CN1322242A - Detergent compositions - Google Patents

Abstract

The present invention relates to detergent compositions comprising 10-60% by weight of a surfactant system and which have a maximum residual index of 25 and a maximum secondary residual index of 15. Based on the amount of detergent components in the composition, the detergent provides good performance in the wash.

Description

Detergent composition

Technical field

The present invention relates to detergent composition, particularly laundry detergent composition.

Background of invention

All washing composition of laundry applications all contain tensio-active agent and washing assistant.Generally, most of washing composition comprise by spraying drying or with washing assistant component and tensio-active agent component the original washing powder by agglomeration or extruder grain preparation for example.Original washing powder also will be handled with post-processing step usually; for example do other granulated detergent components of interpolation, spray for example tensio-active agent of other liquid components; especially nonionogenic tenside and/or with the back dusting step of fine solid particles material, the caking and the cohesiveness of the solid detergent that makes with minimizing.

The pressure of environment causes needs to produce as far as possible effectively washing composition.Use the trend of the higher detergent composition of the density of low amount, for example density be higher than 600g/l or 650g/l or be higher than 700g/l or even higher detergent composition, given prominence to guarantee the be in the suds needs of intact performance of all detergent components.

Yet solid detergent is in case contact tendency formation agglomerate or gel with water.The agglomerate of gelling material sinks in the washing machine hopper then, they are not subjected to mechanical disturbance there, perhaps owing to their usages in washing machine, solid detergent does not dissolve, and product is poor from the feeder compartment or the feed under material feeder and/or the situation washing machine self of washing machine as a result.The application of all detergent components is relatively poor thus.

The inventor finds: in order to overcome this problem, need a kind of combination of performance.This can realize by the method for control washing composition and preparing washing agent, makes when being used to prepare the particle of finished product washing composition with box lunch, has improved the combination of different detergent components, so that has realized maximum performance effect for every kind of detergent components.Minimum and make interaction maximum between other detergent components by the interaction that makes some detergent components, this has caused detergent composition for example to have good solubility and minimum pectisation, thus feed detergent components farthest in washing.This effect has caused good cleaning performance and has made because any fabric damage that high local SYNTHETIC OPTICAL WHITNER concentration causes reduces to minimum.

Summary of the invention

According to the present invention, a kind of solid detergent composition is provided, it comprises 10-60% weight surfactant system and its, and to have maximum residual index be 25, the maximum secondary residual index is 15.

Residual index can calculate with following method:

1 liter of deionized water is put in the detersive power determinator (tergitometer) (ErwekaDT6-R is ' Sotax ' equipment hereinafter referred to as) (USP 711 dissolving standards).Sotax is loaded onto plexiglass cover suppressing evaporation, and with temperature correction to 5 ℃, agitator (stirring rake) is fixed on 200rpm.This stirring rake is fixed with two blades at central shaft, and they are directly opposite one another, thus two blades to make the diameter of stirring rake altogether be 75mm.This stirring rake is positioned at the Sotax equipment center, and the distance of the bottom of stirring rake and detersive power determinator bottom is 25mm.The total height of stirrer paddle is 19mm.Provide a wire basket that has by 20 orders (850 μ) sidewall that Stainless Steel Wire is made and bottom, its diameter 25mm, height 41mm.The Betengent product of packing in the wire basket, the surface of Betengent product are flattened and use impermeable lid that the top seal of wire basket is lived.Then the wire basket is suspended on the central shaft of Sotax and the center fixed position between the sidewall, residing height makes the bottom of wire basket be higher than stirring rake upper surface 7mm.

After 12 minutes, from Sotax equipment, take out the wire basket of assembling and resistates is transferred in the preweighted container.This transfer step must be quantitative, if need, also is to accept with the rinse step of deionized water.This residue is dry in 70-80 ℃ stove, does not have further weight loss until record.Record exsiccant residue weight.Calculate the percentage ratio that residue in the basket accounts for the original sample quality of the detergent composition of putting into Sotax then.The mean value of the percentage residue of two kinds of same sample is residual index.

The residual index of detergent composition of the present invention must be not more than 25, preferably is not more than 20, even more preferably no more than 15.

Secondary residual index is to calculate by the following method:

Use identical equipment, add the 800ml deionized water in the Sotax equipment and make temperature equilibrium to 20 ℃, the speed of agitator is 200rpm.Add 2 gram products in the deionized waters then and be to stir 20 minutes under the 200rpm at agitator speed.After 20 minutes, filter the washing composition sample that contains deionized water by the black fabric annulation of placing in Bu Shi (Buchner) funnel (available from EmpiricalManufacturing Company) of C70, topmost the sidewall of fabric is slick.Taking-up is deceived fabric and is placed on a slice paper from B.Made black fabric at room temperature dry 24 hours.To each experiment, triplicate calculates the residue that stays and accounts for the average percentage that adds the total washing composition sample among the Sotax on black fabric annulation.

The average residue that is obtained by three repeated experiments provides secondary residual index, and it must be 15 to the maximum.Preferably, the maximum secondary residual index is 10, even more preferably, the maximum secondary residual index can be 5 or lower. Builder system

Detergent composition comprises builder system, and it can provide by a kind of washing assistant or more than a kind of mixture of washing assistant.Can use water-soluble and/or the water-insoluble washing assistant.Builder system generally accounts for the 1%-90% weight of detergent composition, preferred 20%-80% weight. Water-soluble or part water soluble detergency promoter

Builder system in the present composition preferably contains water-soluble and/or portion water dissolubility washing-aid compound, and generally its content is 1%-80% weight, and preferred content reaches 50% weight, or reaches 40% or even 35%.The content of preferred water soluble detergency promoter is at least 3% or 8%, but preferably their content is 6%-25% weight.

Detergent composition of the present invention can comprise phosphorated washing assistant material, for example tetrasodium pyrophosphate or more preferably anhydrous sodium tripolyphosphate.The content of phosphate builders can be 0.5%-60%, or 5%-50%, or even 8%-40% weight.Yet general preferred said composition does not have phosphorated washing assistant material.

Crystalline layered silicate also is the part water soluble detergency promoter that is fit to.The preferred crystalline layered silicate of the present invention has general formula: NaMSi _xO _2x+1.yH ₂O wherein M is sodium or hydrogen, and x is the numerical value of 1.9-4, and y is the numerical value of 0-20.This class 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, the x in the above general formula is 2,3 or 4, is preferably 2.M is preferably H, K or Na or its mixture, preferred Na.Most preferred material is α-Na ₂Si ₂O ₅, β-Na ₂Si ₂O ₅Or δ-Na ₂Si ₂O ₅Or its mixture, preferably 75%-Na at least ₂Si ₂O ₅, for example be the NaSKS-6 that buys from Clariant.Crystalline layered silicate material, particularly formula Na ₂Si ₂O ₅Material can randomly comprise other element for example B, P, S, for example obtain by the method for describing among the EP578986-B.

Part water soluble detergency promoter preferred content height to 40% is more preferably up to 35%.When containing them, by the weight of said composition, the preferred present composition comprises 10%-40%, more preferably 12%-35% or even 15%-25% wt part water soluble detergency promoter.

Water soluble detergency promoter comprises organic carboxyl acid and its salt.Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or its sour form, homopolymerization or copolymerization poly carboxylic acid or its salt, wherein poly carboxylic acid comprises and is no more than at least two carboxyls that two carbon atoms separate are opened each other, and the mixture of aforementioned any compound.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer type or oligomer types, but because Cost And Performance, preferred monomers multi-carboxylate usually.Except these water soluble detergency promoters, also can contain the polymeric multi-carboxylate, comprise toxilic acid and acrylic acid homopolymer and multipolymer and their salt.

The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt and the ether derivant thereof of lactic acid, oxyacetic acid.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, Glyoxylic acid hydrate, tartrate, tartronic acid, oxysuccinic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing three carboxyls comprises particularly water-soluble citrate, aconitate and citraconate, and the succinate derivative, as English Patent 1,379,241 described carboxy methoxy-succinic acid salt, the newborn acyloxy succinate described in the English Patent 1389732, HOII P 7205873 described aminosuccinic acid salt, and English Patent 1,387,447 described oxygen multi-carboxylate material, for example 2-oxa-s-1,1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls comprises English Patent 1,261,829 described oxygen disuccinate, 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Comprise the substituent multi-carboxylate of sulfo group and comprise English Patent 1,398,421 and 1,398,422 and U.S. Pat 3,936,448 described sulfo-succinic acid salt derivatives, and English Patent 1,439,000 described sulfonation pyrolytic Citrate trianion.Preferred multi-carboxylate is contained the hydroxycarboxylate of 3 carboxyls of as many as, Citrate trianion more specifically for per molecule.The parent acid of monomer or oligomeric multi-carboxylate's sequestrant or also expect as useful builder component, for example citric acid or Citrate trianion/citric acid mixture with the mixture of its salt.

Most preferred can be acetate, citric acid, oxysuccinic acid and fumaric acid, or their salt or its mixture.The preferred mixture that has its salt and sour form.

Water soluble detergency promoter preferred content height to 40% is more preferably up to 35%.When containing them, the preferred present composition comprises 10%-40%, more preferably 12%-35% or even 15%-25% weight water soluble detergency promoter.

By the weight of said composition, preferred polymeric or oligomeric multi-carboxylate's content is lower than 5%, preferably is lower than 3% or even be lower than 2% or even 0%.

The borate washing assistant and can washing composition store or wash conditions under to produce the boratory washing assistant that forms borate substance that contains be the useful water soluble detergency promoter of the present invention.

Other water soluble detergency promoter materials that are fit to are polymeric polycarboxylic acid or multi-carboxylate, comprise water-soluble homopolymerization or copolymerization poly carboxylic acid or their salt, and wherein poly carboxylic acid comprises and is no more than at least two carboxyls that two carbon atoms separate are opened each other.The polymkeric substance of latter's type is disclosed among the GB-A-1596756.The example of this salt is that MWt is 1000-50000, preferred 10000 or even 7000 the polyacrylate and the multipolymer of (gathering) acrylate and toxilic acid or maleic anhydride, this multipolymer preferred molecular weight is 2000-100000, particularly 40000-80000.

In the preferred embodiment of the invention, the insoluble washing assistant of water-soluble or part, particularly crystalline layered silicate is when existing, at same tensio-active agent, in the intimate mixture of preferred anionic tensio-active agent, exist, for example at least 50% weight to small part.

Find that also compound when highly water-soluble carboxylate-containing or carboxylic acid is present in a kind of or kinds of surface promoting agent and randomly in the intimate mixture of other components the time, the dissolution rate increase of the dissolution rate of this intimate mixture and tensio-active agent and other components.Thus, can realize that tensio-active agent and other components discharge comprehensively fast.

Thus, a kind of preferred particle component in the detergent composition of the present invention can comprise and accounts for the preferred 25%-75% weight of this component weight, more preferably 35%-68%, even more preferably 45%-62% weight crystal layered silicate or water soluble detergency promoter and account for this component weight 25%-75%, more preferably 32%-62%, the more preferably intimate mixture that constitutes of 38%-48% anion surfactant.

This particle component preferred package contains and is less than 10% weight percent free water, preferably is less than 5% or even less than 3% or even less than 2% weight.Free-water described here can be measured by the following method: 5 gram particle components are put into Petri dish, this Petri dish is put into 50 ℃ convection furnace 2 hours, measure then because the weight loss that water evaporates causes.

Anion surfactant preferably comprises 50%-100% weight, preferred 60% or even 75%-100% sulfonate anionic surfactant as described below, the preferred alkyl benzene sulfonate surfactant.Based on the total amount meter of the anion surfactant in the detergent composition, preferably as many as 50% weight or more anion surfactant are mixed in this particle component.

The content of preferred this particle component in detergent composition is the 0.5%-60% weight of composition weight, preferred 3%-50%, more preferably 5%-45%, even more preferably at least 7% weight.

Preferably, in intimate mixture, the weight ratio of crystalline layered silicate and/or one or more water soluble detergency promoters and anion surfactant is 4: 5-7: 3, more preferably 1: 1-2: 1, most preferably 5: 4-3: 2.

This component also can comprise other compositions, for example accounts for this particle component weight 0-25%, generally is not more than 20% or even 15% weight.The definite character of these other compositions and its incorporation will depend on the application of this component or composition and the physical form of this component and composition.Preferred this particulate composition comprise be less than 15% or be lower than 10% or even 5% weight nonionic ethoxylated alcohol surfactant granules, preferably be lower than 15% or even be lower than 10% or even be lower than 5% any nonionogenic tenside.

Preferred this particulate composition comprises and is lower than 10% weight, preferably is lower than 5% weight alumino-silicate materials.If have some alumino-silicate materials, preferably this particulate composition alumino-silicate materials dusting.

This particle component can comprise the polymeric adhesive material, but preferably uses the least possible adhesive material.Preferred this intimate mixture comprises and is less than 25%, preferably is less than 10%, more preferably less than 5% weight, and 0% weight ethylene oxide polymer most preferably.

This particle component preferably has at least 50 microns of average particle size, preferred 150 microns-1500 microns, or more preferably the particle of 80% weight has granularity and has granularity greater than 1180 microns or even 710 microns (on Tyler mesh of sieve mesh 24) greater than 300 microns (on the Tyler mesh (Tyler) of sieve mesh 48 80% weight being arranged) and the particle that is less than 10% weight.

Preferably, the density of this particle component is 380g/ liter-1500g/ liter, or more preferably 500g/ liter-1200g/ liter, more preferably 550g/ liter-900g/ liter.

This particle component can be used as independent particle and is present in the detergent composition of the present invention, or also can further mix with other detergent components, comprises further agglomeration, die mould, makes sheet or extruding.

This intimate mixture or particle component can prepare the combination of for example agglomeration, spraying drying, roll extrusion and/or extruding or these method stepss with the method for this detergent particles of any known preparation.Can randomly follow drying step or dusting step after this technology and/or spray step.The particle of preparation preferably mixes with other detergent components then.

Crystalline layered silicate and/or highly water-soluble washing assistant also can be in and other materials, comprise one or more water soluble detergency promoters as described herein or polymerizable compound for example vinylformic acid and/or toxilic acid polymkeric substance, mineral acid or salt comprise carbonate and vitriol, or other silicate materials comprise in the intimate mixture of amorphous silicate, metasilicate and silico-aluminate on a small quantity.

Preferred part or even all water soluble detergency promoters, particularly monomer or oligomeric (many) carboxylic acids or its salt be with independent particulate form, preferably the mean particle size of this washing assistant material is lower than 150 microns thus, or even is lower than 100 microns.When needs, the water-soluble or part water soluble detergency promoter of a preferred part uses as separant, to reduce the caking of product.

Particularly, when a small amount of insoluble washing assistant is present in the composition, multi-carboxylate's polymkeric substance for example maleic anhydride or toxilic acid polymkeric substance and its multipolymer content in composition with (gather) vinylformic acid and its salt can be the 0.5%-15% of composition weight, preferred 1%-12%, even 2%-8% weight.Thus, insoluble washing assistant of preferably water and polymkeric substance are not present in a kind of intimate mixture each other.

The inventor also finds when the multi-carboxylate polymer exists, preferred this polymkeric substance is included in the intimate mixture with other detergent components, preferably is contained in the spray-dried granules, and it is preparation like this, at first, add then and tight other components that mix carbonate and mixed with polymers. Insoluble washing assistant

The present composition can contain insoluble washing-aid compound.Generally, based on total detergent composition meter, their content is no more than 30% weight, preferably is not more than 25% weight.

Basically the example of water-insoluble washing assistant comprises sodium silicoaluminate.

The aluminosilicate zeolite that is fit to has unit structure cell formula Na _z[(AlO ₂) _z(SiO ₂) _y] .xH ₂O, wherein z and y are at least 6, and the mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.Alumino-silicate materials can be hydrated form, and preferably xln contains 10-28%, preferred 18-22% combination water.

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

Na ₁₂[AlO ₂) ₁₂(SiO ₂) ₁₂] .xH ₂O wherein x is 20-30, particularly 27.X zeolite has formula: Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂O.

Preferred in addition aluminosilicate zeolite is a zeolite MAP builder.Zeolite MAP is stated in EP384070A (Unilever).It is defined as the zeolite P type alkali metal aluminosilicate, and its ratio with silicon and aluminium is not more than 1.33, is preferably 0.9-1.33, more preferably 0.9-1.2.Making us interested especially is silicon and the ratio of aluminium is not more than 1.15, is not more than 1.07 zeolite MAP more specifically.

In preferred situation, the granularity of zeolite MAP detergent builders is represented as d ₅₀, its value is 1.0-10.0 μ m, more preferably 2.0-7.0 μ m, most preferably 2.5-5.0 μ m.d ₅₀Value is meant that 50 weight % particulate diameters are worth less than this.This granularity specifically can be measured or be measured with laser particle size analyzer as the microscope that adopts scanning electron microscope to carry out by the routine analysis technical measurement.Other determines d ₅₀The method of value is stated in EP 384070A.

Find that water-insoluble washing assistant, particularly silico-aluminate have promoted the problem of the overall application difference of detergent composition component.Therefore, they generally mix low amount in detergent composition, or need special processing, so that the effectiveness maximum of all detergent components in detergent composition.

Therefore, in one embodiment of this invention, silico-aluminate washing assistant preferred content is lower than 9% weight, preferably is lower than 6% weight or 4% weight.Even preferably there is not the water-insoluble washing assistant basically.Preferably, detergent composition contains low amount amorphous silicate, for example is lower than 5% weight amorphous sodium silicate of composition, most preferably is lower than 2% weight.

In preferred situation, detergent composition preferably comprises builder system, it comprises and is lower than 30%, or even be lower than 20% or even be lower than 10% weight water-insoluble washing assistant, thus in preferred embodiments, the equipoise of builder system is water soluble detergency promoter and/or part water soluble detergency promoter.

When existing, silico-aluminate can be included in and contain other detergent components for example in the powder component of detergent agglomerate, extrudate or the blowing of tensio-active agent.Even preferably do not exist basically as the silico-aluminate of (doing and add) the particle component separately.

In addition, the preferred existence is less than 3%, or even less than 1.5%, or even less than 0.8% weight amorphous silicate.When existing, amorphous silicate preferably is contained in and contains other detergent components for example in the powder component of detergent agglomerate, extrudate or the blowing of tensio-active agent.The preferred amorphous silicate that does not exist basically as independent particle component.

As described, detergent composition of the present invention preferably comprises at least a particle component, and it contains one or more intimate mixtures water-soluble or part water soluble detergency promoter and one or more tensio-active agents.Preferably, in detergent composition, there are at least two kinds of such particle components.

In other embodiments of the present invention, if need mix insoluble washing assistant, silico-aluminate particularly, for example its content is 5% weight or more, wherein said composition also comprise anion surfactant for example content be 5% weight or more, this detergent composition is preferably such: have at least two kinds of (n) detergent components (i) in the said composition, the degree of mixing (M) of anion surfactant and silico-aluminate washing assistant is 0-0.7, wherein the M=∑ _i ⁿ=1 √ (σ _i. ζ _i) and σ be included in the mark that anion surfactant in the component (i) accounts for composition; ζ is included in the mark that silico-aluminate in the component (i) accounts for composition.

In order to reach good especially washing composition feed, preferred M is 0-0.6, or even 0-0.5.

In this embodiment of the present invention, detergent composition of the present invention comprises at least two kinds of multicomponent components (i.e. the single component of no more than 95% weight in every kind of component), it comprises anion surfactant or silico-aluminate or its mixture, thus if in one or more components, have silico-aluminate and a surfactant mixtures, be lower than 0.7 by the M of the defined mixture of following formula.Therefore, every kind of component comprises part or all of silico-aluminate, all or part of anion surfactant or its mixture, and condition is that M is 0-0.7.

This component comprises the silico-aluminate washing assistant that accounts for composition weight at least 5% altogether and accounts for the anion surfactant of composition weight at least 5%.Preferably, this component comprises and accounts for composition weight at least 7%, or more preferably at least 10% or even 15% silico-aluminate.According to the definite prescription and the working conditions of composition, the present composition even can comprise the more silico-aluminate of a large amount, for example more than 20% or even more than 25%, and still can in washing, provide the washing composition of improvement to discharge.

Preferably account for composition weight at least 7% or more preferably at least 10% or even at least 12% weight anion surfactant be present in this component.According to the definite prescription and the working conditions of composition, the content of preferred anionic tensio-active agent be composition weight 18% or more.

This component is by above-mentioned preparation: by for example agglomeration of any comminution granulation, compacting, spraying drying or extruding altogether. The foaming system

The known any foaming system of prior art all can be used in the detergent composition of the present invention.The preferred foaming system in the particle of the present invention of mixing be included in water exist down can with the acid source of alkali source generated reactive gas.

Comprise in the foaming system under the situation of two or more reactants, preferably they are to provide with intimate mixture, as the foaming system.The component that most preferably bubbles comprises the intimate mixture of anhydrous basically stablizer and bronsted lowry acids and bases bronsted lowry reactant.

The acid source component can be any organic, mineral or mineral acid, or derivatives thereof or its mixture.Preferred acid source component comprises organic acid.Acid source preferably is anhydrous or non-hygroscopic basically, and acid is preferably water miscible.Preferred acid source is a super-dry.The acid source component that is fit to comprises citric acid, oxysuccinic acid, toxilic acid, fumaric acid, aspartic acid, pentanedioic acid, tartrate, succsinic acid or hexanodioic acid, monosodium phosphate, boric acid or derivatives thereof.Citric acid, toxilic acid or oxysuccinic acid are particularly preferred.

Calculate by screening acid source sample on serial Tyler mesh, most preferably, acid source provides has about 75 microns-1180 microns of mean particle size, more preferably 150 microns-710 microns acidic cpd.

As mentioned above; this foaming system preference comprises alkali source; yet; for the object of the invention; be to be understood that alkali source can be that the part of effervescent granules maybe can be a part that comprises this particulate cleaning combination; maybe can be present in the washing soln, described particle or cleaning combination are added in the washing soln.

Can all can be present in any alkali source of acid source generated reactive gas in this particle, described gas can be the known any gas of prior art, comprises nitrogen, oxygen and carbon dioxide gas.Can be the perhydrate SYNTHETIC OPTICAL WHITNER preferably, comprise perborate and silicate material.Alkali source preferably is anhydrous or non-hygroscopic basically.Preferred alkali source is a super-dry.

Preferred this gas is carbonic acid gas, so alkali source carbonate source preferably, and it can be the known any carbonate source of prior art.In preferred embodiments, carbonate source is a carbonate.The example of preferred carbonate is alkaline-earth metal and alkaline carbonate, comprise yellow soda ash or potassium, sodium bicarbonate or potassium, with concentrated crystal soda or potassium and its any mixture, calcium carbonate superfine powder for example is disclosed in the German patent application of announcing on November 15th, 1,973 2321001.Alkali metal percarbonate also is the carbonate source that is fit to, and it can combine existence with one or more other carbonate source.

Carbonate and supercarbonate preferably have amorphous structure.Carbonate and/or supercarbonate can apply with coated material.Preferred carbonate and bicarbonate particles can have 75 microns of mean particle sizes or preferred 150 μ m or bigger, more preferably 250 μ m or bigger, preferred 500 μ m or bigger.Preferred carbonate is such: carbonate or supercarbonate sample are sieved calculating on serial Tyler mesh, the particle that granularity is less than 500 μ m is less than 20% (weight).In addition or except above-mentioned carbonate, carbonate or supercarbonate sample are sieved calculating on serial Tyler mesh, the particle that preferred size is lower than 150 μ m be less than 60% or even 25%, and granularity is less than 5% greater than the particle of 1.18mm, more preferably granularity is less than 20% greater than the particle of 212 μ m.

The acid source that exists in hilum and the mol ratio of alkali source are preferably 50: 1-1: 50, more preferably 20: 1-1: 20, more preferably 10: 1-1: 10, more preferably 5: 1-1: 3, more preferably 3: 1-1: 2, more preferably 2: 1-1: 2. Stablizer

Preferred stablizer is anhydrous stablizer basically.Stablizer can comprise one or more components.Preferred stabilizer comprise to small part be water miscible compound.

Preferably, stablizer is a solid under common condition of storage, and for example the preferred fusing point of this component is higher than 30 ℃, more preferably be higher than 45 ℃ or even more preferably be higher than 50 ℃, preferred stabilizer is such, is forming melts more than 80 ℃ easily.

Preferably, stablizer comprises one or more components, be selected from alcohol alcoxylates, comprise polyoxyethylene glycol and/or polypropylene glycol and alkoxylate alcohol amide, comprise glycollic amide, alkoxylate glycollic amide, alkoxylated fatty acid acid amides or glycollic amide and specific nonionogenic tenside, comprise (poly-hydroxy) fatty acid amide, alcohol alcoxylates tensio-active agent and specific alkyl polysaccharide surfactant and any mixture of these compounds, as described herein.

Preferably, one or more components that comprise in stablizer are that washing composition is active, the cleaning performance that it can help this particle or comprise this particulate cleaning combination.The highly preferred anhydrous basically component that is suitable in the particulate stablizer of the present invention is one or more nonionogenic tensides, be selected from the nonionic alkoxy-based surface-active agent, comprise alcohol alcoxylates tensio-active agent, polyhydroxy fatty acid amide surfactant, fatty acid amide surfactant, alkoxylated fatty acid acid amides, fatty acid alkyl ester and alkyl polysaccharide surfactant, with its mixture, as mentioned below.

In the highly preferred situation of the present invention, stablizer comprises polyhydroxy fatty acid amide and/or polyoxyethylene glycol, and/or alkoxylated fatty acid acid amides and/or Fatty Alcohol(C12-C14 and C12-C18) and 1-15, or the more preferably mixture of the condensation product of 11 mole alkylene oxide, as described in more detail in the description that is fit to tensio-active agent hereinafter.When existing, the ratio of polyhydroxy fatty acid amide and Fatty Alcohol(C12-C14 and C12-C18) condensation product is preferably 20: 1-1: 20, more preferably 10: 1-1: 10, more preferably 8: 1-1: 8, more preferably 6: 1-1: 6, most preferably 2: 1-1: 3.When existing, the ratio of polyhydroxy fatty acid amide and polyoxyethylene glycol is preferably 20: 1-1: 8, more preferably 15: 1-1: 3, more preferably 12: 1-1: 1, more preferably 10: 1-1: 1.When existing, the ratio of polyhydroxy fatty acid amide and alkoxylated fatty acid acid amides is preferably 20: 1-1: 20, more preferably 15: 1-1: 10, more preferably 10: 1-1: 10. Be applicable to the tensio-active agent in the detergent composition

Detergent composition of the present invention can contain one or more tensio-active agents, these tensio-active agents are selected from anion surfactant described as follows, cats product, amphoterics, zwitterionics or nonionogenic tenside and its mixture.

The US 3,929,678 that was issued to Laughlin and Heuring on December 30th, 1975 has provided the general catalogue of these tensio-active agents.Other example provides in " tensio-active agent and washing composition " (I volume and II volume, Schwartz, Perry and Berch).The catalogue of suitable cats product is issued to the US4 of Murphy on March 31st, 1981, provide in 259,217.Some examples see below. Anion surfactant

Any anion surfactant all can mix in the present composition.The anion surfactant here preferably includes at least a sulfate surfactant and/or sulfosalt surfactant or its mixture.The preferred anionic tensio-active agent only comprise alkyl sulfonate surfactants or randomly with lipid acid or its soap salt binding.In addition, preferred said composition only comprises alkyl sulfate surfactant, but preferably has the alkyl surfactants of at least a mid-chain branched here or have at least two kinds of alkyl surfactants.

Definite prescription and its purposes according to said composition; the preferred present composition comprises as above-mentioned particle component; the laminar form of alkyl-sulphate or sulfosalt surfactant preferably; the preferred alkyl benzene sulfonate; its concentration that contains in particle or thin slice is 85%-95%; surplus is vitriol and moisture content, and this particle or thin slice mix with other detergent components or composition.

Other possible anion surfactants comprise isethionate, as fatty acid amide, alkyl succinate and the alkyl sulfo succinate of acyl isethinate, N-acyl taurine salt, methylamino esilate, the monoesters of sulfosuccinate (particularly saturated and unsaturated C ₁₂-C ₁₈Monoesters), the diester of sulfosuccinate (particularly saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also suit, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in butter or obtain by butter.

According to definite prescription and its purposes of composition, the preferred present composition comprises a kind of like this component, and it contains and vitriol and moisture content tight blended high-content alkyl-sulphate or sulfosalt surfactant or its mixture, preferred alkyl benzene sulfonate.For example this component comprises 85%-95% anion sulfate or sulfosalt surfactant and 15%-5% vitriol and moisture content.This component can be laminar, and it can mix or dried adding to wherein with other components of detergent composition of the present invention. The anion sulfoacid salt surfactant

Anionic sulphonate tensio-active agent according to the present invention comprises C ₅-C ₂₀Straight or branched alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Ethylenic sulfonate, sulfonation poly carboxylic acid and its any mixture.

It is highly preferred that C ₁₂-C ₁₆Linear alkylbenzene sulfonate.Preferred salt is sodium and sylvite.

Sulfonated alkyl ester tensio-active agent also is suitable for the present invention, preferably has those of following formula:

R ¹-CH (SO ₃M)-(A) _x-C (O)-OR ²R wherein ¹Be C ₆-C ₂₂Alkyl, R ²Be C ₁-C ₆Alkyl, A are C ₆-C ₂₂Alkylidene group, alkenylene, x are 0 or 1, and M is a positively charged ion.Counter ion M is sodium, potassium or ammonium preferably.

Sulfonated alkyl ester tensio-active agent is the alpha-sulfo alkyl ester of following formula preferably, and x is 0 thus.Preferably, R ¹Be to have a 10-22 carbon atom, the alkyl of preferred 16 carbon atoms or alkenyl, x preferably 0.R ²Ethyl or be more preferably methyl preferably.

The R of preferred this ester ¹Be to derive by the unsaturated fatty acids that preferably has 1,2 or 3 two key to obtain.Further preferably, the R of this ester ¹By naturally occurring lipid acid, preferred palmitinic acid or stearic acid or its mixture are derived and are obtained. The negatively charged ion alkyl sulfate surfactant

Anion sulfate tensio-active agent of the present invention comprises straight chain and side chain primary and secondary alkyl-sulphate and dithionate, have average ethoxylation value is 3 or is lower than 3 alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol oxygen Vinyl Ether vitriol, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide.

The primary alkyl sulphates tensio-active agent is preferably selected from straight chain and side chain uncle C ₁₀-C ₁₈Alkyl-sulphate, more preferably C ₁₁-C ₁₅Straight or branched alkyl-sulphate, or more preferably C ₁₂-C ₁₄Straight-chain alkyl sulfate.

Preferred secondary alkyl sulfate surfactant has following formula: R ³-CH (SO ₄M)-R ⁴R wherein ³Be C ₈-C ₂₀Alkyl, R ⁴Be alkyl, M is a positively charged ion.

Alkyl ethoxy sulfate surfactant is preferably selected from every mole by the C of 0.5-3 moles of ethylene oxide ethoxylation ₁₀-C ₁₈Alkyl-sulphate.More preferably, alkyl ethoxy sulfate surfactant be every mole by 0.5-3, the C of the oxyethane ethoxylation of preferred 1-3 mole ₁₁-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate.

The particularly preferred situation of the present invention is to use the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.Preferred salt is sodium and sylvite. The negatively charged ion wheat surface-active agent of mid-chain branched

The primary alkyl sulphates tensio-active agent that is used for the preferred mid-chain branched of the present invention has formula:

These tensio-active agents have linear primary alkyl-sulphate chain backbone (the longest carbon straight chain that promptly comprises Sulfated carbon atom), its primary alkyl part that preferably comprises 12-19 carbon atom and their branching preferably comprises at least 14 carbon atoms altogether, preferably is no more than 20 carbon atoms.In the surfactant system that comprises more than a kind of these sulfate surfactants, the average total carbon atom number of the primary alkyl of branching part is preferably greater than 14.5-about 17.5.Therefore, this surfactant system preferably comprises the primary alkyl sulphates surfactant compounds of at least a branching, it has the longest carbon straight chain that is no less than 12 carbon atoms or no more than 19 carbon atoms, must be at least 14 with the total number of carbon atoms that comprises side chain, in addition, for the branched primary alkyl part, average total carbon atom number is greater than 14.5-about 17.5.

R, R ¹And R ²Be selected from hydrogen and C independently of one another ₁-C ₃Alkyl (preferred hydrogen or C ₁-C ₂Alkyl, more preferably hydrogen or methyl, and most preferable), condition is R, R ¹And R ²Not all be hydrogen.In addition, when z is 1, R or R at least ¹Not hydrogen.

M is the salifiable positively charged ion of hydrogen or shape, and this depends on synthetic method.

W is the integer of 0-13; X is the integer of 0-13; Y is the integer of 0-13; Z is at least 1 integer; With w+x+y+z be the integer of 8-14.

The primary alkyl sulphates tensio-active agent of preferred mid-chain branched is the primary alkyl sulphates tensio-active agent of 16 carbon altogether, in its skeleton, have 13 carbon and altogether 1,2 or 3 branching unit of 3 carbon atoms (be R, R ¹And/or R ²), (the total number of carbon atoms is at least 16 thus).Preferred branching unit can be a propyl group branching unit or three methyl-branched unit.

Another kind of preferred surfactants is the branched primary alkyl sulphates with following formula:

Comprising the total carbon atom number of side chain is 15-18 and when existing more than a kind of these vitriol, at the average total carbon atom number of branched primary alkyl part with following formula for greater than 14.5-about 17.5; R ¹And R ²Be hydrogen or C independently of one another ₁-C ₃Alkyl; M is a water-soluble cationic; X is 0-11; Y is 0-11; Z is at least 2; With x+y+z be 9-13; Condition is R ¹And R ²Not all be hydrogen. Dianionic surfactant

Dianionic surfactant also is the useful anion surfactant of the present invention, particularly has those of following formula: Wherein R has chain length C ₁-C ₂₈, preferred C ₃-C ₂₄, C most preferably ₈-C ₂₀Optional substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group, or hydrogen; It is C that A and B are independently selected from chain length ₁-C ₂₈, preferred C ₁-C ₅, C most preferably ₁Or C ₂Alkylidene group, alkylene group, (gathering) alkylene oxide group, hydroxyl alkylidene group, aryl alkylene or amido alkylidene group, or covalent linkage, preferred A and B contain at least 2 carbon atoms altogether; A, B and R contain 4 altogether to about 31 carbon atoms; X and Y are selected from carboxylate radical, the anionic group of preferably sulfuric acid root and sulfonate radical; Z is 0 or preferably 1; With M be cationic moiety, preferably replace or unsubstituted ammonium ion or basic metal or alkaline-earth metal ions.

Most preferred dianionic surfactant has following formula, and wherein R is that chain length is C ₁₀-C ₁₈Alkyl, A and B are C independently ₁Or C ₂, X and Y are sulfate radicals, M is potassium, ammonium or sodium ion.

The preferred dianionic surfactant of the present invention comprises:

(a) 3 dithionate compounds, preferred 1,3 C7-C23 (i.e. total carbon atom number in this molecule) straight or branched alkyl or alkenyl dithionate, more preferably it has following formula: Wherein R has chain to be about C ₄-Yue C ₂₀Straight or branched alkyl or alkenyl;

(b) 1,4 dithionate compound, preferred 1,4 C8-C22 straight or branched alkyl or alkenyl dithionate more preferably have following formula: Wherein R has chain to be about C ₄-Yue C ₁₈Straight or branched alkyl or alkenyl; Preferred R is selected from octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and its mixture; With

(c) 1,5 dithionate compound, preferred 1,5 C9-C23 straight or branched alkyl or alkenyl dithionate, more preferably it has following formula:

Wherein R has chain to be about C ₄-Yue C ₁₈Straight or branched alkyl or alkenyl.

Preferred dianionic surfactant of the present invention is the alkoxylate dianionic surfactant.

Alkoxylate dianionic surfactant of the present invention comprises the structural framework of at least 5 carbon atoms, two anion substituents that are attached thereto at least three carbon atoms of spatially being separated by.In the described anion substituent at least one is sulfate radical or the sulfonate radical that links to each other with alkoxyl group.Described structural framework can comprise any group in alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and the amide group of for example alkyl, replacement.Preferred alkoxyl group partly is oxyethyl group, propoxy-and its mixture.

This structural framework preferably comprises 5-32, preferred 7-28, most preferably 12-24 atom.Preferred this structural framework only comprises carbonaceous group, more preferably only comprises alkyl.Most preferably this structural framework only comprises the straight or branched alkyl.

This structural framework is branching preferably.Preferred side chain accounts at least 10% of structural framework weight, and the length of side chain is preferably 1-5 atom, more preferably 1-3, most preferably 1-2 atom (not comprising the sulfate radical or the sulfonate radical that link to each other with side chain).

The preferred alkoxylated dianionic surfactant has formula:

Wherein R has chain length C ₁-C ₂₈, preferred C ₃-C ₂₄, C most preferably ₈-C ₂₀Optional substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group, or hydrogen; A and B are independently selected from has chain length C ₁-C ₂₈, preferred C ₁-C ₅, C most preferably ₁Or C ₂Optional substituted alkyl and alkenyl, or covalent linkage; EO/PO is the alkoxyl group part, is selected from oxyethyl group, propoxy-and blended oxyethyl group/propoxy-group, and wherein in about 10 scopes of about 0-, m or n are at least 1 at least independently for n and m; A and B contain at least 2 atoms altogether; A, B and R contain 4 altogether to about 31 carbon atoms; X and Y are the anionic groups that is selected from sulfate radical and sulfonate radical, and condition is that among X or the Y at least one is sulfate radical; With M be cationic moiety, preferably replace or unsubstituted ammonium ion or basic metal or alkaline-earth metal ions.

Most preferred alkoxylate dianionic surfactant has following formula, and wherein R is that chain length is C ₁₀-C ₁₈Alkyl, A and B are C independently ₁Or C ₂, n and m are 1, and X and Y are sulfate radicals, and M is potassium, ammonium or sodium ion.

Preferred alkoxylated dianionic surfactant of the present invention comprises: ethoxylation and/or propoxylation dithionate compound, and preferred C10-C24 straight or branched alkyl or alkenyl ethoxylation and/or propoxylation dithionate more preferably have following formula:

Wherein R is straight or branched alkyl or the alkenyl that chain is about the about C18 of C6-; EO/PO is the alkoxyl group part, is selected from oxyethyl group, propoxy-and blended oxyethyl group/propoxy-group, and wherein at about 10 scopes of about 0-(preferably about 0-about 5), m or n are 1 at least independently for n and m. The anionic carboxylic acid salt surfactant

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

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

Suitable soap class tensio-active agent comprises secondary soap surfactant, and it comprises the carboxyl unit that links to each other with secondary carbon(atom).Being preferred for secondary soap surfactant of the present invention is to be selected from following water-soluble substances: the water-soluble salt that the water-soluble salt of the water-soluble salt of 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, the water-soluble salt of 2-propyl group-1-n-nonanoic acid, 2-butyl-1-are sad and the water-soluble salt of 2-amyl group-1-enanthic acid.

Some soap class also can be used as suds suppressor and adds. The basic metal sarcosinate surfactant

Other suitable anion surfactants are formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇-straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ion.Preferred examples is the myristyl and the oleoyl methyl sarcosinate of sodium-salt form. The nonionic alkoxy-based surface-active agent

When having nonionogenic tenside, the component of the preferred present composition does not contain by the nonionic alcohol alcoxylates tensio-active agent on spraying.Find to improve thus the feed of composition in washing water and reduced the product caking.Preferred said composition be included in be lower than 30 ℃ or even 40 ℃ be the solid nonionogenic tenside down, preferably it is present in the intimate mixture with other components.

Basically any alkoxy-based non-ionic surface active agent also can be included in the detergent composition of the present invention.Preferred ethoxylation and propoxylation nonionogenic tenside.The preferred alkoxylated tensio-active agent can be selected from the alkylphenol condensation of non-ionic type, the ethoxylated alcohol of non-ionic type, the ethoxylated/propoxylated fatty alcohol of non-ionic type, ethoxylated/propoxylated condenses non-ionic type and propylene glycol, and ethoxylation condensation product non-ionic type and propylene oxide/ethylenediamine adduct.

It is highly preferred that nonionic alcohol alcoxylates tensio-active agent, it is Fatty Alcohol(C12-C14 and C12-C18) and 1-75 mole alkylene oxide, particularly about 50 or the 1-15 mole, preferably to 11 moles, the condensation product of oxyethane and/or propylene oxide specifically, it is included in the highly preferred nonionogenic tenside in the anhydrous component of particulate of the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, and uncle or secondary position comprise 6-22 carbon atom usually.Particularly preferably being the every mol of alcohol and the 2-9 mole of the alkyl with 8-20 carbon atom, specifically is the condensation product of 3 or 5 moles of ethylene oxide. The nonionic polyhydroxy fatty acid amide surfactant

Polyhydroxy fatty acid amide is to be used for the highly preferred nonionogenic tenside of the present invention, particularly has those of following structural formula: R ²CONR ¹Z, wherein R ¹Be H, C _1-18, preferred C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Or C ₇-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is the polyhydroxy alkyl with the straight-chain alkyl that is connected directly to few 3 hydroxyls, or its alkoxy derivative (preferred ethoxylation or propoxylation).Z preferably derives from the reducing sugar in the reductive amination process; More preferably Z is a glycosyl.

Being used for the highly preferred nonionic polyhydroxy fatty acid amide surfactant of the present invention is C ₁₂-C ₁₄, C ₁₅-C ₁₇And/or C ₁₆-C ₁₈Alkyl N-methyl glucose amide.

C particularly ₁₂-C ₁₈Alkyl N-methyl glucose amide and every mol of alcohol and 2-9 mole, the particularly condensation product of 3 or 5 moles of ethylene oxide with the alkyl that contains 8-20 carbon atom.

Polyhydroxy fatty acid amide can prepare with any suitable method.A kind of particularly preferred method is described in detail among the WO9206984. The nonionic fatty acid amide surfactant

Fatty acid amide surfactant or alkoxylated fatty acid acid amides comprise those with following formula: R ⁶CON (R ⁷) (R ⁸), R wherein ⁶For comprising 7-21, preferred 9-17 carbon atom or even the alkyl of 11-13 carbon atom, R ⁷And R ⁸Respectively be independently selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein x is 1-11, preferred 1-7, more preferably 1-5, preferred thus R ⁷With R ⁸Difference, one has x and is 1 or 2, one to have x be 3-11 or preferred 5. Nonionic fatty acid alkyl ester surfactant

Fatty acid alkyl ester comprises having formula R ⁹COO (R ¹⁰) those, R wherein ⁹Be to contain 7-21, preferred 9-17 carbon atom or even the alkyl of 11-13 carbon atom, R ¹⁰Be C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, or-(C ₂H ₄O) _xH, wherein x is 1-11, preferred 1-7, more preferably 1-5, preferred thus R ¹⁰Be methyl or ethyl. The nonionic alkyl polysaccharide surfactant

Alkyl polysaccharide also can be included in the particulate anhydrous material of the present invention, for example be disclosed among the US 4565647 of the Llenado that authorized on January 21st, 1986 those, the hydrophilic polysaccharide base that they have the hydrophobic group that contains 6-30 carbon atom and comprise 1.3-10 sugar unit, for example many glycosides.

Preferred alkyl polyglycoside has following 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 carbon atom; N is 2 or 3; T is 0-10; X is 1.3-8.This glycosyl is preferably obtained by glucose. Cats product

The another kind of preferred component of the present composition is a cats product, and by the weight of said composition, preferably its content is 0.1%-60%, more preferably 0.4%-20%, most preferably 0.5%-5%.

When existing, the ratio of anion surfactant and cats product is preferably 25: 1-1: 3, more preferably 15: 1-1: 1, most preferably 10: 1-1: 1.The ratio of cats product and stablizer is preferably 1: 30-20: 1, more preferably 1: 20-10: 1.

The preferred cationic tensio-active agent is selected from cationic ester tensio-active agent, cation mono alkoxylated amines tensio-active agent, positively charged ion dialkoxy amine tensio-active agent and its mixture. Cation mono alkoxylated amines tensio-active agent

Be used for the cation mono alkoxylated amines tensio-active agent that the present invention chooses wantonly and have general formula: R wherein ¹Be to contain about 18 carbon atoms of the 6-that has an appointment, preferred about 16 carbon atoms of 6-, the most preferably from about alkyl or the alkenyl of about 11 carbon atoms of 6-; R ²And R ³Each is the alkyl that contains about 3 carbon atoms of 1-independently, preferable methyl; R ⁴Be selected from hydrogen (preferably), methyl and ethyl, X-provides electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A is selected from C ₁-C ₄Alkoxyl group, particularly oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and its mixture; P is that 1-is about 30, and preferred 1-is about 15, and most preferably 1-about 8.

Be used for highly preferred cation mono alkoxylated amines tensio-active agent of the present invention and have following formula: R wherein ¹Be C ₆-C ₁₈Alkyl and their mixture, preferred C ₆-C ₁₄, C particularly ₆-C ₁₁Alkyl, preferred C ₈And C ₁₀Alkyl, X provide any suitable negatively charged ion of charge balance, preferred chlorine or bromine.

As described, the compound of the above-mentioned type comprises wherein oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy, isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or the unitary mixture of i-Pr displaced those. Positively charged ion dialkoxy amine tensio-active agentBe used for positively charged ion dialkoxy amine tensio-active agent of the present invention and have general formula:

R wherein ¹Be to contain about 18 carbon atoms of the 6-that has an appointment, preferred about 16 carbon atoms of 6-, more preferably 6-is about 11, most preferably from about the alkyl of about 10 carbon atoms of 8-or alkenyl part; R ²Be the alkyl that contains 1-3 carbon atom, preferable methyl; R ³And R ⁴Can change independently, they are selected from hydrogen (preferably), methyl and ethyl; X-is enough to provide electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A and A ' can change independently, respectively are selected from C ₁-C ₄Alkoxyl group, particularly oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and their mixture; P is that 1-is about 30, and preferred 1-is about 4, and q is that 1-is about 30, and preferred 1-is about 4, and most preferably p and q are 1.

Be used for the highly preferred positively charged ion dialkoxy of the present invention amine tensio-active agent and have following formula:

R wherein ¹Be C ₆-C ₁₈Alkyl and its mixture, preferred C ₆, C ₈, C ₁₀, C ₁₂, C ₁₄Alkyl and its mixture, X provides any suitable negatively charged ion of charge balance, preferred chlorine.About above-mentioned positively charged ion dialkoxy amine formula, in preferred compound, R ¹Be by (cocounut oil) C ₁₂-C ₁₄The lipid acid of moieties obtains, R ²Be methyl, ApR ³And A ' _pR ⁴All are monosubstituted ethoxies.

Be applicable to that other positively charged ion dialkoxy amine tensio-active agents of the present invention comprise the compound of following formula: R wherein ¹Be C ₆-C ₁₈Alkyl, preferred C ₆-C ₁₄Alkyl, p are that 1-is about 3 independently, and q is that 1-is about 3, R ²Be C ₁-C ₃Alkyl, preferable methyl, X is a negatively charged ion, particularly chlorine or bromine.

Other compounds of the above-mentioned type comprise wherein oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or the unitary mixture of i-Pr displaced those. Amphoterics

Be used for the amphoterics that the present invention is fit to and comprise amine oxide surfactant and alkyl both sexes carboxylic acid.

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

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

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

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

Detergent composition of the present invention can comprise prior art more known other decontamination actives or compositions.The definite character of these other components and its incorporation will depend on the physical form of composition and the definite character of its washing operation that is used for.

Other preferred components comprise spices, whitening agent or dyestuff or its mixture, and they can be sprayed onto on the concrete component of the present invention.

The present composition preferably contains one or more other detergent components, is selected from tensio-active agent, SYNTHETIC OPTICAL WHITNER, washing assistant, sequestrant, (other) alkali source, organic polyhydroxyl compound, enzyme, whitening agent, suds suppressor, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor. Heavy metal ion chelating agent

Heavy metal ion chelating agent also is other components that the present invention is suitable for.So-called heavy metal ion chelating agent has been meant the component of chelating heavy metal ion effect at this paper.These components also can have calcium and magnesium sequestering power, but preferably they demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

The content of heavy metal ion chelating agent is generally the 0.005-10% of present composition weight, preferred 0.1%-5%, more preferably 0.25-7.5%, most preferably 0.3-2%.

Be used for the heavy metal ion chelating agent that the present invention is fit to and include organic phosphonates, as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt.

Preferred diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1 in the above-mentioned substance, 1-diphosphonate, 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid and 1,1-hydroxyl ethane dimethylene phosphonic acids.

Other are applicable to that heavy metal ion chelating agent of the present invention comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxy propylidene diamines disuccinic acid or its any salt.

Other are applicable to that heavy metal ion chelating agent of the present invention is an iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid, and as EP-A-317,542 and EP-A-399, described in 133.At EP-A-5126, the iminodiethanoic acid described in 102-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are applicable to the present invention.At EP-A-509, the Beta-alanine-N described in 382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are fit to.

EP-A-476,257 have described the suitable sequestrant based on amino.EP-A-510,311 have described the suitable sequestrant that is obtained by collagen, Keratin sulfate or casein.EP-A-528,859 have described a kind of suitable alkyl imino oxalic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is fit to.Glycine acid amides-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDC) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is fit to.

Particularly preferably be diethylene triaminepentaacetic acid(DTPA), quadrol-N, N '-disuccinic acid (EDDS) and 1, the ammonium salt of 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or its basic metal, alkaline-earth metal, ammonium or replacement, or its mixture. The perhydrate SYNTHETIC OPTICAL WHITNER

Preferred detergent composition of the present invention comprises peroxygen bleach, preferably includes hydrogen peroxide cource and bleach precursor or activator.Because the present invention has improved the release of product in washing, it has increased bleaching effectiveness and has reduced the fabric damage that is caused by the SYNTHETIC OPTICAL WHITNER that exists in the washing composition.

Preferred hydrogen peroxide cource is the perhydrate SYNTHETIC OPTICAL WHITNER, for example peroxyboric acid metal-salt, more preferably percarbonic acid metal-salt, particularly sodium salt.Perborate can be monohydrate or tetrahydrate.SPC-D has corresponding to 2Na ₂CO ₃-3H ₂O ₂Chemical formula, it can be purchased by crystalline solid forms.

Particularly percarbonate is preferably coated.The coating-forming agent that is fit to is that prior art is known, comprises silicate, magnesium salts and carbonate.

Peroxide Potassium peroxysulfate, its sodium salt are the optional inorganic perhydrate salts of another kind that is used for detergent composition of the present invention. The organic peroxide acid bleach systems

Present composition preferable feature is the organic peroxide acid bleach systems.In a kind of embodiment preferred, bleach systems contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Situ reaction by precursor and hydrogen peroxide cource can produce organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER, perborate bleach for example of the present invention.In another preferred embodiment, the ready-formed organic peroxide acid is introduced directly in the composition.Also can imagine the composition that contains with the mixture of ready-formed organic peroxide acid blended hydrogen peroxide cource and organic peroxy acid precursor. Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that produces peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually, peroxyacid bleach precursor is expressed from the next: Wherein, L is a leavings group, and X is any functional group substantially, makes the peroxy acid structure that produces when crossing hydrolysis be:

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

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

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

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

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

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

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

Preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, N ¹, N ¹-tetra-acetylatedization Alkylenediamine, wherein, alkylidene group comprises 1-6 carbon atom, and particularly wherein alkylidene group comprises those compounds of 1,2 and 6 carbon atom.Preferred especially tetraacetyl ethylene diamine (TAED).TAED preferably is not present in the agglomerated particle of the present invention, comprises in this particulate detergent composition but preferably be present in.

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

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

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.Suitable O-acylations peroxybenzoic acid precursors compound comprises and replacing and unsubstituted benzoyloxy benzene sulfonate; and Sorbitol Powder, glucose and all sugar are carried out benzoylated product with benzoylation reagent; those compounds of inferior acid amide type comprise the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other are useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid. Prefabricated organic peroxide acid

Detergent composition of the present invention also can comprise the ready-formed organic peroxide acid except that comprising organic peroxyacid bleach precursor compound or as selecting in addition, in the weight of the present composition, its content is generally 1-15%, more preferably 1-10%.

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

Wherein, R ¹Be alkyl, aryl or the alkaryl with 1-14 carbon atom, R ²Be alkylidene group, arylidene and the alkyl arylene with 1-14 carbon atom, R ⁵For H or have alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy acid compound that such acid amides replaces is disclosed among the EP-A-0170386.

Other organic peroxide acids comprise diacyl and four acyl peroxides, particularly diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.Single-as and two to cross nonane diacid, single-or two cross undecane dicarboxylic acid and the amino oxy hexanoic acid of crossing of N-naphthoyl also is suitable for the present invention.Enzyme

Can be used for another kind of preferred ingredient of the present invention is one or more additional enzymes.

Preferred additional enzymes material comprises the commercial lipase of purchasing, at, amylase, neutrality and Sumizyme MP, cellulase, restriction endonuclease (endolase), esterase, polygalacturonase, Sumylact L and the peroxidase that is routinely added in the detergent composition.Suitable enzyme is discussed in US3519570 and 3533139 to some extent. Organic polyhydroxyl compound

Organic polyhydroxyl compound is preferred other components of the present composition.

The so-called herein organic polyhydroxyl compound meaning is meant any basically organic polyhydroxyl compound that is used as tackiness agent, dispersion agent, anti redeposition agent and soil-suspending agent in detergent composition usually, be included in any high molecular organic polyhydroxyl compound that is stated as the clay flocculating agent herein, comprise ethoxylation (gathering) the amine clay class washing agent/anti redeposition agent of quaternary.

Press composition weight meter, the incorporation of organic polyhydroxyl compound in detergent composition of the present invention is generally 0.01-30%, preferred 0.1-15%, more preferably 0.5-10%.

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

Polyamino compound can be used for the present invention, comprises those materials that obtained by aspartate-derived, for example EP-A-305282, EP-A-305283 and EP-A-351629 described those.

Comprising the ter-polymers, particularly molecular-weight average that are selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol monomeric unit is 5, and 000-10, those of 000 also are applicable to the present invention.

Other organic polyhydroxyl compounds that are fit to add in the detergent composition of the present invention comprise derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.

Other useful organic polyhydroxyl compounds are that polyoxyethylene glycol, particularly molecular weight are 1000-10000, more preferably 2000-8000, most preferably from about those polyoxyethylene glycol of 4000.

The highly preferred polymeric component of the present invention is the U.S. Pat 5415807 according to the U.S. Pat 4968451 of Scheibel etc. and Gosselink etc., particularly according to the cotton and the non-cotton dirt release agent polymkeric substance of U.S. Patent application 60/051517.

Be used for another kind of organic compound of the present invention, it is a kind of preferred clay suspending agent/anti redeposition agent, and it can be cationic ethoxy monoamine and the diamines with following formula:

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

Be used for other dispersion agent/anti redeposition agents of the present invention and be described in EP-B-111965, US4659802 and US 4664848. Press down foam system

When detergent composition of the present invention is mixed with the composition of machine washing usefulness, can comprise a kind of foam system that presses down, by the weight of composition, its content is 0.01-15%, preferred 0.02-10%, more preferably 0.05-3%.

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

Defoaming compounds is meant that to detergent composition solution for example inhibiting any compound or its mixture are played in foaming that produces when particularly stirring this solution or foaming.

Being used for the particularly preferred defoaming compounds of the present invention is the polysiloxane defoaming compounds, and it is defined as any defoaming compounds that comprises the polysiloxane component at this paper.This polysiloxane defoaming compounds generally also contains silica component.Used herein and also be that the term " polysiloxane " of industrial common employing comprises the various relative high molecular weight polymers that contain siloxane unit and all kinds alkyl.Preferred polysiloxane defoaming compounds is a siloxanes, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocking.

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

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

The preferred foam system that presses down comprises: (a) defoaming compounds, and preferred polysiloxane defoaming compounds most preferably comprises the polysiloxane defoaming compounds of following composition:

(i) polydimethylsiloxane, its content accounts for the 50-99% of polysiloxane defoaming compounds weight, preferred 75-95%; With

(ii) silicon-dioxide, its content accounts for the 1-50% of polysiloxane/silicon-dioxide defoaming compounds weight, preferred 5-25%;

The incorporation of wherein said silicon-dioxide/polysiloxane defoaming compounds is 5%-50%, preferred 10%-40% weight; (b) a kind of compound dispersing agent, most preferably comprise silicone glycol rake formula multipolymer (rakecopolymer), its polyoxyalkylene content is 72-78%, and the ratio of oxygen ethene and oxypropylene is 1: 0.9-1: 1.1, its content is 0.5-10%, preferred 1-10% weight; Particularly preferred the type silicone glycol rake formula multipolymer is DCO544, is purchased with trade(brand)name DCO544 from DOW Corning company;

(c) a kind of inertia carrying object compound, most preferably it comprises C ₁₆-C ₁₈Ethoxylated alcohol, its ethoxylation degree are 5-50, preferred 8-15, and its content is 5-80%, preferred 10-70% weight.

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

Other highly preferred foam systems that press down comprise polydimethylsiloxane or polysiloxane mixture for example polydimethylsiloxane, silico-aluminate and multi-carboxy acid copolymer, for example lactic acid (laic) and acrylic acid multipolymer. The polymeric dye transfer inhibitor

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

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

The present composition also randomly contains the hydrophilic white dyes of known some type of prior art of 0.005% to 5% weight of having an appointment. The polymerization dirt release agent

Can randomly use the polymerization dirt release agent in the present composition, hereinafter referred is " SRA ".If you are using, SRA ' s generally accounts for 0.01% to 10.0% weight of composition, is typically 0.1% to 5% weight, preferred 0.2% to 3.0% weight.

The hydrophobic part that preferred SRA ' s generally has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic and is deposited on the hydrophobic fiber and keeps being attached thereto in whole washing and rinse cycle, so it is as the fixture of hydrophilic segment.This can be so that handle institute's spot easier being cleaned in washing process afterwards of generation subsequently with SRA.

Preferred SRA ' s comprises the terephthalate of oligomerisation, and it generally by comprising the method preparation of at least a transesterify/oligomerisation reaction, carries out under metal catalyst such as titanium alkoxide (IV) usually.This ester can use can by one, two, three, four or more position add other monomers preparations of ester structure, certainly, do not form fine and close full crosslinking structure.

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

SRA ' s also comprises: the simple copolymerization block thing of ethylene terephthalate or terephthalic acid propylene glycol ester and polyoxyethylene or polyoxypropylene terephthalate, referring to the U.S. Pat 3959230 of the Hays on May 25th, 1976 and the U.S. Pat 3893929 of the Basadur on July 8th, 1975; Derivatived cellulose such as the hydroxy ethers cellulose polymer compound bought from Dow by METHOCEL; C1-C4 alkylcellulose and C4 hydroxy alkyl cellulose are referring to the people's such as Nicol on December 28th, 1976 U.S. Pat 4000093; And methyl cellulose ether, it is about 2.3 for about 1.6-that its each anhydroglucose unit has average substitution degree (methyl), the aqueous solution by 2% 20 ℃ down the soltion viscosities of mensuration be about 120 centipoises of about 80-.This material can be buied by METOLOSESM100 and METOLOSE SM200, and they are the trade(brand)names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK production.

Another kind of SRA ' s comprises: (I) use vulcabond coupler and polyester construction banded nonionic terephthalate, referring to people's such as people's such as Violland U.S. Pat 4201824 and Lagasse U.S. Pat 4240918; (II) have the SRA ' s of carboxylicesters end group, it transforms terminal hydroxy group and becomes the trimellitate preparation by trimellitic acid 1,2-anhydride is added among known SRA ' s.By suitable selecting catalyst, trimellitic acid 1,2-anhydride forms the end group banded key with polymkeric substance, and this is to carry out by the isolated carboxylicesters of trimellitic acid 1,2-anhydride rather than by opening the acid anhydride key.Nonionic or negatively charged ion SRA ' s can be used as starting raw material, as long as have can esterified hydroxyl end groups for they, referring to people's such as Tung U.S. Pat 4525524.Other type comprises: (III) link the SRA ' s based on the negatively charged ion terephthalate of urethanes, referring to people's such as Violland U.S. Pat 4201824. Other optional ingredients

Other optional ingredients that are fit to be included in the present composition comprise spices, spot jewelry, pigment or dyestuff, filling salt, and sodium sulfate is preferred filling salt.In addition, can contain a small amount of (for example being lower than about 20% weight) neutralizing agent, buffer reagent, phase modifier, hydrotropic agent, enzyme stabilizers, polyacid, foaming regulator, opalizer, antioxidant, sterilant and dyestuff, for example those (they quote for referencial use at this paper) of describing in the U.S. Pat 4285841 of the Barrat that authorizes on August 25th, 1981 etc.It is highly preferred that the spices of encapsulate, preferably include starch encapsulate thing.

In the present composition, when dyestuff and/or spices were directed onto on the another kind of component, preferably this component did not comprise the nonionic alcohol alcoxylates tensio-active agent of sprinkling. The form of composition

The present composition can pass through prepared in various methods, comprise mixed composition, comprise that all cpds that will comprise in the detergent component is dried mixed, for example agglomeration of die mould (compaction), push, make sheet or spraying drying, or the mixing of these technology, component of the present invention thus also can comprise extruding and agglomeration, or spraying drying prepare by for example die mould.

Composition of the present invention can be taked various solid-state physics forms, wraps for example sheet, thin slice, lozenge and bar, and preferred said composition is particle or sheet.

The present composition also can be used for or the use that combines with compositions of additives that the bleaching compositions of additives for example comprises chlorine bleach.

Said composition preferably has density greater than 350g/l, more preferably greater than 450g/l, or even greater than 570g/l.

Below be some embodiment according to detergent composition of the present invention. That uses among the embodiment writes a Chinese character in simplified form

In the detergent composition of following example, the component symbol of writing a Chinese character in simplified form has following implication: LAS: straight chain C _11-13Sodium alkyl benzene sulfonate LAS (I): contain straight chain C _11-13The thin slice LAS (II) of sodium alkyl benzene sulfonate (90%) and sodium sulfate and moisture content: straight chain C _11-13Alkyl benzene sulphonate (ABS) potassium MES: α-sulfonated C ₁₈Fatty acid methyl ester TAS: tallow alkyl sodium sulfate C _XyAS: C _1X-C _1YSodium alkyl sulfate C46SAS: C ₁₄-C ₁₆Secondary (2,3) sodium alkyl sulfate C _XyE _zS: with the C of Z moles of ethylene oxide condensation _1X-C _1ySodium alkyl sulfate C _XYE _Z: with the condensation of average Z moles of ethylene oxide mainly be the C of straight chain _1X-C _1yPrimary alconol QAS: R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₁₂-C ₁₄QAS1: R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH) o, R ₂=C ₈-C ₁₁SADS: formula 2-(R) C ₄H ₇-1,4-(SO ₄-) ₂C ₁₄-C ₂₂Alkyl two sodium sulfate, wherein R=C ₁₀

-C ₁₈SADE2S: formula 2-(R) C ₄H ₇-1,4-(SO ₄-) ₂C ₁₄-C ₂₂Alkyl two sodium sulfate, wherein R=C ₁₀

-C ₁₈, condensation z moles of ethylene oxide APA: C ₈-C ₁₀Amido propyl-dimethyl amine soap: straight-chain alkyl carboxylic acid's sodium obtains STS by 80/20 mixture of butter and coconut fatty acid: toluenesulfonic acid sodium salt CFAA: C ₁₂-C ₁₄(cocounut oil) alkyl N-methyl glucose amide TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide TPKFA: C ₁₆-C ₁₈The full cut lipid acid of topping STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The hydrated sodium aluminosilicate of O, primary particle size are 0.1-10

Micron (weight of representing by moisture-free basis) NaSKS-6 (I): formula δ-Na ₂Si ₂O ₅Crystalline layered silicate, its average particle size is 18 microns, extremely

The granularity of few 90% (weight) is lower than 65.6 microns NaSKS-6 (II): formula δ-Na ₂Si ₂O ₅Crystalline layered silicate, its average particle size is 18 microns, extremely

The granularity of few 90% (weight) is lower than 42.1 microns citric acids: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: granularity is a 200-900 micron anhydrous sodium carbonate supercarbonate: size-grade distribution is at the anhydrous sodium bicarbonate silicate of 400-1200 micron: amorphous sodium silicate (SiO ₂: Na ₂O ratio=2.0: 1) vitriol: anhydrous sodium sulphate sal epsom: anhydrous magnesium sulfate Citrate trianion: citrate trisodium dihydrate, activity 86.4%, size-grade distribution is little at 425-850

Rice MA/AA: 1: 4 toxilic acid/acrylic copolymer, the about 70000MA/AA of molecular-weight average (1): 4: 6 toxilic acid/acrylic copolymer, the about 10000AA of molecular-weight average: the polyacrylic acid sodium polymer CMC of molecular-weight average 4500: the plain ether of sodium carboxyme-thylcellulose fibre: the polymerization degree is 650 methyl cellulose ether, is purchased by Shin Etsu Chemicals

Get proteolytic enzyme: by the albumen water of Novo Industries A/S with trade(brand)name Savinase sale

Separate enzyme, have 3.3% weight organized enzyme proteolytic enzyme I: the proteolytic ferment of in WO95/10591, describing, have 4% weight organized enzyme,

Sell Alcalase by Genencor Int.Inc.: the proteolytic ferment by Novo Industries A/S sells has 5.3% weight

Amount organized enzyme cellulase: by the cellulase of Novo Industries A/S with trade(brand)name Carezyme sale,

Has 0.23% weight organized enzyme amylase: by the shallow lake of Novo Industries A/S with trade(brand)name Termamyl 120T sale

The powder enzyme has 1.6% weight organized enzyme amylase II: disclosed amylase lipase in PCT/US9703635: by the lipolytic enzyme of Novo Industries A/S with trade(brand)name Lipolase sale,

Has 2.0% weight organized enzyme lipase (1): sell with trade(brand)name Lipolase Ultra by Novo Industries A/S

Lipolytic enzyme has 2.0% weight organized enzyme Endolase: endoglucanase, sell by Novo Industries A/S, and have 1.5%

Weight organized enzyme PB4: standard type NaBO ₂.3H ₂O.H ₂O ₂Sodium perborate tetrahydrate PB1: standard type NaBO ₂.H ₂O ₂Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER SPC-D: standard type 2Na ₂CO ₃3H ₂O ₂SPC-D DOBS: the last of the ten Heavenly stems acyloxy benzene sulfonate; sodium-salt form DPDA: diperoxy dodecanedioic acid NOBS: nonanoly acyloxy benzene sulfonate; sodium-salt form NACA-OBS: (6-nonanoyl caproyl) oxygen benzene sulfonate LOBS: 12 carbon acyloxy benzene sulfonate DOBS of sodium-salt form: the acyloxy benzene sulfonate DOBA in the last of the ten Heavenly stems of sodium-salt form: caprinoyl aminobenzoic acid TAED: tetraacetyl ethylene diamine DTPA: diethylene triaminepentaacetic acid(DTPA) DTPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shan all with trade(brand)name Dequest

2060 sell EDDS: quadrol-N, N '-disuccinic acid, (S, S) isomer, the photoactivated SYNTHETIC OPTICAL WHITNER of sodium-salt form: encapsulate soluble polymer or by its sulfonation phthalocyanine phthalocyanine zinc that carries or encapsulate in solubility

Polymkeric substance or the aluminum phthalocyanine whitening agent that carries by it 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-phenylamino-6-morpholino-1,3,5-triazines-2-yl) amino) stilbene-

2:2 '-disulfonic acid disodium HEDP: hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid PEG _x: polyoxyethylene glycol, molecular weight is x (general 4000) PEO: polyoxyethylene, molecular-weight average 50000TEPAE: ethoxylation tetren PVI: polyvinyl imidazol, molecular-weight average 20000PVP: polyvinylpyrrolidonepolymers polymers, molecular-weight average 60000PVNO: polyvinylpyridine N-oxide polymer, molecular-weight average 50000PVPVI: the multipolymer of Polyvinylpyrolidone (PVP) and vinyl imidazole, molecular-weight average 20000QEA: two ((C ₂H ₅O)-(C ₂H ₄O) (CH n) ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two ((C ₂H ₅O)-(C ₂H ₄O)) _nN=20-30SRP1 wherein: the end capped polyester SRP2 of negatively charged ion: diethoxyization is gathered (phthalic acid 1,2 inferior propyl ester) lack segmented copolymer PEI: polyethylene imine based, molecular-weight average 1800, the average ethoxylation of each nitrogen-atoms

Degree is 7 ethylene oxy residue polysiloxane defoamers: the polydimethylsiloxane foam control agent with as the polysiloxane-oxyalkylene copolymerization of dispersion agent

The mixture of thing, the weight ratio of described foam control agent and described dispersion agent are 10: 1-

100: 1 opalizers: water base single styrene latex mixture, by BASF Aktiengesellschaft

Sell wax with trade(brand)name Lytron 621: paraffin Embodiment 1

Preparing washing agent composition, the powder that it comprises blowing comprises the agglomerate of crystalline layered silicate and anion surfactant, effervescent granules and do bleach activator particles, SPC-D, Trisodium Citrate and the suds suppressor that mixes.

Prepare each particulate matter and under the mixing of gentleness, for example in Nautamixer, do and mixed at least 4 minutes. The powder of preparation blowing

Finally the powder of blowing is composed as follows: Component % in the blowing powderSodium n-alkylbenzenesulfonate (LAS) 20 acrylic acid/maleic acid 5 sodium sulphate 16 sodium carbonate 31 natrium citricums 20 water 8

Powder with the blowing of standard spray drying method for preparation.Above component water is mixed into slip.This hydrous slurry is with intermittence or continuous processing preparation.In this case, use batch mixer or " crutcher ", wherein various detergent components are dissolved in the water, or water makes slip, obtain containing the slip of 35% water.The content of water can be in about 60% weight range of about 20%-, the about 40% weight water of preferably about 30%-.In this embodiment, to add the interpolation of making hydrous slurry in the water to be as above listed in the final composition of powder of blowing to component in proper order.With the pumping under high pressure of this hydrous slurry, enter in the spray-drying tower then, remove excessive water there, generate flowable powder-like product (powder of blowing) by atomizing nozzle.Sieve out fine powder by sieve. The preparation of crystalline layered silicate/anionic surfactant granules

The agglomerate that comprises 70%SKS6 and 30%LAS with conventional agglomeration method preparation. The preparation of effervescent granules

Preparation has the particle of following composition: Component Component %Oxysuccinic acid 44 sodium bicarbonates 40 yellow soda ash 16

Prepare particle by rolled-on method.The raw material of ratio shown in above is sent under 80kN pressure in the Pharmapaktor L200/50P pressure roller machine, and it is fixed with the slick roller of concave surface, and this roller is provided with 0.3mm axial groove line.The made then thin slice grinding mill FC200 that quotes carries out compacting, and this equipment has the mesh size of selection, to produce required particle size.Sieve this product, remove fine powder.

These three kinds of components and following other listed dried components that add are pressed the following mixed of giving, make detergent composition of the present invention. Component % in detergent compositionSpray-dired 42 bleach-activating agent 3 SPC-D, 15 Trisodium Citrate 10SKS6/LAS particles, 10 suds suppressor particles (95%PEG, 5% polysiloxane), 4 effervescent granules 16 Embodiment 2

Provide among the prescription A-D of the other embodiment of detergent composition of the present invention in following table, it has also illustrated the method for preparing this embodiment.

	?A	?B	?C	?D
					The blowing powder
LAS	10.0	?10.0	?5.0	?8.0
					TAS	-	?1.0	?-	?1.0
MBAS	-	?-	?-	?-
					C 45AS	-	?-	?-	?-
C 45AE 3S	-	?-	?-	?-
					QAS	-	?-
DTPA, HEDP and/or EDDS	0.3	?0.3	?0.3	?0.3
					MgSO4	0.5	?0.4	?0.5	?0.5
Trisodium Citrate	10.0	?12.0	?-	?-
					Yellow soda ash	15.0	?8.0	?10.0	?7.0
Sodium sulfate	5.0	?5.0	?5.0	?5.0
					Water glass 1.6R	-	?-	?-	?-
Zeolite A	-	?-	?16.0	?18.0
					SKS-6	-	?-	?-	?-
MA/AA or AA	1.0	?2.0	?1.0	?2.0
					PEG?4000	-	?2.0	?-	?2.0
QEA	1.0	?-	?1.0	?-
					Whitening agent	0.05	?0.05	?0.05	?0.05
Silicone oil	0.01	?0.01	?0.01	?0.01

					Agglomerate
SKS-6	?6.0	?5.0	?6.0	?8.0
					LAS	?4.0	?5.0	?4.0	?5.0
					Do and add grain fraction
Toxilic acid/carbonate (40: 20: 40)	?8.0	?10.0	?8.0	?10.0
					QEA	?-	?-	?-	?-
NACAOBS	?3.0	?-	?3.0	?-
					NOBS	?-	?3.0	?-	?3.0
TAED	?2.5	?-	?2.5	?-
					MBAS	?-	?-	?-	?-
LAS(I)	?5.0	?3.0	?10.0	?10.0
Spray
					Whitening agent	?0.2	?0.2	?0.2	?0.2
Dyestuff	?-	?-	?-	?-
					C24AE5	?-	?-	?-	?-
Perfume	?-	?-	?-	?-
Do and add
					Citrate trianion	?4.0	?-	?-	?-
Percarbonate	?15.0	?3.0	?15.0	?3.0
					Perborate	?-	?-	?-	?-
Photobleach	?0.02	?0.02	?0.02	?0.02
					Enzyme (Mierocrystalline cellulose, amylase,	?1.5	?0.3	?1.3	?0.3

Proteolytic enzyme, lipase)
					Carbonate	-	?-	?0.0	?10.0
Essence (encapsulate)	0.6	?0.5	?0.6	?0.5
					Suds suppressor	1.0	?0.6	?1.0	?0.6
Soap	0.5	?0.2	?0.5	?0.2
					Citric acid	-	?-	?-	?-
Painted carbonate (blue, green)	0.5	?0.5	?0.5	?0.5
					SKS-6	-	?-	?-	?-
Filler to 100%

Claims (18)

CLAIMS 1. A solid detergent composition comprising 10-60% by weight of a surfactant system and which has a maximum residual index of 25 and a maximum secondary residual index of 15. 2. A detergent composition according to claim 1 having a maximum residue index of 20. 3. A detergent composition according to claim 2 having a maximum residue index of 15. 4. A detergent composition according to any preceding claim having a maximum secondary residue index of 10. 5. A detergent composition according to any preceding claim comprising a builder system comprising 60-100% by weight of water-soluble builder or mixtures thereof. 6. A detergent composition according to any preceding claim comprising less than 9% by weight of aluminosilicate builder, calculated on the total detergent composition. 7. A detergent composition according to any preceding claim comprising less than 5% by weight amorphous sodium silicate, calculated on the total detergent composition. 8. A detergent composition according to any preceding claim, wherein at least part of the surfactant system is present in the detergent composition as a granular component comprising a surfactant in close contact with at least part of the builder system. mixture. 9. A detergent composition according to any preceding claim comprising an aluminosilicate builder and an anionic surfactant, the detergent composition comprising (n) component (i), n being at least 2, silica-alumina The total amount of salt builder in the detergent composition is at least 5% by weight, the total amount of anionic surfactant in the detergent composition is at least 5% by weight, anionic surfactant and aluminosilicate builder The degree of mixing (M) of the lotion is 0-0.7, and M is ∑ _i ⁿ =1√(σ _i .ζ _i ), wherein σ is the fraction of the anionic surfactant in the component (i) that accounts for the composition; ζ is the fraction of aluminosilicate in component (i) in the composition. 10. A detergent composition according to claim 9, wherein M is 0-0.5. 11. A detergent composition according to any preceding claim comprising a granule comprising 35% to 68% by weight of crystalline layered silicate, 32% to 55% by weight of anionic surfactant and a maximum free water content of Less than 10% by weight. 12. A detergent composition according to any preceding claim comprising a nonionic surfactant which is sprayed onto preformed granules comprising surfactant and solid carrier material. 13. A detergent composition according to any preceding claim, further comprising a cationic surfactant. 14. A detergent composition according to any preceding claim which is substantially free of alkyl sulphate surfactants. 15. A detergent composition according to any preceding claim comprising a sudsing component comprising an intimate mixture of a substantially anhydrous stabilizer and sudsing system. 16. A detergent composition according to any preceding claim comprising a source of percarbonate bleach. 17. A detergent composition according to any preceding claim in the form of a detergent tablet. 18. Use of a detergent composition as defined in any preceding claim for cleaning soils in a washing method.