 of Wayne St.John September 27 nineteen sixty.Monocarboxylic acid lipid acid and its salt as suds suppressor generally have 10 to about 24 carbon atoms, the hydrocarbyl chain of preferred 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt such as sodium, potassium and lithium salts, ammonium and alkanol ammonium salt.

Other suitable anti-alveolation compound comprises for example high molecular weight fatty acid ester (for example fatty acid triglyceride), the fatty acid ester of monohydroxy-alcohol, aliphatic C ₁₈-C ₄₀Ketone (for example stearone), N-alkylation aminotriazine, for example three to six alkyl melamines or two to the tetraalkyl diammonium chloride for triazine, they are product, two stearic amides and single stearyl di(2-ethylhexyl)phosphate basic metal (for example sodium, potassium, lithium) salt and single stearyl phosphoric acid ester that cyanuric chloride and 2 or 3 moles contain the uncle of 1 to 24 carbon atom or secondary amine, propylene oxide.

The multipolymer of oxyethane and propylene oxide especially has 10 to 16 carbon atom alkyl chain lengths, ethoxylation degrees and is 3 to 30, the propoxylation degree is that 1 to 10 blended ethoxylated/propoxylated fatty alcohol also is to be used for the anti-alveolation compound that the present invention suits.

Be applicable to that the anti-alveolation compound of 2-alkyl-alcanols of the present invention is described among the DE4021265.Be applicable to that 2-alkyl-alcanols of the present invention is by the C that has terminal hydroxyl groups ₆-C ₁₆Alkyl chain constitutes, this alkyl chain on two positions by C ₁-C ₁₀Alkyl replaces.The mixture of 2-alkyl-alcanols can be used in the present composition.

The preferred foam system that presses down comprises

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

(i) be the 50%-90% of the anti-alveolation compound of polysiloxane weight, preferred 75%-95% polydimethylsiloxane; With

(ii) be the 1%-50% of the anti-alveolation compound of polysiloxane/silicon-dioxide weight, preferred 5%-25% (weight) silicon-dioxide; The incorporation of the anti-alveolation compound of wherein said silicon-dioxide/polysiloxane is 5%-50%, preferred 10%-40% (weight);

(b) compound dispersing agent, most preferably comprise polysiloxane ethylene glycol rake formula multipolymer, it has polyoxy alkylidene content is 72-78%, the ratio of oxyethane and propylene oxide is 1: 0.9 to 1: 1.1, the content of this compound dispersing agent is 0.5%-10%, preferred 1%-10% (weight), and particularly preferred this class polysiloxane rake formula multipolymer is DCO544, can be buied by DOWCorning commercial, trade mark is DCO544;

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

Comprise the alkylation polysiloxane of open type more than this paper and the mixture of solid silica in the useful preferred granular suds suppressing agent system of this paper.

Solid silica can be pyrogenic silica, precipitated silica or the silicon-dioxide that makes by the gel formation technology.It is 0.1 to 50 micron that suitable silica dioxide granule has average particle size, and preferred 1 to 20 micron, surface-area is at least 50m ²/ g, these silica dioxide granules are by being bonded directly to the treatment process on the silicon-dioxide or being made into hydrophobic with the method for polyorganosiloxane resin with dialkyl group silyl and/or trialkylsilkl.The preferred use has hydrophobic silica dioxide granule of being of dimethyl and/or trimethyl silyl.The preferred anti-alveolation compound particle that is included in the detergent composition of the present invention suits to contain a certain amount of silicon-dioxide, and the weight ratio that makes silicon-dioxide and polysiloxane is at 1: 100 to 3: 10, between preferred 1: 50 to 1: 7.

The typical example of the granular suds suppressing system that other is suitable is hydrophobic silanization (most preferably trimethyl silicone hydride) silicon-dioxide, and it has granularity is 10 millimicrons to 20 millimicrons, and specific surface area is at 50m ²More than/the g, be and have the intimate mixture that molecular weight is about 500 to about 200,000 dimethylpolysiloxanefluids fluids that wherein the weight ratio of the silicon-dioxide of polysiloxane and silanization is about 1: 1 to about 1: 2.

Most preferred granular suds suppressing system is described among the EP-A-0210731, comprising the anti-alveolation compound of polysiloxane and having fusing point is 50 ℃ to 85 ℃ organic carrier material, and wherein the organic carrier material comprises monoglyceride and has the lipid acid that contains 12 to 20 carbon atom carbochains.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein the organic carrier material is to have lipid acid or alcohol or its mixture that contains 12 to 20 carbon atom carbochains, and it has fusing point is 45 ℃ to 80 ℃.

Other most preferred granular suds suppressing system is described in the european patent application 91870007.1 of pending trial of the Procter and GambleCompany by name of company, this system comprises the anti-alveolation compound of polysiloxane, carrier substance, organic coating material and glycerine, and wherein the weight ratio of the anti-alveolation compound of glycerine and polysiloxane is 1: 2 to 3: 1.The European application 91201342.0 of pending trial also discloses most preferred granular suds suppressing system, comprise the anti-alveolation compound of polysiloxane, carrier substance, organic coating material and crystallization or amorphous aluminosilicate, wherein the weight ratio of the anti-alveolation compound of silico-aluminate and polysiloxane is 1: 3 to 3: 1.Preferred carrier substance in two kinds of most preferred particle foam control agents described above is a starch.

The example that is used for granular suds suppressing system of the present invention is that it comprises following (i), combination (ii), (iii) and (iv) by the particle agglomerates component of agglomeration method preparation:

(i) 5%-30%, the preferred anti-alveolation compound of 8%-15% (weight) polysiloxane component, the preferably mixture of itself and polydimethylsiloxane and silicon-dioxide;

(ii) 50%-90%, preferred 60%-80% (weight) carrier component, preferred starch;

(iii) 5%-30%, preferred 10%-20% (weight) agglomerate binder compound component, this compound of the present invention can be generally as any compound or its mixture of agglomerate tackiness agent, and most preferably said agglomerate binder compound comprises that having ethoxylation degree is 50 to 100 C ₁₆-C ₁₈Ethoxylated alcohol; With

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

Detergent composition of the present invention also can comprise 0.01%-10%, preferred 0.05%-0.5% (weight) dye transfer polymerization retarder.

This dye transfer polymerization retarder is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its mixture of polyamine-N-oxide polymer, N-vinyl pyrrolidone and N-vinyl imidazole.A) polyamine N-oxide pllymers

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

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

-O-,-S-,-N-; X is 0 or 1; R is aliphatic group, ethoxylation aliphatic group, aromatic group, heterocycle or alicyclic radical or its any combination, the nitrogen in the N-O group can be attached at that R goes up or wherein the nitrogen in the N-O group be the part of these groups.

The N-O group can be represented with following general structural formula: R wherein ₁, R ₂And R ₃Be aliphatic group, aromatic group, heterocycle or alicyclic radical or its mixing, x or/and y or/and z is 0 or 1, the part that the nitrogen in the N-O group can link thereon or wherein the nitrogen in the N-O group constitutes these groups wherein.The N-O group can be the part of polymerizable unit (P) or be connected on the polymer main chain, or the two combination.

The suitable polyamine N-oxide that the N-O group constitutes a polymerizable unit part comprises polyamine N-oxide, and wherein R is selected from aliphatic group, aromatic group, alicyclic ring or heterocyclic group.Class in this polyamine-N-oxide compound comprises one group of polyamine N-oxide, and wherein the nitrogen in the N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is those of heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and its derivative.

Another kind of in this polyamine N-oxide comprises the one group polyamine N-oxide of nitrogen access node to the R group in the N-O group wherein.

Other suitable polyamine N-oxide is the polyamine oxide compound, and the N-O group is connected on its polymerisable unit.

These polyamine N-oxide preferred type are the polyamine N-oxide with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen in the N-O functional group is the part of this R group.The example of these types is polyamine oxide compounds, and wherein R is heterogeneous ring compound such as pyridine, pyrroles, imidazoles and its derivative.

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

Can use any main polymer chain, as long as the amine oxide polymers that forms is water miscible and has the character that suppresses dye transfer.The example of suitable polymer main chain is polyethylene, polyalkylene class, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.

The ratio that amine of the present invention-N-oxide polymer generally has amine and amine n-oxide is 10: 1 to 1: 1,000,000.Yet the amount of the amine oxide group in the polyoxygenated amine polymer can change according to suitable co-polymerization or suitable N-oxidisability.Preferred amines is 2: 3 to 1: 1 with the ratio of amine n-oxide, 000,000, and more preferably 1: 4 to 1: 1000000, most preferably 1: 7 to 1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and wherein a kind of monomer type is an amine n-oxide, and other monomer type is amine n-oxide or is not.The amine oxide unit of polyamine N-oxide has pKa＜10, preferred pKa＜7, more preferably pKa＜6.

Can obtain the almost polyoxygenated amine of any polymerization degree.This polymerization degree is not crucial, as long as this material has the water-soluble and suspension dyestuff ability that needs.General its molecular-weight average is 500 to 1000,000, and is preferred 1,000 to 50,000, more preferably 2,000 to 30,000, most preferably 3,000 to 20,000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

The preferred polymkeric substance of Shi Yonging comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer in the present invention, and wherein to have molecular-weight average be 5,000 to 50 to this polymkeric substance, 000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000, the mol ratio that preferred N-vinyl imidazole N-vinylpyrrolidone copolymer has N-vinyl imidazole and N-vinyl pyrrolidone is 1 to 0.2, more preferably be 0.8 to 0.3, most preferably 0.6 to 0.4.C) Polyvinylpyrolidone (PVP)

Detergent composition of the present invention can use also that to have molecular-weight average be 2,500 to 400,000, and is preferred 5,000 to 200,000, and more preferably 5,000 to 50,000,5,000 to 15,000 polyvinylpyrrolidone (" PVP ") most preferably.Suitable Polyvinylpyrolidone (PVP) commercial can be available from ISP Corporation, New York, NY and Montreal, Canada, name of product are PVP K-15 (the adhesion molecules amount is 10,000), (molecular-weight average is 40 to PVP K-30,000), (molecular-weight average is 160 to PVP K-60,000), PVP K-90 (molecular-weight average is 360,000).PVP K-15 also can be available from ISP Corporation.Can comprise Sokalan HP 165 and Sokalan HP 12 by other suitable polyvinylpyrrolidone that BASF Cooperation buys commercial.

The amount of the polyvinylpyrrolidone that can mix in detergent composition of the present invention is the 0.01%-5% (weight) of detergent composition, preferred 0.05%-3% (weight), more preferably 0.1% to 2% (weight).The amount of the polyvinylpyrrolidone that discharges in washing soln is preferably 0.5ppm to 250ppm, preferred 2.5ppm to 150ppm, more preferably 5ppm to 100ppm.D) Ju Yi Xi oxazolidinone

Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the dye transfer polymerization retarder.It is 2,500 to 400,000 that this Ju Yi Xi oxazolidone has molecular-weight average, preferred 5,000 to 200,000, more preferably 5,000 to 50,000, most preferably 5,000 to 15,000.

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

Detergent composition of the present invention also can use polyvinyl imidazole as the dye transfer polymerization retarder.It is 2,500 to 400,000 that this polyvinyl imidazole preferably has molecular-weight average, more preferably 5,000 to 50,000, most preferably 5,000 to 15,000.

The amount of the polyvinyl imidazole that mixes in detergent composition can be 0.01%-5% (weight), preferred 0.05%-3% (weight), more preferably 0.1%-2% (weight).The amount of the polyvinyl imidazole that discharges in washing soln is 0.5ppm to 250ppm, preferred 2.5ppm to 150ppm, more preferably 5ppm to 100ppm.White dyes

Detergent composition of the present invention also can randomly contain the wetting ability white dyes that 0.005% to 5% (weight) of having an appointment also provides some type that suppresses the dye transfer effect.If use, the present composition will preferably include this white dyes of about 0.01%-1% (weight).

Useful in the present invention hydrophilic white dyes is to have those of following structural formula:

R wherein ₁Be selected from anilino, N-2-double hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-double hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino (morphilino), chlorine and amino; M is salt-forming cation such as sodium or potassium.

When in following formula, R ₁Be anilino, R ₂Be the N-2-double hydroxyethyl, when M was positively charged ion such as sodium, this whitening agent was 4.4 '-two ((4-anilino-6-(N-2-double hydroxyethyl)-S-triazine-2-yl) amino)-2,2 '-Stilbene disulfonic acid and its disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade mark is Tinopal-UNPA-GX.Tinopal-UNPA-GX is a preferred wetting ability white dyes useful in the detergent composition of the present invention.

When in following formula, R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino-, M is a positively charged ion, during as sodium, this whitening agent is 4.4 '-two ((4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-S-triazine-2-yl) amino) 2.2 '-the Stilbene disulfonic acid disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade mark is Tinopal 5BM-GX.

When in following formula, R ₁Be anilino, R ₂Be morpholino (morphilino), when M was positively charged ion such as sodium, this whitening agent was 4.4 '-two ((4-anilino-6-morpholino-S-triazine-2-yl) amino) 2.2 '-the Stilbene disulfonic acid sodium salt.This concrete whitening agent is sold by Ciba Geigy Corporation commercial, and trade mark is Tinopal AMS-GX.

Be selected for these specific white dyess of the present invention when the performance benefit that especially effectively suppresses dye transfer is provided when selecteed polymeric dye transfer inhibitor mentioned above is used in combination.The combination of this selecteed polymeric material (for example PVNO and/or PVPVI) and this selecteed white dyes (for example Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) all provides the significantly good inhibition to dye transfer in wash water solution than any of this two kinds of detergent composition components of independent use.Do not accept opinion and keep within bounds, believe that the mode of action of this whitening agent is:, therefore be deposited on relatively apace on these fabrics because they have high affinity to the fabric in the washing soln.Whitening agent is deposited on the degree on the fabric in the washing soln and is defined with the parameter that is called " expending coefficient ".This expend coefficient refer generally to be deposited on the fabric the whitening agent material a) with initial whitening agent concentration b in wash water solution) ratio.Have the high relatively whitening agent that expends coefficient and in this class technology contents of the present invention, be suitable for suppressing dye transfer most.

Certainly, should recognize that also other types of conventional white dyes of these compounds can randomly be used for the present composition and " brighten " benefit so that conventional fabric to be provided, and in fact not suppress the effect of dye transfer.This application is conventional and is known for the preparation of washing composition.Softening agent

Fabric softener also can mix in the laundry detergent composition of the present invention.These reagent can be inorganic or organic types.The illustrated example of inorganic softening agent is the smectic clays that is disclosed among the GB-A-1400898.The organic fabric softening agent comprises the water-insoluble tertiary amine that is disclosed among GB-A-1514276 and the EP-B-0011340.

The content of smectic clays is generally 5%-15%, 8%-12% (weight) more preferably, and it is with mixing material that component adds and add in the rest part of prescription as doing.The incorporation of for example water-insoluble tertiary amine of organic fabric softening agent or two long-chain acid amides materials is 0.5%-5% (weight), be generally 1%-3% (weight), and the add-on of high molecular weight polyethylene oxide material and water-soluble cationic material is 0.1%-2%, is generally 0.15%-1.5% (weight).Other optional ingredient

Suitable other optional ingredient that is included in the present composition comprises spices, pigment and filling salt, and sodium sulfate is preferred filling salt.Composition forms

Detergent composition of the present invention can be mixed with form such as powder, particle, cream, liquid, lamellar body and the gel of any needs.Liquid composition

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

Detergent composition of the present invention also can be the form of gel.This based composition is about 750,000 to prepare to about 4,000,000 polyalkenyl polyethers with having molecular weight generally.Solids composition

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

The granularity of the component of particulate composition of the present invention should be preferably such: diameter is no more than 5% greater than the particle of 1.4mm, and diameter is less than the particle of 0.15mm no more than 5%.

The bulk density of granular detergent composition of the present invention is generally 450g/l at least, the more general 600g/l that is at least, more preferably 650g/l to 1200g/l.

Bulk density is measured with simple funnel and cup device, constituting of this device: the plate valve that firmly is embossed in the conical hopper on the pedestal and installs than low-end at funnel, this plate valve can make the inclusion in the funnel flow in the axially aligned cylindrical cup that is placed under this funnel.Funnel is corresponding higher and be 130mm and 40mm than the height of lower end.It is installed on the pedestal, thus its than low side at the above 140mm of pedestal high surfaces.Cup has total height 90mm, and interior height is 87mm, and interior diameter is 84mm.It is 500ml that this glass demarcated volume.

For measuring, with hand powder is packed in the funnel, open plate valve and make the powder cup that overfills.Shift out the filler cup from this base,, remove excess powder than the upper edge from cup by this glass with the instrument such as the cutter on vertical edges edge.This filler cup of weighing then doubles the numerical value that obtains powder weight, and the tap density of representing with g/l just is provided.Carry out replication on demand.Preparation technology-particulate composition

Generally, granular detergent composition of the present invention can pass through prepared in various methods, and this method comprises dry mix, spray-drying process, agglomeration technique and comminution granulation.Washing methods

The present composition can be used for any washing or purging method substantially, comprises the method with washing machine and wash up machine.Method with the wash up machine

Preferred method with the wash up machine comprises and is used in the aqueous solution dissolving or has disperseed the wash up machine of the present invention of significant quantity to handle the article of being with dirt with the aqueous solution of composition that it is selected from porcelain, glassware, holloware and cutlery and its mixture.The wash up machine of significant quantity is dissolving or disperse 8g to 60g product in the washing soln of 3 to 10 liters of volumes with the general meaning of composition, and this is common product dosage and the washing soln volume that uses in wash up machine method in routine usually.Method with washing machine

The method with washing machine herein comprises that the aqueous solution that is used in the aqueous solution dissolving or has disperseed the laundry detergent composition of the present invention of significant quantity handles the clothing of being with dirt in washing machine.Washing composition is to add in the washing soln by the dispersing chamber of washing machine or by decollator.The general meaning of the detergent composition of significant quantity is dissolving or disperse 40g to 300g product in the washing soln of 5 to 65 liters of volumes, and this is common product dosage and the washing soln volume that uses in the washing machine method in routine usually.

In the preferred washing methods of the present invention, the decollator that contains the significant quantity Betengent product was put in before cycles of washing begins in the bucket of preferred front-loading washing machine.

Decollator is a container that Betengent product is housed, and it is used to directly release products in the bucket of washing machine.Its volume capacity should be equipped with normally used enough Betengent products in washing methods.

When washing machine was loaded into clothing, the decollator that Betengent product is housed was placed in the bucket.When the washing machine cycles of washing begins, water be injected in the bucket and bucket by periodic rotation.The design of decollator should be such: it can retain dried Betengent product, but allows this product to discharge along with the rotation of stirring as bucket in the cycles of washing process, and this also is that it immerses the result in washing water.

For Betengent product is discharged in washing process, this decollator can have a plurality of perforates, and product can pass through from opening.In addition, this decollator can by to the liquid permeable but the material of solid phase prod impermeability is made, it allows dissolved product to discharge.Preferably when cycles of washing begins, the Betengent product snap-out release, thus in this stage of cycles of washing, in washing machine drum, provide moment high local concentrations component such as water-soluble washing assistant and heavy metal ion chelating agent component.

Preferred decollator is reusable, and its design should make the integrity that keeps container in drying regime and cycles of washing process.Be used for particularly preferred decollator of the present invention and be described in following patent: GB-B-2,157,719, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.Be published in Manufacturing Chemist by J.Bland, in November, 1989, the particularly preferred decollator that is applicable to the granular detergent product also described in the article of p41-46, and this granular detergent product is general known grain type product.

Especially preferred decollator is disclosed in european patent application 0343069 ﹠amp; In 0343070.The latter applies for disclosing a kind of decollator, and it comprises a flexible boot by the bag shaped structure that the regulation aperture is arranged that stretches out in the sustained ring, and this aperture can allow sack to be equipped with to be used for the product of q.s in the cycles of washing first time of washing process.The part washing medium flows in the bag by aperture, dissolved product, and solution outwards flows in the washing medium by aperture then.This sustained ring is equipped with the undissolved product outflow of a protective cover to prevent to wet, and this device generally comprises the wall of the circumferentially extending that stretches out in the central boss by a spoke wheel structure or similar structures, and its mesospore has the spiral structure.The pre-treatment washing methods

In pre-treatment washing methods of the present invention, the basic thing of band dirt/spot by with significant quantity contain the heavy metal ion chelating, but do not contain the preprocessing solution processing of bleaching components.This solution alternative contains other non-SYNTHETIC OPTICAL WHITNER detergent component, as tensio-active agent, washing assistant, enzyme and washing composition polymkeric substance.Preferred this solution also contains water soluble detergency promoter.

The content of the heavy metal ion chelating agent in this preprocessing solution is generally 0.0005%-1%, is preferably greater than 0.05%.

Make preprocessing solution and dirt base thing keep in touch working lipe at interval.This timed interval was generally 10 seconds to 1800 seconds, more preferably was 60 seconds to 600 seconds.

With suitable washing methods washing dirt base thing, wherein use the detergent composition that contains SYNTHETIC OPTICAL WHITNER then.This washing methods can be for example described herein any with washing machine method or with the method for wash up machine.

In detergent composition, the component symbol of abbreviation has following connotation:

XYAS: C _1X-C _1YSodium alkyl sulfate

24EY: condensation has the C of average Y moles of ethylene oxide ₁₂-C ₁₄

It mainly is the primary alconol of straight chain

XYEZ: condensation has the C of average Z moles of ethylene oxide _1X-C _1Y

It mainly is the primary alconol of straight chain

XYEZS: every mole of condensation has the C of average Z moles of ethylene oxide _1X-

C _1YSodium alkyl sulfate

TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide

Silicate: amorphous sodium silicate (SiO ₂: Na ₂The O ratio is 2.0)

NaSKS-6:: formula δ-Na ₂Si ₂O ₅Crystalline layered silicate

Carbonate: anhydrous sodium carbonate Polycarboxylate: 1: 4 toxilic acid/acrylic acid multipolymer, molecular-weight average is

About 80,000Zeolite A: the sodium silicoaluminate of hydration, its formula is:

Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O, main granularity exists

1 to 10 micron Citrate: citrate trisodium dihydrate Percarbonate: use formula Na ₂SO ₄NNa ₂CO ₃The empirical formula (particle of snap-out release) that mixing salt coats is 2Na ₂CO ₃3H ₂The anhydrous SPC-D SYNTHETIC OPTICAL WHITNER of O, its

In n be 0.29, percarbonate and mixing salt weight ratio be

39: 1Percarbonate: with water glass (Si ₂O: Na ₂The O ratio is 2: 1) the anhydrous SPC-D SYNTHETIC OPTICAL WHITNER that coats of coating layer (particle of Shi Fanging at a slow speed), percarbonate with

The weight ratio of water glass is 39: 1TAED: tetraacetyl ethylene diamine TAED: by with citric acid and molecular weight being (PEG) particle of agglomeration TAED to form of 4000 polyoxyethylene glycol (particle of Shi Fanging at a slow speed), TAED:

The components by weight of citric acid: PEG is 75: 10: 15,

There is the citric acid coating layer this particle outside, agglomerate and citric acid

The weight ratio of coating layer is 95: 5.Benzoyl Caprolactam: with citric acid and molecular weight is the particle that 4000 polyoxyethylene glycol (PEG) (particle of Shi Fanging at a slow speed) agglomeration benzoyl caprolactam (BzCl) forms,

The components by weight of BzCl: citric acid: PEG is 63: 21:

16, there is the citric acid coating layer this particle outside, agglomerate and lemon

The weight ratio of lemon acid coating layer is 95: 5TAED: with part neutral polycarboxylate agglomeration TAED (particle of snap-out release) grain to form, the ratio of TAED and polycarboxylate is 93: 7, should

There is the polycarboxylate coating layer particle outside, agglomerate and coating layer

Weight ratio is 96: 4EDDS: spraying drying EDDS and MgSO ₄The particle that forms, (particle of snap-out release) EDDS and MgSO ₄Weight ratio is 26: 74Protease: the trade mark of being sold by Novo Industries A/S is

The proteolytic enzyme of Savinase, activity are 13 KNPU/gAmylase: the trade mark of being sold by Novo Industries A/S is

The amylase of Termamyl 60T, the active 300KNU/gCellulase of being: the activity of being sold by Novo Industries A/S is 1000

The cellulase Lipase of CEVU/g: the trade mark of being sold by Novo Industries A/S is

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

Isomer PVNO: comprise vinyl imidazole (imidaxol) and vinyl pyrrolidone

Poly-(4-vinylpridine)-N-oxide copolymer

Thing, molecular-weight average is 10,000Granular Suds: 12% polysiloxane/silicon-dioxide, 18% Stearyl alcohol, Suppressor 70% starch, it is particulate state Nonionic: have average degree of ethoxylation and be 3.8 and average propoxylation degree

Be 4.5 C ₁₃-C ₁₅Blended ethoxylated/propoxylated fat

Fat alcohol is that the trade mark of being sold by BASF GmbH is Plurafac

LF404 (low foaming).Metasilicate: Starso (SiO ₂: Na ₂The O ratio is 1.0) Phosphate: tripoly phosphate sodium STPP 480N: the random copolymers of 3: 7 vinylformic acid/methacrylic acids, average

Molecular weight is about 3,500.PBI: granular to postpone to discharge the lack of water mistake of hydrogen peroxide with die mould

Sodium Tetraborate monohydrate Cationic lactam: the trialkyl ammonium methylene radical C that has tosylate ₅-alkyl

The positively charged ion peroxyacid bleach precursor DETPMP of hexanolactam: diethylenetriamine five (methylene phosphonic acid), by Monsanto

Sell, trade mark is Dequest 2060Bismuth nitrate: Bismuth trinitrate salt

Paraffin: paraffin oil, the trade mark of being sold by Wintershall is Winog 70

BSA: starch (decomposition) enzyme, sell by Novo Industries A/S

Trade mark be LE17 (about 1% enzymic activity)

Sulphate: anhydrous sodium sulphate

PH:, record in 1% distilled water solution at 20 ℃.

Embodiment 1

Prepare following laundry detergent composition, represented numerical value is the percentage ratio that calculates by the weight of composition: composition A is a Comparative composition, and composition B to E is the present composition:

	??A	????B	????C	????D	????E
?45AS/25AS(3∶1)	??9.1	????9.1	????9.1	????9.1	????7.0
						?35AE3S	??2.3	????2.3	????2.3	????2.3	????2.0
?24E5	??4.5	????4.5	????4.5	????4.5	????6.0
						?TFAA	??2.0	????2.0	????2.0	????2.0	????-
?Zeolite??A	??13.2	????13.2	????13.2	????13.2	????15.0
						Na SKS-6/ citric acid (79: 21)	??15.6	????15.6	????15.6	????15.6	????13.0
?Carbonate	??7.6	????7.6	????7.6	????7.6	????8.0
						TAED (particle of snap-out release)	??6.3	????-	????-	????-	????-
TAED (particle of Shi Fanging at a slow speed)	??-	????5.0	????-	????2.3	????3.5
						Benzoyl Caprolactam (particle of Shi Fanging at a slow speed)	??-	????-	????5.0	????2.7	????-
Percarbonate (particle of snap-out release)	??22.5	????-	????-	????22.5	????-
						Percarbonate (particle of Shi Fanging at a slow speed)	??-	????22.5	????22.5	????-	????-

?PBl	????-	????-	????-	????-	????16.0
						?DETPMP	????0.5	????-	????-	????-	????0.3
EDDS (particle of snap-out release)	????-	????0.8	????0.3	????0.75	????-
						?Protease	????0.55	????1.27	????0.55	????1.27	????1.5
?Lipase	????0.15	????0.15	????0.15	????0.15	????0.2
						?Cellulase	????0.28	????0.28	????0.28	????0.28	????0.4
?Amylase	????0.27	????0.27	????0.27	????0.27	????0.4
						?Polycarboxylate	????5.1	????5.1	????5.1	????5.1	????4.0
?CMC	????0.4	????0.4	????0.4	????0.4	????0.4
						?PVNO	????0.03	????0.03	????0.03	????0.03	????-
?Granular?suds?suppressor	????1.5	????1.5	????1.5	????1.5	????1.5
						Minor component/miscellaneous to 100%

Below be product A to the resulting T50 numerical value of each product of D (showing) with stopwatch:

????T50	????A	????B	????C	????D
					Peroxy acid	????130	????190	????205	????240
????AVO	????95	????225	????230	????115
					Washing assistant (citric acid)	????90	????60	????60	????60
Heavy metal ion chelating agent (DETPMP or EDDS)	????150	????30	????30	????60

The preparation of the removal cloth specimen of simultaneous test test method-spot three white cotton sheets of heavy-dirty liquid-detergent pre-wash that do not contain abiotic SYNTHETIC OPTICAL WHITNER.Cut the test cloth specimen that many packet sizes are 6cm * 6cm from every, every group has six these test cloth specimens.Spot put on every group of cloth specimen rightly (for example coat).

In addition, also can use the cloth specimen of studying resulting pre-preparation by EMPA.

Stack up is said, uses following many group cloth specimens:

Enzymatic spot:

Grass;

The spot that can bleach:

EMPA blood;

EMPA blood, milk and ink;

The grease spot:

Dirty machine oil;

The footwear polishing material;

These many tissue substances cloth specimens in automatic washing machine through a cycles of washing.Estimate the greasiness removal of cloth specimen then by 4 Scheffe scales by panel of experts.Each group and the average result that compares as the paired combination of the prior art compositions A of common reference have been listed below.

More particularly, use Miele 698 WM automatic washing machines and select 40 ℃ short cycling programs.Use 12 ° of Geman hardness (Ca: Mg=3: 1) water.Use divides the 75g washing composition that sheds from be put in loading intermediary granulette diverting device.Piece of cloth sample in every type with 2.7kg slightly the cloth sheet of dirt (1 week of family expenses) ballast weight wash.Simultaneous test-removal spot

Use above decontamination stain test method, comparative composition B with as the prior art compositions A of reference for the effect of removing dissimilar spots.

The result who obtains is as follows:

The spot type	Decontamination stain effect (PSU)
		EMPA blood	????+1.8 *
????EMPA?BMI	????+0.6
		Grass	????+0.7
Dirty machine oil	????+0.6
		The footwear polishing material	????+0.7

^*Validity is under 95% confidence level.Embodiment 2

The wash up machine composition (umber by weight) that contains SYNTHETIC OPTICAL WHITNER below produced according to the present invention.

	?????A	?????B	?????C	????D	?????E	????F	????G
								?Citrate	????15.0	????15.0	????15.0	????15.0	????15.0	????15.0	????-
?480N	????6.0	????6.0	????6.0	????6.0	????6.0	????6.0	????-
								?Carbonate	????17.5	????17.5	????17.5	????17.5	????17.5	????17.5	????-
?Phosphate	????-	????-	????-	????-	????-	????-	????38.0
								Silicate (presses SiO 2Meter)	????8.0	????8.0	????8.0	????8.0	????8.0	????8.0	????14.0
Metasilicate (presses SiO 2Meter)	????1.2	????1.2	????1.2	????1.2	????1.2	????1.2	????2.5
								The particle that the PB1-slow release is put (AvO)	????1.2	????1.2	????1.5	????1.5	????1.5	????2.2	????1.2
TAED (particle that slow release is put)	????2.2	????2.2	????2.2	????3.5	????-	????2.2	????2.2
								?Cationic?lactam	????-	????-	????-	????-	????3.3	????-	????-
?Pareffin	????0.5	????0.5	????0.5	????0.5	????0.5	????0.5	????0.5
								?Bismuth?nitrate	????-	????0.2	????0.2	????0.2	????0.3	????0.4	????0.2
?Protease	????2.0	????2.0	????2.0	????2.0	????2.0	????2.0	????2.0
								?Amylase	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5	????-
?BSA	????-	????-	????-	????-	????-	????-	????1.5
								?DETPMP	????0.13	????0.13	????0.13	????0.13	????0.13	????0.13	????-
?HEDP	????1.0	????1.0	????1.0	????1.0	????1.0	????1.0	????-
								?Nonionic	????2.0	????2.0	????2.0	????2.0	????2.0	????2.0	????1.5
?Sulphate	????23.0	????22.8	????22.4	????22.7	????22.2	????21.5	????0.3
								Comprise the miscellaneous of moisture content to balance
PH (1% solution)	????10.7	????10.7	????10.7	????10.7	????10.7	????10.7	????11.0

Embodiment 3:

Carry out following representational beaker test method and contact the difference that will cause between the outward appearance of removing spot with heavy metal ion chelating agent with hydrogen peroxide bleaching solution continuously in order with the fabric of whether measuring with spot.

Cloth specimen is immersed in the strong tea solution preparation in advance by the cotton sample of dirt.Contain the magnesium of a large amount in the tea stain, and the basic thing that is considered to be difficult to from band dirt/spot is removed.

Each 1000ml beaker is added the solution of the EDDS that contains 0.5% (weight) concentration individually and is equivalent to the superoxol of 2%AvO.Every heavy metal species ion chelating agent and bleaching agent solution are cushioned and cause pH is 10.5, and this is the pH that generally runs into " in the wash environment " in clothes washing method.

Many groups are dipped into a kind of by the cloth specimen of dirt in advance or immerse in order in these two kinds of solution.Soak time in every kind of solution is 20 minutes.Use rare every kind of soak of NaOH solution rinsing then.

At length say, use following washing/immersion scheme:

Group	Scheme
????A	Only in liquid lime chloride, soak
		????B	Only in EDDS solution, soak
????C	Be immersed in the liquid lime chloride, be immersed in then in the EDDS solution
		????D	Be immersed in the EDDS solution, be immersed in the liquid lime chloride then

Use Macbeth to divide photo etching to measure yellow, white and a, b and l value, by relatively estimating the resulting decontamination stain of every kind of washing/immersion scheme result with clean calico sample.Below be the result who obtains

	By the cloth specimen of dirt	????A	????B	????C	????D
Yellow	????55.1	????35.7	????36.7	????29.4	????19.3
						White	????-141.2	????-92.1	????-94.1	????-75.0	????-50.1
????1	????-9.7	????-5.8	????-8.6	????-4.5	????-3.4
						????a	????3.5	????-.3	????2.3	????0.0	????-0.7
????b	????23.8	????16.1	????15.5	????13.4	????8.9

Yellow hanging down on the occasion of, a and b value needs.White is on the occasion of needing more greatly with 1 value.

The decontamination stain result who this shows cloth specimen D group is better than the resulting result of cloth specimen A-C.Therefore the fabric that has confirmed the band dirt sequentially contacts with the solution that contains heavy metal ion chelating agent with before the solution that contains SYNTHETIC OPTICAL WHITNER contacts, and can obtain the enhancing to the greasiness removal performance.

Embodiment 4

Following representative test method has confirmed to be had fast (promptly with containing when the cloth specimen of band spot, before the Betengent product washing of SYNTHETIC OPTICAL WHITNER uncontrollable speed release), used to contain the solution-treated of heavy metal ion chelating agent, but obtained significant removal performance bleach spot.

Cloth specimen is immersed in the strong tea solution preparation in advance by the cotton print of dirt.Contain the magnesium of a large amount in the tea stain, and the basic thing that is considered to be difficult to from band dirt/spot is removed.

Each 1000ml beaker is added into and is buffered to pH is 10.5 the EDDS solution that contains 0.005% (weight) concentration, and this pH is the pH that generally runs into " in the wash environment " in clothes washing method.

Many groups by the EDDS solution rinsing of the cloth specimen of dirt process, are used the Betengent product that contains SYNTHETIC OPTICAL WHITNER in advance then, wash with a whole set of clothes washing method.Be set 2 or 5 minutes during rinsing in EDDS solution.This clothes washing method is included in the main washing of in the Miele washing machine under the softening water condition of using 40 ℃.The Betengent product that uses in this washing methods has the SYNTHETIC OPTICAL WHITNER of snap-out release and has the composition of embodiment 1 prescription A.

Done with reference to estimating in advance by the cloth specimen of dirt before washing, by the cloth specimen of dirt in advance with many groups that only handle through a whole set of clothes washing method with the pre-rinsing effect of heavy metal ion chelating agent solution.

Use the 4-point Scheffe scale of known application evaluation (panel) unit of keeping the score (PSU), but the % value that the range estimation evaluation is removed spot to the removal and the calculating of use Macbeth spectrometer of bleach spot.

Below be resulting result:

Rinsing/washing scheme	The % of greasiness removal	The washing of the relative only process of PSU (Scheffe)
Only through washing	????87	????-
			Rinsing is 2 minutes in EDDS solution, then washing	????92	????+3 *
Rinsing is 5 minutes in EDDS solution, then washing	????97	????+3 *

^*Validity is under 95% confidence level.

Cloth specimen contact with heavy metal ion chelating agent before with the Betengent product washing that contains SYNTHETIC OPTICAL WHITNER, can be observed tangible removal benefit to the spot that can bleach.

Embodiment 5:

Repeat washing/rinsing scheme of embodiment 3, difference is as follows:

1. 0.005%EDDS solution is contained the solution replacement of 0.005%EDDS and 0.05% Trisodium Citrate, and it also is buffered to pH is 10.5.

2. the rinsing time was set to 3 minutes.

3. use the cloth specimen (cotton) of using following spot dirt one by one:

(a) blood (EMPA)

(b) coffee

(c) red wine

(d) cocoa powder

(e) blood, milk and ink (EMPA)

Cloth specimen (a) and (e) obtain by EMPA tissue.Cloth specimen (b) to (d) is by obtaining on the 15cm that spot is coated in prewashing * 15cm white cotton sheet sample.

Use the testing program of this modification, estimate the cloth specimen of band spot and before washing, use the pre-rinsing effect of solution that contains heavy metal ion chelating agent/washing assistant, only pass through clothes washing method with the cloth specimen of identical this band dirt, not relatively through the result of any pre-rinsing step gained.

Use the Macbeth spectrophotometer to estimate the greasiness removal result, calculate decontamination stain % value.

Obtain following result:

Rinsing/washing scheme		% decontamination stain
		Blood	Coffee	Red wine	Cocoa powder	????BMI
Only through washing		????78	????76	????100	??36	????70
							Rinsing 3 minutes in EDDS/ washing assistant solution before washing		????100	????78	????100	??34	????78

This shows and use the rinse step in washing assistant/heavy metal ion chelating agent solution, the decontamination that can be enhanced stain performance when before washing step.

Claims (1)

1. a washing methods comprises the following steps:

(1) solution that will contain the no SYNTHETIC OPTICAL WHITNER of 0.005-1 weight % heavy metal ion chelating agent is supplied with the basic thing of being with dirt;

(2) the basic thing of this solution and said band dirt is kept in touch; With

(3) use the detergent composition that contains SYNTHETIC OPTICAL WHITNER to wash the basic thing of said band dirt then; Wherein, described heavy metal ion chelating agent is selected from quadrol-N, N '-disuccinic acid, quadrol-N, the salt of N '-disuccinic acid or their mixture.