CN1150453A

CN1150453A - Detergents containing builder and delayed release peroxyacid bleach source

Info

Publication number: CN1150453A
Application number: CN 95193546
Authority: CN
Inventors: B·斯托达特; J·杰弗里; J·S·帕克
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-04-13
Filing date: 1995-03-24
Publication date: 1997-05-21
Also published as: EP0755431A1; WO1995028465A1; JPH09512045A; EP0755431A4; GB9407532D0; CA2187304A1

Abstract

There is provided a detergent composition containing (a) a water-soluble builder; and (b) an organic peroxyacid bleach source, wherein a means is provided for delaying the release to a wash solution of said peroxyacid bleach relative to the release of said water-soluble builder. A pretreat wash method is also provided.

Description

The washing composition of the peroxyacid bleach source that contains washing assistant and postpone to discharge

The present invention relates to contain the detergent composition of water soluble detergency promoter and peroxyacid bleach source, the method for the release of said peroxyacid bleach in washing soln with respect to the hang-over n. of said washing assistant that make wherein is provided.

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 colour stability that is washed fabric.Can comprise fading or partial " irregular " bleached area of illuminating colour on the fabric for the influence of fabric color stability.

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 finds by the generation to any unwelcome influence of fabric color stability of using peroxyacid bleach to cause in washing methods relevant with the character of organic peroxide acid, and is also relevant with rate of release and the absolute magnitude of the peroxy acid that in washing soln exist of peroxyacid bleach in washing soln.

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 influence of 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 realize by a kind of negative effect of the stain that can bleach being removed ability.

But the applicant has now found that and uses the composition that contains water soluble detergency promoter and peroxyacid bleach source in the present invention, and, wherein provide to make the release of peroxyacid bleach in washing soln, can reach to strengthen and remove the stain effect that to bleach with respect to the method for the hang-over n. of water soluble detergency promoter.

In addition, in the laundry washing methods, use said composition, the problem of fabric color stability is reduced.

In addition, the applicant finds that the solution pre-treatment with containing water-soluble washing assistant can obtain the removal benefit to the stain that can bleach before the basic thing of band dirt is being used the washing methods washing of the Betengent product that contains SYNTHETIC OPTICAL WHITNER.

Therefore, but an object of the present 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 negative impact to fabric color stability shows lower tendency.

A relevant purpose of the present invention provides the stain pretreatment process, is included in before the Betengent product washing that contains SYNTHETIC OPTICAL WHITNER, with the basic thing of the solution pre-treatment band dirt that contains water-soluble washing assistant.Summary of the invention

According to the present invention, a kind of detergent composition is provided, it contains: (a) water soluble detergency promoter; (b) organic peroxide acid bleach source body, the method of the release of said peroxyacid bleach in washing soln with respect to the hang-over n. of said water soluble detergency promoter that make wherein is provided, so that in T50 test method described herein, the time that the concentration of said water soluble detergency promoter reaches its ultimate density 50% is lower than 120 seconds, and the concentration of said peroxyacid bleach reached the time of its ultimate density 50% greater than 180 seconds.

According to the present invention, a kind of detergent composition is provided, it contains: (a) water soluble detergency promoter; (b) organic peroxide acid bleach source body wherein provides the method for the release of said peroxyacid bleach in washing soln with respect to the hang-over n. of said water soluble detergency promoter that make, so that in T50 test method described herein, the concentration that the concentration of said water soluble detergency promoter reaches the said peroxy acid of time ratio of its ultimate density 50% reaches low at least 100 seconds required of the time of its ultimate density 50%, preferably at least 120 seconds, more preferably at least 150 seconds.

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

According to a further aspect in the invention, provide a kind of washing methods, the step that comprises is: the composition solution that (1) will contain the no SYNTHETIC OPTICAL WHITNER of water soluble detergency promoter is supplied with the basic thing of band dirt; (2) make the basic thing of said solution and said band dirt keep in touch the effective timed interval; (3) with comprising that the washing methods that uses the detergent composition that contains SYNTHETIC OPTICAL WHITNER washs the basic thing of said band dirt.The water soluble detergency promoter compound

Detergent composition of the present invention contains the water solvent washing-aid compound of promising main ingredient, and generally its content is the 1%-80% (weight) of composition, preferred 2%-60% (weight), most preferably 2%-40% (weight).

Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or their sour form, the poly carboxylic acid of homopolymerization or copolymerization or their salt.Wherein poly carboxylic acid comprises at least two carboxyls, carbonate, supercarbonate, borate, phosphoric acid salt, silicate and the aforementioned mixture arbitrarily that is separated from each other by no more than 2 carbon atoms.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomeric or the oligomerization type, but because Time, Cost And Performance, monomeric multi-carboxylate 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 ether derivant.The multi-carboxylate of containing 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 multi-carboxylate of containing three carboxyls comprises, especially water miscible Citrate trianion, aconitate and citraconate and succinate derivative, as in English Patent 1,379, the carboxyl methoxy succinate of describing in 241, in English Patent 1,389, newborn oxygen base (lactoxy) succinate of describing in 732 and the aminosuccinic acid salt of in Holland's application 7205873, describing, with oxo multi-carboxylate material, as 2-oxa--1,1,3-tricarballylic acid salt, it is described in English Patent 1,387, in 447.

The multi-carboxylate of containing four carboxyls comprises oxygen di-succinate, and it is disclosed in English Patent 1,261, in 829, and 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,33-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and be included in English Patent 1,398, disclosed sulfo-succinic acid salt derivative and in English Patent 1,439 in 421 and 1,398,422 and U.S.3,936,448, the sulfonated pyrolytic Citrate trianion of describing in 000.

Alicyclic ring and heterocycle multi-carboxylate comprise pentane-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.Aromatic multi-carboxy acid's salt comprises mellitic acid, 1,2,4, disclosed phthalic acid derivative in 5-pyromellitic acid and the English Patent 1,425,343.

In above-mentioned multi-carboxylate, 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 multi-carboxylate's sequestrant of monomeric 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 disclosed yellow soda ash and concentrated crystal soda and its mixture and calcium carbonate superfine powder in the disclosed German patent application 2,321,001 on November 15th, 1973.

The specific examples of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, poly-partially/sodium phosphate, wherein the polymerization degree is 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.The bleaching type

Detergent composition of the present invention contains the organic peroxide acid bleach source body as main ingredient.This peroxyacid bleach source can be organic peroxide acid itself, maybe can be the peroxyacid bleach precursor compound.

When the peroxyacid bleach source body was the peroxyacid bleach precursor compound, peroxy acid produced by this precursor and hydrogen peroxide cource body situ reaction, and suitable hydrogen peroxide cource body comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.Peroxyacid bleach precursor

Peroxyacid bleach precursor (bleach-activating agent) is preferred peroxide acid source body of the present invention.The common incorporation of peroxyacid bleach precursor is the 1%-20% (weight) of said composition, more preferably 2%-5% (weight), most preferably 3%-10% (weight).

Suitable peroxyacid bleach precursor generally contains one or more N-or O-carboxyl groups, and this precursor can be selected from broad variety, and suitable type comprises the acyl derivative of acid anhydride, ester, imide 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 acylate of sorbyl alcohol, glucose and all carbohydrates and benzozlating agent and acetylizing agent also suits.

Concrete O-acylations precursor compound comprises 2; 3; 3-trimethyl acetyl oxygen base benzene sulfonate, benzoyloxy benzene sulfonate, nonanoyl-6-amino-hexylyloxy benzene sulfonate, the tetra-acetylated glucose benzoyl peroxide of a benzoyl and any above-mentioned cationic derivative, it comprises alkylammonium derivative and penta-acetyl glucose.Tetra hydro Phthalic anhydride is the acid anhydride type precursor that suits.

The concrete cationic derivative of O-acyl group precursor compound comprises the alkylammonium derivative of 2-(N, N, N-trimethyl ammonium) ethyl 4-sulfo group phenyl-carbonic acid na chloride and benzoyloxy benzene sulfonate, comprises 4-(trimethyl ammonium) methyl-derivatives.

Useful N-acyl compounds be disclosed in GB-A-855735,907356 and GB-A-1246338 in.

The preferred precursor compound of imide type comprises urea and the N that N-benzoyl succinimide, four benzoyl quadrols, N-benzoyl replace, N, N ¹, N ¹, 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.

The precursor compound of the N-acidylate of lactams is disclosed among the GB-A-955735 by generality.The wideest content of the present invention comprises uses useful arbitrarily lactan as peroxyacid precursor, and preferred material comprises hexanolactam and Valerolactim.

The lactan precursor of suitable N-acidylate has formula:

Wherein n is 0 to about 8, and is preferred 0 to 2, R ⁶For H, contain alkyl, aryl, alkoxy aryl or the alkaryl of 1 to 12 carbon atom, or contain the phenyl of the replacement of 6 to 18 carbon atoms.

Suitable caprolactam bleach agent precursor has formula:

R wherein ¹Be H or contain 1 to 12 carbon atom, alkyl, aryl, alkoxy aryl or the alkaryl of preferred 6 to 12 carbon atoms, most preferably R ¹Be phenyl.

Suitable Valerolactim has formula:

R wherein ¹Be H or contain 1 to 12 carbon atom, alkyl, aryl, alkoxy aryl or the alkaryl of preferred 6 to 12 carbon atoms.In highly preferred embodiment, R ¹Be selected from phenyl, heptyl, octyl group, nonyl, 2,4,4-tri-methyl-amyl, decyl and its mixture.

Most preferred material is to be generally those materials of solid under＜30 ℃; phenyl derivatives particularly; be the benzoyl analogue of benzoyl Valerolactim, benzoyl caprolactam and their replacements, as chlorine, aminoalkyl group, alkyl, aryl and alkoxy derivative.

R wherein ¹Part contains at least 6, and the hexanolactam of preferred 6 to 12 carbon atoms and Valerolactim precursor substance provide through hydrolysis has hydrophobic peroxy acid, and it can nucleophilic and removing oil body dirt.R wherein ¹The precursor compound that contains 1 to 6 carbon atom provides the wetting ability albic material, and it is effective especially for bleaching beverage dirt.General weight ratio is 1: 5 to 5: 1, and the mixture of the mixture of preferred 1: 1 " hydrophobic " and " hydrophilic " hexanolactam and " hydrophobic " and " hydrophilic " Valerolactim can be used for this paper and remove blended spot benefit to provide.

Hexanolactam very preferably and Valerolactim precursor comprise benzoyl caprolactam; the nonanoyl hexanolactam; the benzoyl Valerolactim; the nonanoyl Valerolactim; 3; 5; 5-trimethyl acetyl base hexanolactam; 3; 5,5-trimethyl acetyl base Valerolactim; the capryloyl hexanolactam; the capryloyl Valerolactim; the decanoyl hexanolactam; the decanoyl Valerolactim; the undecylene acyl caprolactam; undecylene acyl group Valerolactim; (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate; (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate; (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and its mixture.The example of the benzoyl lactan of replacement very preferably comprises the methyl benzoyl hexanolactam; the methyl benzoyl Valerolactim; ethylamino benzonitrile acyl group hexanolactam; ethylamino benzonitrile acyl group Valerolactim; the propyl group benzoyl caprolactam; propylbenzene formyl radical Valerolactim; the sec.-propyl benzoyl caprolactam; isopropyl benzene formyl radical Valerolactim; the butyl benzoyl caprolactam; butylbenzene formyl radical Valerolactim; tertiary butyl benzoyl caprolactam; tert.-butylbenzene formyl radical Valerolactim; the amyl group benzoyl caprolactam; amylbenzene formyl radical Valerolactim; the hexyl benzoyl caprolactam; hexyl benzene formyl radical Valerolactim; the ethoxy benzonitrile acyl caprolactam; phenetole formyl radical Valerolactim; the propoxy-benzoyl caprolactam; propoxy-benzoyl Valerolactim; isopropoxy benzoyl hexanolactam; isopropoxy benzoyl Valerolactim; the butoxy benzoyl caprolactam; butyl phenyl ether formyl radical Valerolactim; the tert.-butoxy benzoyl caprolactam; tert.-butoxy benzoyl Valerolactim; the pentyloxy benzoyl caprolactam; amyl phenyl ether formyl radical Valerolactim; the hexyloxy benzoyl caprolactam; hexyloxy benzoyl Valerolactim; 2; 4; 6-trichlorine benzoyl caprolactam; 2; 4; 6-trichlorobenzene formyl radical Valerolactim; penta fluoro benzene formyl radical hexanolactam; penta fluoro benzene formyl radical Valerolactim; dichloro-benzoyl base hexanolactam; dimethoxy benzoyl hexanolactam; 4-chlorobenzene formacyl hexanolactam; 2; 4-dichloro-benzoyl base hexanolactam; the terephthaloyl dicaprolactam; penta fluoro benzene formyl radical hexanolactam; penta fluoro benzene formyl radical Valerolactim; dichloro-benzoyl base Valerolactim; dimethoxy benzoyl Valerolactim; 4-chlorobenzene formacyl Valerolactim; 2,4 dichloro benzene formyl radical Valerolactim; terephthaloyl two Valerolactims; 4-nitro benzoyl hexanolactam; 4-nitro benzoyl Valerolactim and its mixture.

Suitable imidazoles comprises that the useful peroxyacid precursor that contains the N-acyl group of N-benzoyl imidazoles and N-benzoyl benzoglyoxaline and other comprises N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

The compound that the acid amides that another kind of preferred peroxy acid bleach immunomodulator compounds is following general formula replaces:

Or

R wherein ¹Be 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, L can be necessary any leavings group.R ¹Preferably contain 6-12 carbon atom.R ²Preferably contain 4-8 carbon atom.R ¹Can be the aryl of straight or branched alkyl, replacement or contain side chain, substituting group or alkaryl that the two all has, and can derive from synthetics or natural goods, comprise for example animal tallow.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 L group must have enough reactivities for the reaction that takes place in the Best Times scope (for example cycles of washing).Yet if the L reactivity is too strong, this activator is difficult to the stable bleaching composition that is used for.These features generally are corresponding with the pKa of the conjugate acid of leavings group, but also are known for the exception of this rule.The leavings group that generally has these behaviors is that those their conjugate acids have pKa at about 4-13, preferably about 6-11, the most preferably from about group of 8-11.

Preferred bleach precursor is those wherein R ¹, R ²And R ⁵Be selected from as defined precursor and L in the compound of acid amides replacement:

With its mixture, wherein R ¹Be alkyl, aryl or the alkaryl that contains 1 to 14 carbon atom, R ³Be the alkyl chain that contains 1 to 8 carbon atom, R ⁴Be H or R ³, Y is H or solubilizing group.

Preferred solubilizing group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ₃) ₄X ^-And O＜-N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be the alkyl chain that contains 1-4 carbon atom, M provides deliquescent positively charged ion to bleach-activating agent, and X provides deliquescent positively charged ion to bleach-activating agent.M is basic metal, ammonium or replacement ammonium cation preferably, and sodium and potassium are most preferred, and X is halogenide, oxyhydroxide, Methylsulfate or acetate negatively charged ion.It should be noted that the bleach-activating agent that has the leavings group that does not contain solubilizing group should be scattered in the liquid lime chloride dissolving to help them well.

The example of the preferred bleach-activating agent of following formula comprises (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and its mixture.

Other preferred precursor compound comprises those precursor compounds of benzoxazine type, and it has formula:

The precursor compound that comprises the benzoxazine type of replacement:

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

Particularly preferred benzoxazine type precursor is: Organic peroxide acid

This detergent composition also can contain the 1%-15% that is generally composition weight, more preferably the 1%-10% organic peroxide acid.

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

R wherein ¹Be 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 aryl of straight or branched alkyl, replacement or contain side chain, substituting group or alkaryl that the two all has, and can derive from synthetics or natural goods, comprise for example animal tallow.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 that for example disclosed diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid, list and two are crossed nonane diacid in EP-A-0341947, list and two is crossed brassylic acid, single peroxide phthalic acid, peroxybenzoic acid and their salt.Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

The present composition preferably includes the inorganic perhydrate salt as the hydrogen peroxide cource body, especially when organic peroxy acid source body is the peroxyacid bleach precursor compound.

Inorganic perhydrate salt normally mixes with the form of sodium salt, and its amount is the 1%-40% of composition weight, more preferably 2%-30%, most preferably 5%-25%.

The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.This inorganic perhydrate 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 composition 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 ₂.3H ₂The tetrahydrate form of O.

SPC-D, it is a preferred perhydrate included in the detergent composition of the present invention, is to have corresponding to 2Na ₂CO ₃.3H ₂O ₂The addition compound of formula, commercial what buy is crystalline solid.SPC-D is most preferably mixed in this based composition so that its stability in product to be provided with the form that coats.

In product, provide stable suitable coating material to comprise the mixing salt of water-soluble alkali vitriol and carbonate.Yet this coating material makes percarbonic acid SYNTHETIC OPTICAL WHITNER snap-out release in washing soln, therefore discharges for the delay that provides percarbonate bleach in washing soln, and coating is not the method that suits.Coating material and method for coating have been 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 in 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, and it has general formula: NaSO ₄.n.Na 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.

Crossing a Potassium Persulphate is another kind of inorganic perhydrate salt useful in the detergent composition of the present invention.Bleaching catalyst

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

This bleaching catalyst is used for the compositions and methods of the invention with catalytically effective amount." 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.Thereby 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.Therefore, 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 warm water or even cold water.Certainly, 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 mmole Mn 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, bleach precursor and Mn catalyst and boratory use under lower perborate consumption condition, are compared with the product that does not have the manganese salt catalyst, 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 said bleach catalyst, wherein the example of heavy metal cation is copper, iron or manganese positively charged ion, has few or do not have the active assistant metal positively charged ion of bleach catalyst such as zinc or aluminium cations, with the stability constant of definition 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 the title complex of manganese 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 european patent application and discloses in 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.

Also can be chosen in bleach catalysts useful in the present composition and be used for the present invention.The example of suitable bleach catalysts is referring to U.S.4, and 246,612 and U.S.5,227,084.

Also referring to U.S.5,194,416, it discloses monokaryon manganese (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 manganese (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 the title complex bleaching catalyst of the ligand that comprises transition metal and non-(greatly) ring.Said ligand has formula:

R wherein ¹, R ², R ³And R ⁴Be selected from the alkyl and the aryl of H, replacement respectively, so that R ¹-N=C-R ²And R ³-C=N-R ⁴Each self-forming five or six-ring.This ring can further be substituted.B is an abutment, and it is selected from O, S, CR ⁵R ⁶, NR ⁷And C=0, wherein R ⁵, R ⁶And R ⁷Be respectively H, alkyl or aryl, it comprises group replacement or unsubstituted.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 '-two pyridine amine ligands.Preferred bleaching catalyst comprises Co, Cu, the two pyridine methane of Mn, Fe-and two pyridine amine coordination thing.Catalyzer very preferably comprises Co (2,2 '-two pyridine amine) Cl ₂, the two pyridine amine-cobalts of two (isothiocyanatos) (II), three pairs of pyridine amine-cobalts (II) perchlorate, Co (2, the two pyridine amine of 2-) ₂O ₂ClO ₄, two (2,2 '-two pyridine amine) copper (II) perchlorate, three (two-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 ^IV(2,2 '-dipyridyl) ₂]-(ClO ₄) ₃

Bleaching catalyst 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 bleaching catalyst.The present invention can use the water-soluble salt easily arbitrarily of manganese.Manganese (II), (III), (IV) and/or (V) on technical scale, be easy to obtain.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 the mol ratio ligand: manganese salt 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 (if needs, at N ₂Down), 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 suitable ligand of using than the big excessive mole number of 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 european patent application and discloses in 549,271.

The structure of the manganese coordination thing of catalytically bleaching of the present invention is illustrated, can infer the coordination compound that it comprises inner complex or other hydration, and they are to be interacted by the carboxyl of ligand and nitrogen-atoms and manganese positively charged ion to produce.In addition, the cationic, oxidized attitude of manganese is not known definite 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, to have multinuclear material and/or " cage " shape structure.The active manganese ligand material of what structure 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 bleaching catalyst for example is described in, and european patent application discloses 408,131 (cobalt complex catalyzer), european patent application discloses 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 catalysts that are adsorbed on silico-aluminate) are disclosed, U.S.4,601,845 (being loaded with the silico-aluminate of manganese and zinc or magnesium salts), 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).Relative release dynamics

A main aspect of the present invention provides the method for the release of peroxyacid bleach in washing soln with respect to the hang-over n. of water soluble detergency promoter.

Said method can comprise the method that the delay peroxyacid bleach discharges in washing soln.

Said in addition method can comprise the method that increases the rate of release of water soluble detergency promoter in solution.Postpone the rate of release method

This method can provide peroxyacid bleach source itself to postpone to discharge in washing soln.In addition, when peroxide acid source body was the peroxyacid precursor compound, the method that this delay discharges can comprise the method for crossing hydrolysis reaction on the spot that suppresses or stop release peroxy 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 component that provides the coating material that postpones to discharge to coat any suitable with appointed can be provided the method that postpones to discharge.This coating material can comprise as the material of poorly water-soluble 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 coating material is arbitrarily: 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, soybean 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, its 2%-10% that should be provided as percarbonate weight that provides as the aqueous solution (normally 3%-5%) silicate solid.Coating material also can comprise Magnesium Silicate q-agent.

The 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 arbitrarily.Suitable tackiness agent comprises C ₁₀-C ₂₀Alcohol ethoxylate, its every mol of alcohol contains 5-100 moles of ethylene oxide, more preferably C 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, 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 two glyceryl ethers also have C ₁₀-C ₂₀Lipid acid.

Derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose 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 conventional can use, and it 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 to change the physical property of 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 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, preferably has average particulate diameter and be 800 to 1200 microns particle.

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

All proper method of the speed that the increase water soluble detergency promoter discharges in solution all are conceived to.

The coating material coating any suitable component that provides enhancing to discharge with selected can be provided the method that strengthens release.Therefore, 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 water soluble detergency promoter to strengthen its solvability and rate of release.

Suitable scheme can comprise that careful selection contains the granularity of any component of water soluble detergency promoter.To depend on the composition of grain fraction and need satisfy the kinetics that required enhancing discharges the selection of granularity.It is desirable to granularity and should be lower than 1200 microns, preferably have average particulate diameter and be 1100 to 500 microns particle.

Provide the other scheme that postpones method for releasing to comprise suitable selection to any other component in the detergent composition matrix, or to containing the suitable selection of any grain fraction of water soluble detergency promoter, 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.Postpone the release dynamics parameter

The release that derives from the peroxyacid bleach component of peroxyacid bleach source is such with respect to the release of water soluble detergency promoter component: in this article in the T50 test method of Miao Shuing, the concentration of said water soluble detergency promoter reaches its ultimate density 50% required time and is lower than 120 seconds, preferably be lower than 90 seconds, more preferably be lower than 60 seconds, the concentration of said peroxyacid bleach reached its ultimate density 50% required time greater than 180 seconds, preferred 180-480 second, more preferably 240-360 second.

The present invention very preferably aspect in, the release of SYNTHETIC OPTICAL WHITNER is such: in T50 test method described herein, the total amount that can get oxygen (AVO) reached 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 water soluble detergency promoter component discharges: in T50 test method described herein, the concentration of said water soluble detergency promoter reaches its ultimate density 50% required time and is lower than 120 seconds, preferably be lower than 90 seconds, more preferably be lower than 60 seconds, said concentration of hydrogen peroxide reached its ultimate density 50% required time greater than 180 seconds, preferred 180 to 480 seconds, more preferably 240 to 360 seconds.

The final wash concentration of water soluble detergency promoter is generally 0.0005%-0.4%, preferred 0.005%-0.35%, more preferably 0.01-0.3%.

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 peroxyacid precursor is generally 0.001% to 0.08% (weight) arbitrarily, 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.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 accurately be determined at add composition in the water in the beaker after, related component in solution at random and ultimate density.

This analytical procedure can comprise those methods of monitoring the component concentrations amount continuously, comprises for example flash ranging and three degree conduction (conductrimetric) methods.

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, stop its dissolution process as temperature, use the tested component concentrations in any means such as the chemical titration resultant then by quick reduction titration resultant.

Can use suitable method of drawing, comprise curve fitting method, this suitable method can be calculated the TA value by the original 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.The detergent component that adds

Detergent composition of the present invention also can contain the detergent component of interpolation.These accurate feature and its incorporations that add component will depend on the physical form of composition and the character of its washing operation that is used for.

The present composition can 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 the detergent component of one or more interpolations, and it is selected from enzyme, suds suppressor, lime soap dispersing agent, dirt suspension and the anti redeposition agent and the corrosion inhibitor of tensio-active agent, water-insoluble washing assistant, heavy metal ion inner complex, organic polymer, interpolation.Laundry composition also can contain the softening agent as the detergent component that adds.Tensio-active agent

Detergent composition of the present invention can contain as the tensio-active agent that adds detergent component, 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).

Any enzyme component that exists in the tensio-active agent of preferred preparation and the composition is compatible.In liquid or gelatinous composition, most preferably Pei Zhi tensio-active agent can promote or these compositions of not degrading at least in any stability of enzyme.

The species generality 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 " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch show).Suitable cats product be disclosed in the U.S.P.4 that authorized Murphy on March 31st, 1981 for example, in 259,217.

When having 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 (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.Resinous acid and hydrogenated resin acid also suit, as rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in the animal oil or are obtained by animal oil.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 thiazolinyl glycerine 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) vitriol of glucosamine sulfate and alkyl polysaccharide, for example vitriol of alkyl polyglycoside (this paper has also described the compound of non-ionic non-sulfuric acidization).

Alkyl ethoxy sulfate surfactant is preferably selected from C ₆-C ₁₈Alkyl-sulphate, its every mole by about 0.5 to about 20 moles of ethylene oxide ethoxylations.More preferably alkyl ethoxy sulfate surfactant is C ₆-C ₁₈Alkyl-sulphate, its every mole 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 ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil thiazolinyl glycerol sulfonate and its any mixture.The anionic carboxylic acid salt surfactant

Be suitable for anionic carboxylate tensio-active agent of the present invention and comprise alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (" alkyl carboxyl "), secondary soaps especially described herein.

Be preferred for alkyl ethoxy carboxylate of the present invention and comprise having formula RO (CH ₂CH ₂O) _xCH ₂COO ^-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 is lower than about 20%; X is lower than about 25% greater than 7 amount of substance, when mean value R is C ₁₃Or when lower, mean value x is about 2 to 4; When mean value R greater than C ₁₃The time, mean value 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 multi-carboxylate 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, methyl acidic group, 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 structure further illustrates the secondary soap of some preferred secondary soap surfactant: A. class very preferably and 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. another kind of preferred secondary soap comprises carboxyl substituent those carboxylic compounds on the cyclic hydrocarbon radical unit, i.e. formula R ⁵-R ⁶-CO0M secondary soap, 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 each R is C ₁-C ₄Alkyl, k, n, o, q are the integers 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 an any suitable, especially water solubilising counterion.

Be used for the water-soluble salt that particularly preferred secondary soap surfactant of the present invention is selected from following acid: 2-methyl isophthalic acid-ten-alkanoic 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 surfactant

Other suitable anion surfactant is formula R-CON (R ') 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 oleyl methyl Sodium sarcosinate.Nonionogenic tenside

Any nonionogenic tenside useful substantially to the decontamination purpose all can be included in the composition.The typical case of useful nonionogenic tenside, unrestricted type have below been listed.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 oxygen baseization) derivative.Z preferably reducing sugar from reductive amination process obtains; More preferably Z is a glycosyl.The nonionic alkylphenol condensation

The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are 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 oxyalkylene.The nonionic ethoxylated alcohol tensio-active agent

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, and generally contain 6 to 22 carbon atoms.Particularly preferably be and have every mol of alcohol and about 2 the condensation products that contain 8 to 20 carbon atom alkyls to about 10 moles of ethylene oxide.The nonionic ethoxylated/propoxylated fatty alcohol surfactant

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.The condenses of nonionic EO/PO and 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.The condensation product of nonionic EO and propylene oxide/ethylenediamine adduct

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 class nonionogenic tenside

Be applicable to that alkyl polysaccharide class 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 group 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 polyose hydrophilic group of about 2.7 saccharidess, for example many 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.(at 2-, 3-, positions such as 4-have obtained glucose or semi-lactosi with respect to glucoside or galactoside to hydrophobic group like this by attack randomly).Key between the saccharides can be positioned at the 2-on a kind of position and formerly the saccharides unit on the saccharides unit of interpolation, between the 3-, 4-and/or 6.

Preferred alkyl polyglycoside 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 nonionic fatty acid amide surfactant

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.Both sexes (amphoteric) tensio-active agent

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 both sexes dicarboxylic acid of the present invention is by Miranol, Inc., Dayton, Miranol (TM) the C2M Conc that NJ produces.Amine oxide surfactant

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 polyoxyethylene group of preferred 1 ethylene oxide group.R ⁵Group can be connected to each other, and for example forms ring structure by oxygen or nitrogen-atoms.

These amine oxide surfactants especially comprise C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₈Alkoxyethyl dihydroxy ethyl amine oxide.This class examples of substances comprises dimethyl octyl group 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 dimethyl amine oxide compound, butter dimethyl amine 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 phosphonium 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 Oleum Cocois 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]-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 _12-18Own ammonium salt of Dimethyl Ammonium 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.The 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.Both sexes (ampholytic) tensio-active agent

Amphoterics can be impregnated 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 for 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 the insoluble detergent compound that helps, 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 NaSKS-6.

The crystalline layered sodium silicate material is preferably as being present in the granular 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) ₂(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 material is a hydrated form, crystallized form preferably, and it contains 10%-28%, more preferably the combination water of 18%-22%.

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, X zeolite, 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.X zeolite has formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] .276H ₂O.Heavy metal ion chelating agent

Detergent composition of the present invention can contain the heavy metal ion chelating agent as the preferred optional component.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 iron sequestering power, but preferably they to showing selectivity in conjunction with heavy metal ion such as iron, manganese 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 they sour form or as with the form of the title complex/salt of suitable counter cation such as basic metal or alkaline-earth metal ions, ammonium or the ammonium that replaces or its any mixture.Preferred salt/title complex arbitrarily 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), basic metal ethane-1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt of amino alkylidenyl.

Preferably diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene radical phosphoric acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1,1 diphosphate 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 magnesium salts or its 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.

Other the heavy metal ion chelating agent that is applicable to this paper is an iminodiacetic acid derivatives, such as at EP-A-317, and 2-hydroxyethyl oxalic acid or the glycerine thiazolinyl iminodiethanoic acid described in 542 and EP-A-399,133.

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 have described the sequestrant of suitable 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, the 4-tricarboxylic acid also suits.G-NH2-N, N '-disuccinic acid (GADS) also suits.Enzyme

Other useful optional components is the enzyme of one or more interpolations in detergent composition.

The preferred enzyme material that adds comprises lipase, amylase, neutrality and Sumizyme MP, esterase, 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 buied 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 mix according in the composition of the present invention by the amount that is the 0.0001%-4% organized enzyme 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(brand)name of for example selling by Gist-Brocades be Rapidase those and be those of Termamyl and BAN by the trade(brand)name that Novo Industries A/S sells.Amylase can mix according in the composition of the present invention by the amount that is the 0.0001%-2% organized enzyme 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, commercially available by Novo Industri A/S, Bagsvaerd, (Denmark) buys, and trade(brand)name 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 that about 0.001%-is about 10%, and preferably about 0.005%-is about 8%, most preferably from about 0.01%-about 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), its be added into be for the chlorine bleach material damage enzyme that prevents from many water supply, to exist with 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 of ammonium cation or sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide 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 use other conventional scavenging agent such as hydrosulfate, nitrate, muriate, hydrogen peroxide cource body such as sodium perborate tetrahydrate, Sodium peroxoborate-hydrate and SPC-D if necessary, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc. and its mixture.Organic polymer

Organic polymer is the particularly preferred component of detergent composition of the present invention.The organic polymer meaning is meant 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 polymer 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% pair 10%.

The example of organic polymer comprises water miscible all organic or the poly carboxylic acid of copolymerization or their salt, and wherein poly carboxylic acid comprises at least two by no more than two carboxyls that carbon atom is 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 the multipolymer of the polyacrylate of molecular weight 2000-5000 and they and maleic anhydride, and the molecular weight of this multipolymer is 20,000 to 100,000, especially 40,000 to 80,000.

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

The polyamino compound 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.

Other organic polymer 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 polymer 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 be prevent lipid acid basic metal, ammonium or amine salt by calcium or the sedimentary class material of 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 by H.C.Borghetty and C.A.Bergman, the article of being shown, U.S. oiling association will, 27 volumes, 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 method in following comment: W.N.Linfield, tensio-active agent science book series, 7 volumes, p3; W.N.Linfield, tensio-active agent detects, 27 volumes, p159-161 (1990); And M.K.Nagarajan, W.F.Masler, makeup and toiletry, 104 volumes, p71-73, (1989).Need to disperse by the 0.025g sodium oleate at 30ml333ppm CaCO ₃(Ca: Mg=3: 2) weight of the sedimental dispersion agent of calcium soap that forms in the water of equivalent hardness and sodium oleate weight percent are LSDP.

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 LSDP 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 LutensolAO12 and Lutensol AO30 by the trade(brand)name that BASF GmbH sells.

Be applicable to that polymerization lime soap dispersing agent of the present invention is described in the article of being shown by M.K.Nagarajan and W.F.Masler, makeup and toiletry, 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 based mixtures 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 of the present invention was used for the use in washing machine composition by preparation, 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 known anti-alveolation compound arbitrarily substantially, comprises for example anti-alveolation compound of siloxanes, 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 the present invention uses 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 monoester fat carboxylic acid and its water-soluble salt.These materials are described in to be authorized in the United States Patent (USP) 2,954,347 of WayneSt.John September 27 nineteen sixty.Monobasic aliphatic carboxylic 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 products that cyanuric chloride and 2 or 3 moles contain the uncle of 1 to 24 carbon atom or secondary amine, propylene oxide, two stearic amides and single stearyl di(2-ethylhexyl)phosphate basic metal (for example sodium, potassium, lithium) salt and single stearyl phosphoric acid ester.

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 ₆-C ₁₆Alkyl chain constitutes, this alkyl chain on certain position 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, and 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% 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 comb-type copolymers, 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 comb-type copolymers is DCO544, can be buied by DOWCorning commercial, trade(brand)name 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;

The useful preferred granular suds suppressing agent system of this paper comprises the alkylation polysiloxane of the above open type of this paper and the mixture of solid silica.

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 nanometer to 20 nanometers, and specific surface area is at 50m ²More than/the g, be and have the intimate mixture that molecular weight is about dimethylpolysiloxanefluids fluids of 500 to 200,000 that wherein the weight ratio of the silicon-dioxide of dimethyl polysiloxane and silanization is about 1: 1 to about 1: 2.

Granular suds suppressing system very preferably 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 glycerine and has the monoesters of 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 granular suds suppressing system very preferably 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 granular suds suppressing system very preferably, 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 vector material in two kinds of particle foam control agents very preferably 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%, preferred 8%-15% (weight) polysiloxane compound component preferably includes the 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 the binder compound of said agglomerate 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 the R-N-O group is the part of this polymerizable unit, or the two combination.

R is aliphatic group, ethoxylation aliphatic group, aromatic group, heterocycle or alicyclic radical or its arbitrary combination, and the nitrogen in the N-O group can be attached on the R or the nitrogen in the N-O group is the part of these groups.

The N-O group can be represented with following formula: R wherein ₁, R ₂And R ₃Be aliphatic group, aromatic group, heterocycle or alicyclic radical or its mixing, x or/and y or/and z is 0 or 1, wherein the nitrogen in the N-O group can link thereon or the N-O group in nitrogen constitute the part of these groups.The N-O group can be the part of polymerizable unit (P) or be connected on the polymeric skeleton, 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 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 the nitrogen access node in the N-O group to the R group.

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 aromatics, heterocycle or alicyclic group, and wherein the nitrogen in the N-O functional group is connected in 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 polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the character that suppresses dye transfer.The example of suitable polymeric skeleton is polyvinyls, 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: 1000,000.Yet the amount of the amine oxide group in the polyoxygenated amine polymer can change according to suitable co-polymerization or suitable N-oxidisability.The ratio of preferred amines and amine n-oxide is 2: 3 to 1: 1000000, more preferably 1: 4 to 1: 1000000, and 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 strict, as long as this material has water-soluble and the 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 50,000 to this polymkeric substance, 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 is 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 is PVP K-15 (viscosity molecular weight is 10,000), PVP K-30 (molecular-weight average is 40,000), (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 SokalanHP165 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 the polyvinyl oxazolidone 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 oxazolidinone that discharges in washing soln is generally 0.5ppm to 250ppm, preferred 2.5ppm to 150ppm, more preferably 5ppm to 100ppm.E) polyvinyl imidazol

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

The amount of the polyvinyl imidazol 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 imidazol 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 hydrophilic 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, 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(brand)name 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, and 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 '-stilbene disulfonic acid disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade(brand)name is Tinopal 5BM-GX.

When in following formula, R ₁Be anilino, R ₂Be morpholino, 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 '-stilbene disulfonic acid sodium salt.This concrete whitening agent is sold by Ciba GeigyCorporation commercial, and trade(brand)name 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; Because they have high affinity to the fabric in the washing soln, therefore be deposited on relatively apace on these fabrics.Whitening agent is deposited on the degree on the fabric in the washing soln and is defined with the parameter that is called " exhausting coefficient ".This exhaust 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 exhausts coefficient and in this class technology contents of the present invention, be suitable for suppressing dye transfer most.

Certainly, can be appreciated 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 do 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 components

Suitable other optional components that is included in the present composition comprises spices, pigment and filling salt, and sodium sulfate is preferred filling salt.The form of composition

Detergent composition of the present invention can be mixed with form such as powder, particle, cream, liquid, tablet and the gel of any suitable.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 tap 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 650gg/l to 1200g/l.

Tap density is that common funnel and cup device are measured, constituting of this device: by the conical hopper of firm mold pressing on a pedestal and the plate valve of installing 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.Higher respectively and be 130mm and 40mm at funnel 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.From this structure, shift out the cup that is full of,, therefrom remove excess powder than the upper edge by this glass with the apparatus such as the cutter on vertical edges edge.This cup that is full of of weighing then, the numerical value that obtains powder weight is doubled the tap density of representing with g/l just is provided.Carry out replication on demand.Preparation method-particulate composition

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

The present composition can be used for washing or purging method arbitrarily 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 that the wash up machine of the present invention that is used in dissolving in the aqueous solution or has decomposed significant quantity handles the article of being with dirt with the aqueous solution of composition, and 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 composition meaning, 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 detergent composition of the significant quantity meaning 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 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 the high local concentrations product.

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 especially preferred decollator of the present invention and be described in following patent: GB-B-2,157,717, 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 generally known " particle " type products.

Especially preferred decollator is disclosed in european patent application and discloses 0343069 ﹠amp; In 0343070.The latter applies for disclosing a kind of decollator, and it comprises the resilient sleeve 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 middle wheel 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 is by the water soluble detergency promoter that contains of significant quantity, but the preprocessing solution that does not contain bleaching components is handled.This solution can be chosen wantonly and contain other non-SYNTHETIC OPTICAL WHITNER detergent component, as tensio-active agent, washing assistant, heavy metal ion chelating agent, enzyme and washing composition polymkeric substance.

The content of the water soluble detergency promoter in this preprocessing solution is generally 0.05%-80%, is preferably greater than 1%.

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 Betengent product 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 to give a definition:

XYAS:C _1X-C _1YSodium alkyl sulfate

25EY: with the C of average Y moles of ethylene oxide condensation ₁₂-C ₁₅Mainly

Be the primary alconol XYEZ of straight chain: with the C of average Z moles of ethylene oxide condensation _1X-C _1YMainly

Be the primary alconol XYEZS of straight chain: with the C of average per molecule Z moles of ethylene oxide condensation _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: the anhydrous sodium carbonate multi-carboxylate: 1: 4 toxilic acid/acrylic copolymer, molecular-weight average is for approximately

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

Na ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂O, main granularity exists

Citrate trianion between 1 to 10 micron: citrate trisodium dihydrate percarbonate: covered Na ₂SO ₄.n.Na ₂CO ₃Mixing salt empirical formula be (particle of snap-out release) 2Na ₂CO ₃.3H ₂The anhydrous SPC-D SYNTHETIC OPTICAL WHITNER of O, its

In n be 0.29, percarbonate and mixing salt part by weight be

39: 1 percarbonate: be coated with water glass (Si ₂O: Na ₂The O ratio is 2: 1) bag (particle of Shi Fanging at a slow speed) coating anhydrous SPC-D SYNTHETIC OPTICAL WHITNER, percarbonate and silicic acid

The weight ratio of sodium is 39: 1TAED tetraacetyl ethylene diamine TAED: with citric acid and molecular weight is the particle that 4000 polyoxyethylene glycol (PEG) (particle of Shi Fanging at a slow speed) agglomeration TAED forms, TAED: citric acid:

The weight ratio of PEG is 75: 10: 15, this particle outside

The citric acid coating layer is arranged, the weight of agglomerate and citric acid coating layer

Amount is than being 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 weight ratio of BzCl: citric acid: PEG is 63: 21: 16,

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

The weight ratio of coating layer is 95: 5TAED: with (particle of snap-out release) grain that part neutral multi-carboxylate agglomeration TAED forms, TAED and multi-carboxylate's ratio is 93: 7, should

There is multi-carboxylate's coating layer the 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: 74 proteolytic enzyme: the trade(brand)name of being sold by Novo Industries A/S is

The proteolytic enzyme of Savinase, activity are 13 KNPU/g amylase: the trade(brand)name of being sold by Novo Industries A/S is

The starch of Termamyl 60T, enzymic activity are the 300KNU/g cellulase: the activity of being sold by Novo Industries A/S is 1000

The cellulase lipase of CEVU/g: the trade(brand)name of being sold by Novo Industries A/S is

The lipolytic enzyme of Lipolase, activity is 165KLU/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 and vinylpyrrolidone copolymers

The poly-granular suds suppressor of (4-vinylpridine)-N-oxide compound: 12% polysiloxane/silicon-dioxide, 18% stearyl alcohol, 70%

Starch, it is particulate state embodiment 1

Prepare following laundry detergent composition, represented numerical value is the percentage ratio that calculates by composition weight.Citric acid and multi-carboxylate are water soluble detergency promoters.Composition A is a prior art compositions, and composition B to D is the present composition.

	????A	????B	????C	????D
	????A	????B	????C	????D	????45AS/25AS(3∶1)	????9.1	????9.1	????9.1	????9.1
????35AE3S	????2.3	????2.3	????2.3	????2.3	????45AS/25AS(3∶1)	????9.1	????9.1	????9.1	????9.1
????35AE3S	????2.3	????2.3	????2.3	????2.3	????24E5	????4.5	????4.5	????4.5	????4.5
????TFAA	????2.0	????2.0	????2.0	????2.0	????24E5	????4.5	????4.5	????4.5	????4.5
????TFAA	????2.0	????2.0	????2.0	????2.0	Zeolite A	????13.2	????13.2	????13.2	????13.2
Na SKS-6/ citric acid (79: 21)	????15.6	????15.6	????15.6	????15.6	Zeolite A	????13.2	????13.2	????13.2	????13.2
Na SKS-6/ citric acid (79: 21)	????15.6	????15.6	????15.6	????15.6	Carbonate	????7.6	????7.6	????7.6	????7.6
TAED (particle of snap-out release)	????6.3	?????-	??????-	?????-	Carbonate	????7.6	????7.6	????7.6	????7.6
TAED (particle of snap-out release)	????6.3	?????-	??????-	?????-	TAED (particle of Shi Fanging at a slow speed)	?????-	????5.0	??????-	????2.3
Benzoyl caprolactam (particle of Shi Fanging at a slow speed)	?????-	?????-	????5.0	????2.7	TAED (particle of Shi Fanging at a slow speed)	?????-	????5.0	??????-	????2.3
	?????-	?????-	????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	?????-	Percarbonate (particle of snap-out release)	????22.5	?????-	??????-	????22.5
Percarbonate (particle of Shi Fanging at a slow speed)	?????-	????22.5	????22.5	?????-	????DETPMP	????0.5	????0.8	??????-	?????-
EDDS (particle of snap-out release)	?????-	?????-	????0.3	????0.75	????DETPMP	????0.5	????0.8	??????-	?????-
EDDS (particle of snap-out release)	?????-	?????-	????0.3	????0.75	Proteolytic enzyme	????0.55	????1.27	????0.55	????1.27
Lipase	????0.15	????0.15	????0.15	????0.15	Proteolytic enzyme	????0.55	????1.27	????0.55	????1.27
Lipase	????0.15	????0.15	????0.15	????0.15	Cellulase	????0.28	????0.28	????0.28	????0.28
Amylase	????0.27	????0.27	????0.27	????0.27	Cellulase	????0.28	????0.28	????0.28	????0.28
Amylase	????0.27	????0.27	????0.27	????0.27	The multi-carboxylate	????5.1	????5.1	????5.1	????5.1
????CMC	????0.4	????0.4	????0.4	????0.4	The multi-carboxylate	????5.1	????5.1	????5.1	????5.1
????CMC	????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	????PVNO	????0.03	????0.03	????0.03	????0.03
Granular suds suppressor	????1.5	????1.5	????1.5	????1.5	Minor component/micro substance to 100%

Below be the T50 numerical value (with stopwatch show) of the product A of acquisition to D

	????A	????B	????C	????D
	????A	????B	????C	????D	Peroxy acid	????130	????190	????205	????240
????AVO	????95	????225	????230	????115	Peroxy acid	????130	????190	????205	????240
????AVO	????95	????225	????230	????115	Washing assistant (citric acid)	????90	????60	????60	????60

Embodiment 2

The cloth print is immersed the cotton print that preparation is stain in advance in the strong tea solution.The tea stain contains high-load manganese, and the basic thing that is considered to be difficult to from band dirt/spot is removed.

The cloth print that this is stain is in advance contained the pre-treatment of 5% (weight) sodium citrate aqueous solution with about 10ml.This solution and cloth print were kept in touch 10 minutes.Wash this cloth print with clothes washing method then, this method is included in a main washing using 40 ℃ of softening waters in the Miele washing machine.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.

Claims

1. detergent composition, it contains:

(a) water soluble detergency promoter; With

(b) organic peroxide acid bleach source body wherein provides the method for the release of said peroxyacid bleach in washing soln with respect to the hang-over n. of said water soluble detergency promoter that make, so that in T50 test method described herein, the time that the concentration of said water soluble detergency promoter reaches its ultimate density 50% is lower than 120 seconds, and the concentration of said peroxyacid bleach reached the time of its ultimate density 50% greater than 180 seconds.

2. detergent composition, it contains:

(a) water soluble detergency promoter; With

(b) organic peroxide acid bleach source body wherein provides the method for the release of said peroxyacid bleach in washing soln with respect to the hang-over n. of said water soluble detergency promoter that make, so that in T50 test method described herein, the concentration that the concentration of said water soluble detergency promoter reaches the said peroxyacid bleach of time ratio of its ultimate density 50% reaches low at least 100 seconds required of the time of its ultimate density 50%.

3. according to each detergent composition in claim 1 or 2, wherein said organic peroxide acid bleach source body comprises following combination:

(i) hydrogen peroxide cource body; With

(ii) peroxyacid bleach precursor compound.

4. according to the detergent composition of claim 3, wherein said peroxyacid bleach source is the peroxybenzoic acid precursors compound.

5. according to the detergent composition of claim 3, wherein said peroxyacid bleach precursor compound has cationic charge.

6. according to the detergent composition of claim 5, wherein said peroxyacid bleach precursor is chlorination 2 (N, N, N-trimethyl ammonium) ethyl 4-sulfo group phenyl-carbonic acid sodium or 4 (trimethyl ammonium) toluyl oxygen base benzene sulfonate.

7. according to the detergent composition of claim 3, wherein said peroxyacid bleach precursor compound is selected from:

A) bleach precursor or its mixture of the replacement of the acid amides of following general formula:

R wherein ¹Be to contain have an appointment 1 alkyl, aryl or alkaryl, R to about 14 carbon atoms ²Be to contain have an appointment 1 alkylidene group, arylidene or alkyl arylene, R to about 14 carbon atoms ⁵Be H or contain about 1 alkyl, aryl or alkaryl that L is a leavings group to about 10 carbon atoms;

B) the benzoxazine type bleach precursor of following formula:

R wherein ₁Be H, alkyl, alkaryl, aryl, aralkyl and R wherein 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 H or alkyl and carbonyl functional group;

C) the lactan bleach precursor of the N-acidylate of following formula: Wherein n is 0 to about 8, preferred 0 to about 2, R ⁶Be H, contain alkyl, aryl, alkoxy aryl or the alkaryl of 1 to 12 carbon atom, or contain 6 the phenyl of having an appointment to the replacement of about 18 carbon atoms; And a), b) and any mixture c).

8. according to each detergent composition among the claim 1-7, it also contains bleaching catalyst.

9. detergent composition according to Claim 8, wherein said bleaching catalyst is selected from 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) ₂Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (OCH ₃) ₃-(PF ₆); Co (2,2 '-two pyridyl amine) Cl ₂The two pyridyl amine-cobalts of two (isothiocyanatos) (II); Terpyridyl base amine-cobalt (II) perchlorate; Co (2, the two pyridyl amine of 2-) ₂-O ₂ClO ₄Two (2,2 '-two pyridyl amine) copper (II) perchlorate; Three (connection-2-pyridyl amine) iron (II) perchloric acid manganese; Manganese gluconate; Mn (CF ₃SO ₃) ₂Co (NH ₃) ₅Cl; Have the double-core Mn title complex of four-N-dentate and two-N-dentate ligand, comprise N ₄Mn ^III(u-O) ₂Mn ^IVN ₄ ⁺[(2,2 '-dipyridyl) ₂Mn ^III(u-O) ₂Mn ^IV(2,2 '-dipyridyl) ₂)-(ClO ₄) ₃And its mixture.

10. washing methods, it step that comprises is:

(1) composition solution that will contain the no SYNTHETIC OPTICAL WHITNER of water soluble detergency promoter is executed to the basic thing of band dirt;

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

(3) with comprising that the washing methods that uses the detergent composition that contains SYNTHETIC OPTICAL WHITNER washs the basic thing of said band dirt.