CN100366715C - Detergent particle - Google Patents

Abstract

The invention relates to improve dispensing of a detergent composition or particle by the use of a hydrotrope in a detergent composition or particle, comprising a surfactant component, preferably comprising an anionic sulphonate surfactant, and wherein on addition of the hydrotrope to the surfactant component, the viscosity of the surfactant component in water is reduced. The invention also relates to a detergent particle for use in detergent compositions, comprising an anionic sulphonate surfactant, present at a level of from 0.01 % to 20 % by weight of the particle, and a hydrotrope, present at a level of from 0.01 % to 45.0 % by weight of the particle, wherein of from 0.0 % to 30 % by weight of the particle of a phosphate component is present.

Description

Detergent particles

Technical field

The present invention relates to be used for the detergent particles of detergent composition, it contains a kind of anion sulfoacid salt surfactant and a kind of hydrotropic agent, wherein also has the phosphate component by particle weight calculating 0.0% to 30%.The invention still further relates to and use a kind of hydrotropic agent in detergent composition or particle, reduce the viscosity of the viscous mixture that contains surface active agent composition and water, this viscous mixture forms when surface active agent composition contacts with water.

The background of invention

The requirement that improves washing composition always being arranged in the middle of the human consumer of washing composition, make it to have better cleaning performance, is again economical in using simultaneously.Like this, the washing composition producer just is faced with their washing composition of improvement and unlikely owing to using more expensive component or production method to increase the such challenge of production cost.

Have been found that one of washing composition, particularly laundry and main difficulty that the human consumer met of dishwashing detergent product be divider, distribution device or or even in (tableware) washing machine, form the residue or the insoluble agglomerate of washing composition, particularly form the gel resistates.This phenomenon does not wish to take place, thereby may cause uncleanly outward appearance to machine because these resistatess or gel are difficult to remove from machine.Also have, the formation of resistates, insoluble agglomerate or gel can cause the uneconomic use of Betengent product: Betengent product is transported in the washing water by halves can cause relatively poor cleaning performance, removes non-consumer and additionally adds some Betengent products again in washing water.This is not the effective or economic usage of Betengent product, and is neither the human consumer desirable.

Like this, just require to improve the transmission performance of detergent composition in the water.A kind of scheme that addresses this problem is to improve the solubleness of washing composition.This has caused the change of washing composition composition and compound method.Yet, form gel or insoluble agglomerate even rapid dissolved washing composition also trends towards bonding together when at first contacting with water.Even dissolving more rapidly can cause the not minimizing of the duration of contact of lysate and water, this can not address this problem fully.Washing composition still has relatively poor transmission performance as a result.Washing composition relatively poor transmission problem in wash water also can solve by the distribution that improves washing composition.

The applicant has been found that this problem becomes when being used in the granular detergent composition even more obvious when surface active agent composition, particularly anion surfactant (it may be a part or most of water-soluble).This problem further increases when used anion surfactant is the anion sulfoacid salt surfactant.When this (anionic sulphonate) tensio-active agent is present in the dry granules, problem even also serious.Believe that gel formation can cause by the anion sulfoacid salt surfactant, because be that it becomes " gel " rather than is dissolved in the water fully when contacting with water.Other component of this phenomenon possibility overslaugh washing composition is transferred in the washing water.Further, believe when sulfosalt surfactant is present in the dry granules that the formation of gel even can increase is because dry granules is hygroscopic.After this gel that forms is difficult to distribute, and causes forming resistates and insoluble agglomerate in machine, particularly in divider or distribution device.

The applicant has now found that the problem of gel formation and bad distributivity can be resolved or improves by mix hydrotropic agent in the detergent particles of detergent composition or particularly this toward containing (anionic sulphonate) tensio-active agent.

Generally, hydrotropic agent is known in this area, and it is the compound with this character of solubleness of the compound that can increase microsolubility.Hydrotropic agent was in washing composition, particularly the various uses in liquid washing agent was described.WO 95/30730 has described hydrotropic agent as the phase stabilizing additive in the liquid washing agent.US 3,926, and 827 have described the component of hydrotropic agent as the maintenance oxygen bubbles, thereby give washing composition bigger volume.GB 1591516 has described hydrotropic agent as processing aid with the mobile detergent mixture that gains freedom.Yet, also do not know in the art to use hydrotropic agent in the granular detergent composition that contains the anion sulfoacid salt surfactant, to obtain the improved distribution performance of detergent composition.

In the present invention, believe that hydrotropic agent has reduced by the viscosity that is present in the gel that forms when (iodate) tensio-active agent in detergent particles or the detergent composition contacts with water.Like this, in machine, form insoluble agglomerate or gel or resistates and produced improved detergent composition and be assigned to the performance of going in the washing water by reducing.Washing composition agglomerate, resistates or gel are in machine, particularly the minimizing in divider or distribution device promptly causes outward appearance and the more effective performance of detergent composition that washing machine more cleans.

All documents of quoting in this manual all are incorporated herein by reference at relative section.

Summary of the present invention

According to the present invention, provide a kind of content that contains to count 0.01% to 20% anion sulfoacid salt surfactant and content by particle weight and count 0.01% to 45.0% hydrotropic detergent particles, also may have phosphate component in the particle by particle weight 0.0% to 30% by particle weight.According to the present invention, this particle can be used in the detergent composition.

The present invention also provides and has improved the detergent composition that distributes character, it is by containing surface active agent composition, preferably comprise and use a kind of hydrotropic agent to realize that (surface active agent composition wherein is preferably at 20 ℃ in a kind of detergent composition of anion sulfoacid salt surfactant or the particle, viscosity in 25% the aqueous solution is at least 15000cP by weight, viscosity usable surface promoting agent viscosity test method is measured), wherein, when in surface active agent composition, adding hydrotropic agent, the viscosity of surface active agent composition will reduce, and preferably reduce by 25% at least.

Detailed description of the present invention

Hydrotropic use

Hydrotropic agent of the present invention is to be used to contain in a kind of detergent composition or particle of surface active agent composition, to reduce the viscosity of surface active agent composition when contacting with water.Preferably, this hydrotropic agent is added to and reduces its viscosity in water in the surface active agent composition.The present invention preferably reaches such effect, and promptly surface active agent composition is at least 15000cP at 20 ℃, initial viscosity in 25% the aqueous solution by weight, and the tensio-active agent viscosity test that will describe below this is available is measured; When hydrotropic agent was used in the surface active agent composition, viscosity should reduce by 25% than initial viscosity.

This surface active agent composition comprises one or more and is selected from the following tensio-active agent that will describe.

Preferably, hydrotropic agent is used to spray-dired particle, wherein contain a kind of anion sulfoacid salt surfactant, it forms the heavy-gravity mixture that comprises tensio-active agent and water when contacting with water, it 20 ℃, have the viscosity of 15000cP at least in 25% the aqueous solution by weight, usable surface promoting agent viscosity test is measured.

The tensio-active agent viscosity test

In the tensio-active agent viscosity test, contain the surface active agent composition of detergent composition or particulate all surface promoting agent, by ratio and the content in each comfortable aqueous solution, can measure its viscosity.

At first, measure the viscosity A of surface active agent composition in water:

Restrain tensio-active agents to 10 and contain 0.5 gram NaSO ₄With 0.5 gram NaCO ₃30 the gram deionized waters 20 ℃ of mixing.The slurries that obtain placed for 30 seconds.The viscosity of slurries is measured with a Brookfield Digital Viscometer (DVII type), and this viscometer is furnished with the axle of a cover different diameter, and adjustable speed setter is arranged.Can select speed 12, axle 3.Axle reduced to make entering the mark of slurries on the axle that limits, and make it in 10 seconds, reach balance.Reading then with the centipoise is unit (cP, 1cP=0.01 pool=10 ^-3Nsm ²) viscosity A.

In a preferred embodiment of the present invention, the viscosity A of surface active agent composition is 15000cP at least, more preferably 18000cP at least.

Secondly, measure above-mentioned surface active agent composition and the hydrotropic agent viscosity B in water:

10 gram surface active agent compositions and x are restrained hydrotropic agent and contain 0.5 gram NaSO ₄With 0.5 gram NaCO ₃30 the gram deionized waters 20 ℃ of mixing.The slurries that obtain placed for 30 seconds.Brookfield Digital Viscometer of usefulness (DVII type) is measured the viscosity of slurries under the condition of speed 12, axle 3 as top.Axle is lowered to the axle scale that enters in the slurries up to limiting, and makes it reach balance in 10 seconds.Read then with the metric viscosity B of centipoise (cP).

Compare viscosity A and B value then, determine the reduction of viscosity with following formula:

For the present invention, that hydrotropic agent and consumption thereof should preferably reduce the viscosity to is few 25%, preferably more than 30%, most preferably more than 40%.

Detergent particles

Particle of the present invention can be used in the detergent composition.This detergent composition can mainly contain this particle, but preferred this detergent composition comprises this particle and other component, and the latter has different chemical constitutions, alternatively comprises hydrotropic agent and anion sulfoacid salt surfactant.

Preferably, the content of particle of the present invention in detergent composition, preferred not phosphatic composition is calculated as 5% to 85% by the weight of composition, and more preferably 10% to 70%, most preferably 30% to 60%.

Preferably, particle of the present invention contains a kind of anion sulfate acid salt surfactant, and the content of its existence calculates by particulate weight and is preferably 0.01% to 50%, and more preferably 1% to 20%, most preferably 2% to 10%.

Particle of the present invention is to be formed by a kind of method of drying step that comprises.The dried particles that this drying step produced generally has and is lower than 6% free water content by weight, preferably is lower than 1%, or more preferably less than 0.5%, most preferably is lower than 0.25%.

Employed here term free water content is to measure like this, promptly the basic detergent particles sample of 5 grams is placed in the Petri dish, sample is put in the convection furnace of 50 ℃ (122 ) into 2 hours, then measures because the weightlessness that evaporation of water causes.

Generally, particle of the present invention forms in a kind of like this technology, wherein the slurry that comprises this anion sulfoacid salt surfactant or slurry or the mixture forming particle that mixes and be dried, such as known in the art, a kind of preferable methods is a spraying drying.

Make a kind of preferable methods of this particulate and comprise that preparation contains the aqueous solution dispersion thing of component in the final particle, is commonly referred to slurries or slurry or mixes mixture.For saving energy and increasing the productivity of drying plant, this mixture that mixes should contain high solids content usually as far as possible, and for example 40% to 80%, remaining 20% to 60% is the water of equal amount for example.Can use more water, but just increase the requirement to energy like this, reduce the productivity of tower, the product that obtains may be more tacky and difficult mobile, usually can not obtain desirable low density base-material and final detergent composition particle.

Though can use other drying means, such as drum dried, tray drying, fluidised bed drying, film drying etc., most preferred method is a spraying drying, wherein mixes mixture and (is generally 3 to 50 kg/cm in elevated pressure ³, preferred 20 to 40 kg/cm ³) enter in the drying tower through one or more nozzles under the condition, wherein have the exsiccant air by be used for dry form mix the mixture droplet, it is spherical that particle is become.Replace nozzle, the spraying gun of other design of equal value also can use.Preferred spray tower design is an adverse current type, and tower height is generally 5 to 25 meters, and the warm air that enters is generally the combustion gas product of oil or gas, and its temperature is in 200 ° to 400 ℃ scopes, and the outlet air typical temperature is in 50 ° to 90 ℃ scopes.Also can use the counter-current tower design, wherein can obtain the air themperature of similar entrance and exit.

Generation is mixed the jet size of mixture droplet and should be selected like this, preferred granular size is formed, preferred value is 0.1 millimeter to 3.0 millimeters, preferably, when granular sizes all basically when spray tower takes out all in this scope, the underproof particle of but any size can be removed by screening, also can reduce the particle that its size makes becomes required size, or mixes in the mixture or later mix circulation again in the mixture same.

When having a kind of anion sulfate acid salt surfactant in final particle, this anion sulfate acid salt surfactant should be comprised in hydrotropic agent and anion sulfoacid salt surfactant and mix in the mixture.

Substantially not containing nonionogenic tenside and/or cationic softening agent or cats product to drying process in mixing mixture, may be useful to drying process with atomizing particularly.Like this, particle of the present invention preferably is substantially free of nonionogenic tenside and/or cationic softening agent or cats product.

According to the present invention, this particle contain by particulate weight calculate 0.0% to 30%, more preferably 0.0% to 20%, 0.0% to 8% phosphate component most preferably.Anion sulfoacid salt surfactant and hydrotropic agent are present in and are substantially free of in the phosphatic particle, and this may be useful especially for the present invention.

Alternatively, after drying is finished and is obtained the particle of required magnitude range, can in particle, add other detergent component, preferably by spraying fused component in the cylinder that tilts, it can be the spissated aqueous solution, but preferably not moisture, to the basic granules that is rolling, like this particle promptly by cylinder from top feed end to exhaust end.

This particle can be introduced in the detergent composition with any method known in the art, preferably this particle is joined in other detergent ingredients with dried forms.

The anion sulfoacid salt surfactant

The content of anion sulfoacid salt surfactant in particle counts 0.01% to 20% by particle weight, preferably by 0.5% to 18%, and more preferably by 3% to 15%, most preferably 5% to 15%.

The anion sulfoacid salt surfactant is preferably 50: 1 to 1: 1 to hydrotropic ratio in particle, more preferably 25: 1 to 1: 1, most preferably is 10: 1 to 2: 1.

Here the anionic sulphonate tensio-active agent of Shi Yonging comprises C ₅-C ₂₀Line style or branched alkyl benzene sulphonate (ABS), alkyl ester sulfonic acid, C ₆-C ₂₂Uncle or secondary alkane sulfonic acid, C ₆-C ₂₄The salt of alkene sulfonic acid, sulfonated poly carboxylic acid, alkyl glycerol sulfonic acid (or alternatively using corresponding acids); preferably from butter or cocounut oil deutero-alcohols institute deutero-, fatty acyl group glycerol sulfonate, fatty thiazolinyl glycerol sulfonate and their any mixture.

Positively charged ion in the anion sulfoacid salt surfactant can be hydrogen, ammonium or pure ammonium, but preferred sodium or potassium.

A kind of highly preferred anion sulfoacid salt surfactant is C ₁₀-C ₁₈, preferred C ₁₀-C ₁₆, C most preferably ₁₁-C ₁₃Branched or be more preferably the sodium or the sylvite of the alkyl benzene sulphonate (ABS) of line style.

Hydrotropic agent

According to the present invention, a kind of hydrotropic agent is present in this particle or is used in the particle or in the detergent composition.

This surface active agent composition, or particularly this anion sulfoacid salt surfactant (being contained in the surface active agent composition) are comprised in particle or the detergent composition, as mentioned above, can form the heavy-gravity mixture when contacting with water.Hydrotropic agent is the viscosity that is used for reducing this mixture, like this, when used herein, the term hydrotropic agent is any known hydrotropic agent that means in this area, and it can reduce contains water and surface active agent composition, particularly contains a kind of viscosity of anionic sulphonate surfactant mixtures.

In this class hydrotropic agent, can mention short chain (C ₁-C ₄) alkylaryl sulphonate.

Should be understood that also to comprise sulfonic acid in this present invention.Yet because particulate pH of the present invention generally is at alkaline range, so work as water, even in a small amount, at particle or contain when existing in the process for preparation of grains of composition, the hydrotropic agent component promptly mainly exists with its form of dissociative salt.In other words, though the form that hydrotropic agent can acid is added in the composition and goes, it may appear in the prescription with the form of salt derivative.

The water soluble salt that is used for the present invention comprises the basic metal of sulfonic acid, alkaline-earth metal, alkylamine and ammonium salt.Preferred salt is sodium, potassium and an alcohol salt and their mixture of sulfonic acid.

What specifically, be used for the present invention has tosylate, cumene sulfonate, an xylenesulfonate.Toluenesulphonic acids sodium salt most preferably, preferred toluene-sodium sulfonate.

The content of hydrotropic agent in particle counts 0.01% to 45% by particulate weight, and preferred 0.1% to 15%.More preferably 0.2% to 5%, also more preferably 0.5% to 2%, most preferably 0.8% to 1.8%.

When particle is used in the detergent composition, can comprise other hydrotropic agent in this detergent composition.

The anion sulfate acid salt surfactant

It is preferred and be present in the dry granules of the present invention most preferably that the other anion surfactant of (partly) is the anion sulfate acid salt surfactant to be present in the detergent composition camber.

When this uses, the anion sulfate acid salt surfactant is to mean line style and branched primary and secondary alkyl-sulphate, sulfated alkyl ether, fatty oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of vitriol such as the alkyl polyglucoside of glucosamine sulfate and alkyl polysaccharide class (compound of nonionic non-sulfuric acidization described here).

Alkyl sulfate surfactant most preferably is selected from line style and branched uncle C ₁₀-C ₁₈Alkyl-sulphate, more preferably C ₁₁-C ₁₅Branched alkyl-sulphate and C ₁₂-C ₁₄Straight-chain alkyl sulfate.

A kind of highly preferred sulfate surfactant is by butter or cocounut oil deutero-C by sulfation ₈-C ₁₈Sodium sulfate salt that alcohols produced or sylvite.C by PALM FATTY ACID or stearic fatty acid derived ₁₆-C ₁₈The sodium sulfate of alcohols or sylvite also are highly preferred.

The positively charged ion of anion sulfate acid salt surfactant can be hydrogen, ammonium or pure ammonium, but preferred sodium or potassium.

The preferred content of anion sulfate acid salt surfactant counts 0.01% to 50%, more preferably 1% to 20%, most preferably 2% to 10% by particulate weight.

Other component

Particle and/or contain in the particulate detergent composition of the present invention and also can comprise other composition or component.The precise nature of the washing operation that the amount that the precise nature of these other compositions and they are impregnated in will depend on the physical aspect of final composition and their when using.

As a kind of other composition, this particle preferably contains one or more builders, preferably aluminosilicate salt and/or organic multi-carboxylate's polymkeric substance, alkali source or their mixture.Preferably, be substantially free of nonionic and/or cats product in this particle.

Contain this detergent composition of particulate of the present invention, preferably contain one or more other detergent component, can be selected from other tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, acid source, builder, organic polymer, enzyme, froth suppressor, lime soap dispersing agent, soil-suspending agent, anti redeposition agent and corrosion inhibitor.

The exemplary list of other negatively charged ion, nonionic, both sexes and zwitterionic classes tensio-active agent and species thereof is given in the United States Patent (USP) 3,929,678 that licensed to Laughlin and Heuring on December 30th, 1975.Further example is given in (by Schwartz, I that Perry and Berch showed and II volume) in " tensio-active agent and washing composition " book.The tabulation of suitable cationic surfactants is given in the United States Patent (USP) 4,259,217 that licensed to Murphy on March 31st, 1981.

Other anion surfactant

According to comprising one or more other anion surfactants in detergent composition of the present invention and/or the particle.Basically any anion surfactant that is used for washing purpose can be comprised in this detergent composition or alternatively be included in the particle.These comprise alkyl ethoxy sulfuric acid, carboxylic acid and sarkosine tensio-active agent salt (comprise, for example, the ammonium salt of sodium, potassium, ammonium and replacement such as one, two and the salt of trolamine).

Other anion surfactant comprises fatty acid amide, dialkyl succinylsuccinate salt and the sulfosuccinate of isethionic acid salt such as acyl isethinate, N-acyl amino ethyl sulfonic acid salt, methylamino ethyl sulfonic acid, monoesters (the particularly saturated and undersaturated C of sulfosuccinate ₁₂-C ₁₈Monoesters), the dibasic acid esters of sulfosuccinate (particularly saturated and undersaturated C ₆-C ₁₄Dibasic acid esters), N-acyl sarcosinate class.Resin Acid and hydrogenated resin acids also are suitable, such as rosin, staybelite and be present in or derived from the Resin Acid and the hydrogenated resin acids of butter.

The content of anion surfactant is preferably 4% to 60%, more preferably 6% to 30%, most preferably 10% to 20% by weight in detergent composition.

Alkyl ethoxy sulfate surfactant

Alkyl ethoxy sulfate surfactant preferably is selected from the C of per molecule with 0.5 to 20 moles of ethylene oxide ethoxylation ₁₀-C ₁₈Alkyl-sulphate.More preferably be that this alkyl ethoxy sulfate surfactant is a per molecule with 0.5 to 7, the C of preferred 1 to 5 moles of ethylene oxide ethoxylation ₁₁-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate.

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 kind (" alkyl carboxyl "), secondary soap classes particularly described herein.

Suitable alkyl ethoxy carboxylate class comprises that formula is RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Those compounds, wherein R is a C ₆To C ₁₈Alkyl, x value scope is 0 to 10, ethoxylate is distributed as, calculate based on weight, x be the amount of zero material less than 20%, M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises that formula is RO-(CHR ₁-CHR ₂-O)-R ₃Those compounds, wherein R is a C ₆To C ₁₈Alkyl, x value are 1 to 25, R ₁And R ₂Be selected from hydrogen, methyl acidic group, Succinic Acid base, hydroxy-butanedioic acid base and their mixture, R ₃Be selected from hydrogen, replacement or the unsubstituted hydrocarbon that contains 1 to 8 carbon atom, and their mixture.

Suitable soap surfactants comprises and contains the unitary secondary soap surfactant of the carboxyl that is connected on the secondary carbon(atom).Here the preferred secondary soap surfactant of Shi Yonging is water miscible material, can be selected from 2-methyl isophthalic acid-hendecane carboxylic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water soluble salt of 2-amyl group-1-enanthic acid, some soap also can be comprised and is used as froth suppressor.

The basic metal sarcosinate surfactant

It is R-CON (R that other suitable anion surfactant has formula ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is a C ₅-C ₁₇Line style or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ions.Preferred examples has myristyl and the oil base methyl sarcosinate that exists with their sodium-salt form.

Cats product

Other preferred surfactants that is used for comprising the particulate detergent composition is one or more cats products.Suitable cationic surfactants comprises quaternary surfactant, can be selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein all the other positions on the N are all replaced by methyl, hydroxyethyl or hydroxypropyl.Another kind of preferred cationic surfactants is the C of quaternary ammonium alcohols ₆-C ₁₈The alkyl or alkenyl ester.Such as level Four cholinesterase class.

In comprising the particulate detergent composition, the content of cats product is preferably the weight 0.2% to 20% by composition, and more preferably 0.5% to 15%, also more preferably 1% to 10%, most preferably 1% to 5%.

Nonionogenic tenside

Comprise particulate detergent composition of the present invention and can contain a kind of nonionogenic tenside.Preferably do not contain nonionogenic tenside in the particle.Nonionogenic tenside is sprayable on particle of the present invention, and any basically nonionogenic tenside all can use at this.

In containing the particulate detergent composition, the content of nonionogenic tenside is preferably 1% to 30% by the weight of composition, and more preferably 2% to 25%, also more preferably 3% to 15%, most preferably 4% to 12%.

Oxyalkylated nonionogenic tenside

Basically any oxyalkylated nonionogenic tenside all is adapted at this use.But preferred ethoxylation and propenoxylated nonionogenic tenside.

The tensio-active agent of preferred alkoxylated can be selected from the nonionic condensation product of induced by alkyl hydroxybenzene, the alcohols of nonionic ethoxylation, the aliphatic alcohols of nonionic ethoxylated/propoxylated, the nonionic ethoxylated/propoxylated and condensation product propylene glycol, and the ethoxylate condensation product of non-ionic and propylene oxide/ethylenediamine adduct.

Nonionic alcohol alcoxylates tensio-active agent

The condensation product of aliphatic alcohols and 1 to 25 mole alkylene oxide, particularly oxyethane and/or propylene oxide is suitable for here using.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, uncle's or the second month in a season, and generally contain 6 to 22 carbon atoms.Particularly preferably be the alcohol of the alkyl that contains 8 to 20 carbon atoms and the condensation product of every mol of alcohol 2 to 10 moles of ethylene oxide.

The nonionic polyhydroxy fatty acid amide surfactant

Here the polyhydroxy fatty acid amide of Shi Yonging is that those structural formulas are R ²CONR ¹The compound of Z, wherein: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or their mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be a C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or their mixture; Z is the polyhydroxy alkyl with the line style hydrocarbyl chain that is connected directly to few 3 hydroxyls, or its a kind of oxyalkylated derivative (preferred ethoxylation or propenoxylated).Z preferably in reductive amination process by a kind of reducing sugar institute derived compounds, more preferably Z is the sugar alcohol base.

The nonionic fatty acid amide surfactant

The suitable fatty acids acidamide surfactant comprises that those have formula R ⁶CON (R ⁷) ₂Compound, R wherein ⁶Be an alkyl that contains 7 to 21 carbon atoms, preferred 9 to 17 carbon atoms, each R ⁷Can be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein the x value is in 1 to 3 scope.

The nonionic alkyl polysaccharide surfactant

Suitable as used herein alkyl polysaccharide has been disclosed the United States Patent (USP) 4 of the Llenado of issue on January 21st, 1986,565, in 647, it comprises the hydrophobic group and a polysaccharide that comprises 1-3 to 10 sugar unit, for example the polysaccharide glycosides hydrophilic radical that contain 6 to 30 carbon atoms.

Preferred APG has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _x

R wherein ²Can be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, alkyl wherein contains 10 to 18 carbon atoms; The n value is 2 or 3; The t value is 0 to 10, and the x value is 1.3 to 8.Glycosyl is preferably by the glucose deutero-.

Amphoterics

The selective amphoterics that is used for particle or comprises this particulate detergent composition comprises amine oxide surfactant and alkyl both sexes carboxylic acid.

Suitable amine oxide comprises that those formulas are R ³(OR ⁴) _xN ⁰(R ⁵) ₂Compound, R wherein ³Be selected from alkyl, hydroxyalkyl, acyl group amido propyl group and the alkyl phenyl or their mixture that contain 8 to 26 carbon atoms; R ⁴Be alkylidene group or hydroxy alkylidene or their mixture that contains 2 to 3 carbon atoms; The x value is 0 to 5, preferred 0 to 3; Each R ⁵Be an alkyl or a hydroxyalkyl that contains 1 to 3 carbon atom, or a polyethylene oxide group that contains 1 to 3 ethylene oxide group.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈Amidoalkyl dimethyl oxidation amine.

A suitable example of alkyl both sexes dicarboxylic acid is by Dayton, Miranol (TM) the C2M Conc of the Miranol.Inc manufacturing of NJ..

Zwitterionics

Alternatively, zwitterionics can be impregnated in the detergent composition.These tensio-active agents can broadly be described as the derivative of secondary and tertiary amine, the derivative of the heterocycle second month in a season and tertiary amine, or the derivative of quaternary ammonium salt, season  salt or uncle's sulfonium salt compound.Betaine and sulfo group betaine surfactants are the specific exampless of zwitterionics used herein.

Suitable betaine class is that those formulas are R (R ¹) ₂N ⁺R ²COO ^-Compound, wherein R is a C ₆-C ₁₈Alkyl, each R ¹Generally be C ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred betaine has C _12-18Dimethylammonio hexanoate and C _10-18Amido propane (or ethane) dimethyl (or ethyl) betaine.Complicated betaine surfactants also is adapted at this use.

Water-soluble builder compound

Particle of the present invention and/or detergent composition can comprise water miscible builder compound, the content that it exists in detergent composition generally by the weight of composition count 1% to 80%, preferred 10% to 70%, most preferably 20% to 60%.

Suitable water-soluble builder compound comprises water miscible monomer multi-carboxylate, or the form of their acid, the multi-carboxylic acid of homopolymerization or copolymerization or their salt, poly carboxylic acid wherein contain at least two each other by no more than two carboxyls that carbon atom separated; Borate; Phosphoric acid salt and above-mentioned any mixture.

Carboxylate salt or multi-carboxylate's builder can be monomer or oligopolymer on type, though owing to the monomeric multi-carboxylate of the reason of cost and performance generally is preferred.

The suitable carboxylate salt that contains a carboxyl comprises the water soluble salt of lactic acid, oxyacetic acid and their ether derivant.The multi-carboxylate of containing two carboxyls comprises the water soluble salt of Succinic Acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, dihydroxy acetic acid, tartrate, tartronic acid and fumaric acid and ether carboxylate class and sulfinyl metal carboxylate.The poly carboxylic acid salt that contains three carboxyls comprises that specifically water miscible Citrate trianion, aconitate, citraconate and succinate derivative are such as carboxymethyl oxygen Succinic Acid salt, and it is described in English Patent No.1, in 379,241; Breast acyloxy Succinic Acid salt is described in English Patent No.1, in 389,732; Amino-succinic acid salt is described in the Netherlands patent applications 7205873; Oxidation multi-carboxylate material is such as 2-oxa--1,1, and 3-tricarballylic acid salt is described in English Patent No.1, in 387,447.

The multi-carboxylate of containing four carboxyls comprises and is disclosed in English Patent No.1, the oxygen di-Succinic Acid salt and 1,1,2 in 261,829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt, 1,1,2,3-propane tetracarboxylic acid salt.Containing the substituent multi-carboxylate of sulfo group comprises and is disclosed in English Patent Nos.1,389,421 and 1,398,422 and U.S. Patent No. 3,936,448 in sulfosuccinate derivant, and be described in English Patent No.1, the sulfonation pyrolysis Citrate trianion in 439,000.Preferred multi-carboxylate is contained the hydroxycarboxylate of three carboxyls, Citrate trianion more specifically at the most in the per molecule.

The borate builder and contain washing composition store or wash conditions under can produce the builder of the boratory material of boratory formation, be useful here water-soluble builder.

The suitable example of water-soluble phosphate builder has an alkali metal salt of tripolyphosphate, the sodium of tetra-sodium, potassium and ammonium salt, and ortho-phosphoric sodium and sylvite, the scope of extent of polymerization is partially poly-/sodium phosphate of about 6 to 21, and the salt of phytinic acid.

Partly soluble or insoluble builder compound

Particle of the present invention and/or detergent composition can contain partly soluble or insoluble builder compound, and the content that generally is present in the detergent composition counts 1% to 80% by the weight of composition, and be preferred 10% to 70%, and most preferably 20% to 60%.

In particle, the content that this partly soluble or insoluble builder compound preferably exists counts 5% to 85% by particle weight, and is preferred 15% to 60%, and most preferably 20% to 50%.

The example of most of water-fast builder comprises sodium silicoaluminate.

Suitable aluminosilicate zeolite has structure cell formula Na _z[(AlO ₂) _z(SiO ₂) _y] xH ₂O, wherein z and y value are at least 6, and z is 1.0 to 0.5 to the molar ratio of y, and the x value is at least 5.Preferred 7.5 to 276, more preferably 10 to 264.This alumino-silicate materials is the form of hydration, crystal habit preferably, with bonding scheme comprise 10% to 28%, preferred 18% to 22% moisture.

This aluminosilicate zeolite can be naturally occurring material, but preferably synthetic deutero-.Synthetic crystal aluminosilicate ion-exchange material can trade name zeolite A, zeolite B, the form of zeolite P, X zeolite, zeolite HS and their mixture has been bought.Zeolite A has following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂]·xH ₂O

Wherein the x value is 20 to 30, particularly 27, and the formula of X zeolite is Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂O

Preferably, do not contain crystalline layered silicate in the particle of the present invention.Yet the preferred crystalline layered silicate that is used for the detergent composition here has general formula:

NaMSi _xO _2x+1·yH ₂O

Wherein M is sodium or hydrogen, and the x value is 1.9 to 4, and the y value is 0 to 20.Such crystalline layered sodium silicate is disclosed among the EP-A-0164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.Here the x preferred value in the top general formula is 2,3 or 4, preferably 2.Most preferred material is δ Na ₂Si ₂O ₅, it can have been bought from Hoechst AG company by trade name NaSKS-6.

The perhydrate SYNTHETIC OPTICAL WHITNER

A kind of preferred other composition in detergent composition and/or the detergent particles is the perhydrate SYNTHETIC OPTICAL WHITNER, such as metal perborate, metal percarbonate, particularly sodium salt.Perborate can be monohydrate or tetrahydrate.SPC-D has corresponding to 2Na ₂CO ₃3H ₂O ₂Formula, and can buy from the market by the crystalline solid.

Peroxide-Potassium Persulphate, mistake _ _ _ _ sodium is the other selective inorganic perhydrate salt that is used for the detergent composition here.

The organic peroxide acid bleach system

A kind of preferable feature of detergent particles and/or composition is a kind of organic peroxide acid bleach system.This in a preferred embodiment bleach system comprises hydrogen peroxide cource and a kind of organic peroxide acid bleach precursor compound.Situ reaction by precursor and hydrogen peroxide cource produces organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER, such as the perborate bleach of the present patent application patent.Be that preformed organic peroxide acid is directly mixed in the composition in another kind of embodiment preferred.Also can imagine mixture that contains hydrogen peroxide cource and organic peroxy acid precursor and the composition that is combined with preformed organic peroxide acid.

Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that produces peroxy acid in crossing hydrolysis reaction with hydroperoxidation.General peroxyacid bleach precursor can be represented by the formula:

Wherein L is a kind of leavings group, and X can be any functional group basically, makes the peroxy acid structure that produces when crossing hydrolysis be

The content that the peroxyacid bleach precursor compound preferably mixes counts 0.5% to 20% by the weight of detergent composition, and more preferably 1% to 15%, most preferably 1.5% to 10%.

Suitable peroxyacid bleach precursor compound typically comprises one or more N-or O-acyl group, and this precursor can be selected from the classes of compounds that haves a wide reach.Suitable classification comprises acid anhydride class, ester class, acid imide, the acylated derivatives of lactams and imidazoles and oximes.The example of useful materials is disclosed GB-A-1586789 in these classifications.Suitable ester class is disclosed GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.

Leavings group

After this leavings group is called the L group, must be fully active to crossing hydrolysis reaction, so that the group that reacts in Best Times scope (for example, cycles of washing).But if L is too active, then this activator will be difficult to stabilization and be used for bleaching composition.

Preferred L group is selected from:

And their mixture, wherein R ¹Be alkyl, aryl or an alkylaryl that contains 1 to 14 carbon atom, R ³Be the alkyl chain that contains 1 to 8 carbon atom, R ⁴Be hydrogen or R ³, y is hydrogen or a solubilization radical.Any R ¹, R ³And R ⁴All can be replaced, comprise, for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides, ammonium or alkyl ammonium group by any functional group basically.

Preferred solubilization radical has-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-, and O ← N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be an alkyl chain that contains 1 to 4 carbon atom, M is for bleach-activating agent provides deliquescent positively charged ion, and X provides deliquescent negatively charged ion for bleach-activating agent.Preferably, M is the ammonium cation of basic metal, ammonium or replacement, and wherein sodium and potassium are most preferred, and X is halogenide, oxyhydroxide, methylsulfate or acetate negatively charged ion.

Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids when crossing hydrolysis.Such preferred precursor provides peracetic acid when crossing hydrolysis.

The preferred alkyl peroxycarboxylic acid precursors compound of imide type comprises N, N, and N ', the Alkylenediamine class of N ' tetrem acidylate, alkylidene group wherein contains the compound that contains 1,2 and 6 carbon atom in 1 to 6 carbon atom, particularly those alkylidene groups.Tetra acetyl ethylene diamine (TAED) is particularly preferred.TAED preferably is not present in the agglomerated particle of the present invention, contains in this particulate detergent composition but preferably be present in.

Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (iso-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 that replaces at this acid amides that is suitable for comprises that those have the compound of following general formula:

Or

R wherein ¹Be the alkyl that contains 1 to 14 carbon atom, R ²Be the alkylidene group that contains 1 to 14 carbon atom, R ⁵Be H or an alkyl that contains 1 to 10 carbon atom.L can be any basically leavings group.The bleach activating immunomodulator compounds that such acid amides replaces is described among the 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 that replacement and unsubstituted benzoyloxy benzene sulfonate, sorbyl alcohol, glucose and all carbohydrates carry out the product of benzoylation reaction with benzoylation reagent; and those imide types, comprise the ureas that N-benzoyl succimide, four benzoyl quadrols and N-benzoyl replace.The peroxybenzoic acid precursors of suitable imidazoles type comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

The positively charged ion peroxyacid precursor

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

Typically, the positively charged ion peroxyacid precursor is by with positively charged functional group such as ammonium or alkyl ammonium group, preferred ethyl or ammonium methyl group, replaces a kind of peroxy acid part of suitable peroxyacid precursor compound and forms.The positively charged ion peroxyacid precursor generally is that the form with the salt that forms with suitable negatively charged ion such as halide ions is present in the solid detergent composition.

The peroxyacid precursor compound that replaces with positively charged ion can be the precursor compound of the derivative of peroxybenzoic acid or its replacement like this, as previously described.In addition, this peroxyacid precursor compound can be the alkyl peroxy acids precursor that the acid amides that will describe of alkyl peroxycarboxylic acid precursors compound or a kind of back replaces.

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

The example of preferred cation peroxyacid precursor is described among UK patent application No.9407944.9 and the U.S. Patent application Nos.08/298903,08/298650,08/298904 and 08/298906.

Suitable positively charged ion peroxyacid precursor comprises alkyl or the benzoyloxy benzene sulfonate that any ammonium or alkylammonium replace, the tetra-acetylated glucose benzoyl peroxide of the hexanolactam of N-acylations and a benzoyl.The positively charged ion peroxyacid precursor of preferred N-acylations hexanolactam class comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.

Benzoxazine organic peroxy acid precursor

The also precursor compound that the benzoxazine type is arranged of Shi Yonging, as, for example, being disclosed in EP-A-332, those in 294 and EP-A-482,807 particularly have those of following formula:

R wherein ₁Be H, alkyl, alkylaryl, aryl or arylalkyl.

Preformed organic peroxide acid

Except that organic peroxy acid blanching precursor compound, or substitute as a kind of of it in the organic peroxide acid bleach system, can contain a kind of preformed organic peroxide acid, its content generally counts 1% to 15% by the weight of composition, and more preferably 1% to 10%.

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

R wherein ¹Be alkyl, aryl or the alkylaryl that contains 1 to 14 carbon atom, R ²Be alkylidene group, arylidene and the alkylidene aryl that contains 1 to 14 carbon atom, and R ⁵Be H or alkylaryl or the alkaryl that contains 1 to 10 carbon atom.Such organic peroxy acid compound that acid amides replaces is described among the EP-A-0170386.

Other organic peroxy acids comprises diacyl and four acyl peroxides, particularly diperoxy 12 carbon docosandioic acids, diperoxy n-tetradecane diacid and diperoxy hexadecane diacid.One and two cross nonane diacid, and one and two cross brassylic acid and the amino oxy hexanoic acid of crossing of N-phthaloyl, also are suitable for using here.

Bleaching catalyst

Alternatively contain a kind of bleaching catalyst that comprises transition metal in particle or the composition.A kind of bleaching catalyst of adequate types is a kind of catalyst system, wherein contain and a kind ofly have the active heavy metal cation of certain bleach catalyst such as copper, iron or manganese positively charged ion, a kind ofly have only very little bleach catalyst active or do not have the active assistant metal negatively charged ion of bleach catalyst such as zinc or aluminium cations, and catalysis and assistant metal positively charged ion had the sequestrant of certain stability constant, ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and their water soluble salt specifically.This class catalyzer is disclosed United States Patent (USP) 4,430, in 243.

The bleaching catalyst of other type comprises and is disclosed in United States Patent (USP) 5,246,621 and United States Patent (USP) 5,244,594 in the title complex based on manganese.The preferred examples of these catalyzer comprises Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃And their mixture.Other be described in european patent application No.549, in 272.Comprise 1,5,9-trimethylammonium-1,5,9-three nitrogen heterocyclics 12 carbon alkane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and their mixture in this other ligand that is suitable for.

Can be as the example of suitable bleaching catalyst referring to United States Patent (USP) 4,246,612 and United States Patent (USP) 5,227,084, also can wherein lecture monokaryon manganese (IV) title complex such as Mn (1 referring to United States Patent (USP) 5,194,416,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃(PF ₆).Also have the bleaching catalyst of other type, as be disclosed in United States Patent (USP) 5,114, in 606, be a kind of water miscible manganese (III) and/or title complex (IV), its ligand is the non-carboxylate salt polyol that contains at least three continuous C-OH groups.Other example comprises the title complex that double-core Mn and four-N-dentate and two-N-dentate ligand form, and comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Further suitable bleaching catalyst is described in, for example, and european patent application No.408,131 (cobalt complex catalyzer), european patent application Nos 384,503 and 306,089 (catalysis of metalloporphyrin agent), United States Patent (USP) 4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body title complex), United States Patent (USP) 4,711,748 and european patent application No.224,952 (catalyzer of absorption manganese on aluminosilicate catalyst), United States Patent (USP) 4,601,845 (being loaded with the silico-aluminate of manganese and zinc or magnesium salts), United States Patent (USP) 4,626,373 (manganese/ligand catalyzer), United States Patent (USP) 4,119,557 (iron complex catalyzer) German patent specification 2,054,019 (cobalt sequestrant catalyzer), Canadian Patent 866,191 (salt that contains transition metal), United States Patent (USP) 4,430,243 (with the inner complex of manganese positively charged ion and the formation of non-catalytic metallic cation), United States Patent (USP) 4,728,455 (managanese gluconate catalyzer).

Acid source

A kind of acid source, or tart source can be present in particle or the detergent composition.In the time of in being included in detergent composition or particle, preferably also have a kind of alkali source, its energy and acid source reaction are to produce gas.

The content of acid source calculates by the weight of particle or composition and is preferably 0.5% to 10% in particle or detergent composition, and more preferably 1% to 7%, most preferably 2% to 5%.

This acid source is preferably non-hygroscopic, and it can improve package stability.But-the hydrate acids also is useful at this.Organic acid and their derivative are preferred.This acid is preferably water miscible.Suitable acid comprises citric acid, L-glutamic acid, Succinic Acid or hexanodioic acid, mono phosphoric acid ester sodium salt, sodium pyrosulfate, boric acid or their salt or ester.Citric acid is particularly preferred.

Heavy metal ion chelating agent

Particle of the present invention and/or contain this particulate detergent composition and preferably contain a kind of heavy metal ion chelating agent of selecting component as for the election.Heavy metal ion chelating agent is meant that here its effect is to be used for the component of sequester (chelating) heavy metal ion.These components also can have the sequestering power to calcium and magnesium, but they preferably demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

The general content that exists of heavy metal ion chelating agent is calculated as 0.005% to 20% by the weight of composition, and is preferred 0.1% to 10%, and more preferably 0.25% to 7.5%, most preferably 0.5% to 5%.

The suitable heavy metal ion chelating agent that here uses includes the machine phosphonic acid salt, such as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt.

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

Other suitable heavy metal ion chelating agent comprises nitrilotriacetic acid(NTA) and polyaminocarboxylic acid class as used herein, such as ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylene diamine two Succinic Acid, ethylene diamine two L-glutamic acid, 2-hydroxy propylidene diamines two Succinic Acid or their any salt.Particularly preferably be ethylene diamine-N, the ammonium salt of N '-two Succinic Acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement, or their mixture.

Other suitable heavy metal ion chelating agent has imido oxalic acid derivative such as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid as used herein, and it is described in EP-A-317, in 542 and EP-A-399,133.Be described in EP-A-516, iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant in 102 also are suitable in this use.Be described in EP-A-509, the Beta-alanine-N in 382, N '-oxalic acid, aspartic acid N, N '-oxalic acid, aspartic acid-N-one acetate and imino-diacetic Succinic Acid sequestrant also are suitable.

EP-A-476 has described the suitable sequestrant based on amino in 257.EP-A-510,331 described suitable for collagen protein, Keratin sulfate or casein institute deutero-sequestrant.EP-A-528,859 have described a kind of suitable alkyl imino oxalic acid sequestrant.Dinicotinic acid and 2-phosphinylidyne butane-1,2,4-tricarboxylic acid also are suitable.G-NH2-N, N '-two Succinic Acid (GADS), quadrol-N, N '-two L-glutamic acid (EDDG) and 2-hydroxypropyl quadrol N, N '-two Succinic Acid (HPDDS) also is suitable.

Enzyme

The other preferred ingredient that is used for containing the particulate detergent composition or alternatively be used for particle is one or more other a enzyme.Alternatively, a this kind of enzyme or its part may reside in of the present invention agglomerant or the extruding particle in.

Preferred other enzyme material comprise can buy on the market mix lipase, at, amylase, neutrality and alkaline proteolytic enzyme, esterase, cellulase, polygalacturonase, Sumylact L and peroxidase in the detergent composition usually.Suitable enzyme is discussed at United States Patent (USP) 3,519, in 570 and 3,533,139.

Preferred commercially available proteolytic enzyme comprises the enzyme that those are sold with trade name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark) company, the enzyme of selling with trade name Maxatase, Maxacal, Maxapem by Gist-Brocades company, and the enzyme of selling by Genencor International company and sell with trade name Opticlean and Optimase by Solvay Enzymes company.The amount that proteolytic enzyme mixes in the present composition is counted 0.0001% to 4% organized enzyme by the weight of composition.

Preferred amylase comprises, for example, more at large is described in GB-1, the α-Dian Fenmei that a kind of special bacterial strain by Bacillus licheniformis in 269,839 (the Novo companies) obtains.Preferred commercially available amylase for example comprises, those sell with trade name Rapidase by Gist-Brocades with those enzymes of selling with trade name Termamyl and BAN by Novo Industries A/S company.The amount that amylase mixes in the present composition is counted 0.0001% to 2% organized enzyme by the weight of composition.

The content that lipolytic enzyme exists counts 0.0001% to 2% by the weight of composition, and is preferred 0.001% to 1%, most preferably 0.001% to 0.5% active lipolytic enzyme

Lipase can come from fungi or bacterium, for example, can from the humicola lanuginosa Pseudomonas that produces lipase ( HumicolaSp.), ThermomycesSp., or Rhodopseudomonas ( PseudomonasSp), comprise pseudomonas pseudoalcaligenes ( Pseudomonas Pseudoalcaligenes) or Pseudomonas fluorescens ( Pseudomas Fluorescens) bacterial strain in obtain.Mutant by these chemical or genetically altered bacterial strains here also is useful.A kind of preferred lipase be by pseudomonas pseudoalcaligenes ( Pseudomonas Pseudoalcaligenes) deutero-, it is described among the European patent EP-B-0218272 of mandate.

Here other preferred lipase be by clone from Humicola LanuginosaGene and as host's aspergillus oryzae ( Aspergillus Oryza) in express this gene and obtain, as European patent application EP-A-0258, described in 068 like that, this lipase can have been bought with trade name Lipolase from the Novo Industri A/S company of Denmark Bagsvaerd.This lipase also is described in people's such as Huge-Jensen on the 7th March in 1989 the United States Patent (USP) 4,810,414.

Organic polymer

Organic polymer is particle of the present invention and/or comprises preferred component in addition in this particulate detergent composition, and preferably as the component existence of any grain fraction, their roles are that grain fraction is combined therein.Here organic polymer mainly is to mean any polymerizable organic compound that is used as dispersion agent, anti redeposition agent and soil-suspending agent usually in detergent composition.Comprise the high molecular organic polymer that is described as the clay flocculating agent here.

Mix the content of the organic polymer in the detergent composition of the present invention and count 0.1% to 30% by the weight of composition, preferred 0.5% to 15%, most preferably 1% to 10%.

The example of organic polymer comprises the poly carboxylic acid of water miscible organic homopolymerization or copolymerization or their salt, wherein contains at least two in the poly carboxylic acid each other by no more than two carboxyls that carbon atom separates.One type the polymkeric substance in back is disclosed GB-A-1, in 596,756.The example of this salt has the multipolymer of the polyacrylate of molecular weight 2000-5000 and they and maleic anhydride, and the molecular weight of this analog copolymer is 20,000 to 100,000, and particularly 40,000 to 80,000.

Polyamino compounds here is useful, comprises that those by aspartate-derived compound, are disclosed in EP-A-305 such as those, the compound in 282, EP-A-305,283 and EP-A-351,629.

Contain the terpolymer that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol monomeric unit, particularly those molecular-weight average and be 5,000 to 10,000, also be suitable for using here.

Other organic polymer that is suitable for mixing in the detergent composition here comprises derivatived cellulose, such as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.

Further useful organic polymer has polyethylene glycols, particularly those molecular weight are 1000-10000, more especially 2000 to 8000, and most preferably from about 4000.

Other is at this organic compound as preferred clay suspending agent/anti redeposition agent.Can be ethoxylation cation mono amine and two amines with following formula:

Wherein X is selected from H, C ₁-C ₄This class non-ionic group of alkyl or hydroxyalkyl acrylate or ether and their mixture, a value is 0 to 20, preferred 0 to 4 (for example ethylidene, propylidene, hexa-methylene), the b value is 1 or 0; For cation mono amine (the b value is 0), the n value is at least 16, and representative value is in 20 to 35 scopes; For positively charged ion diamine class (the b value is 1), it is about 12 that the n value is at least, and typical range is about 12 to about 42.

Other dispersion agent/anti redeposition agent used herein has been described in EP-B-011965 and the United States Patent (USP) 4,659,802 and 4,664,848.

Foam inhibition system

When being mixed with when being used for the machine-washing composition, this detergent composition preferably contains a kind of foam inhibition system, and the content of its existence is calculated as 0.01% to 15% by the weight of composition, and is preferred 0.05% to 10%, and most preferably 0.1% to 5%.

Suitable foam inhibition system used herein contains any basically known anti-alveolation compound, comprises, for example, anti-alveolation compound of siloxanes and the anti-alveolation compound of 2-alkyl alkanol.

Here anti-alveolation compound is the mixture that means any compound or compound, and its role is to suppress the solution foaming foam or the foaming of detergent composition, especially when existing under the situation of stirring solution.

Particularly preferred as used herein anti-alveolation compound has the anti-alveolation compound of siloxanes, and it is defined as any anti-alveolation compound that comprises silicone components at this.The anti-alveolation compound of this class siloxanes also contains silica component usually.Term used herein " siloxanes " just as whole industry member indication like that, comprise the polymkeric substance that various relative high-molecular weight contain siloxane unit and various types alkyl.The preferred anti-alveolation compound of siloxanes is polysiloxane-based, polydimethylsiloxane class particularly, and it has trimethyl silyl end-blocking unit.

Other suitable anti-alveolation compound comprises mono carboxylic lipid acid and solubility salt thereof.These materials are described in the United States Patent (USP) 2,954,347 that licenses to Wayne St.John September 27 nineteen sixty.This mono carboxylic lipid acid and its esters are at the hydrocarbyl chain that generally contains 10 to 24 carbon atoms, preferred 12 to 18 carbon atoms when the froth suppressor.Suitable salt comprises alkaline metal salt such as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salt.

Other suitable anti-alveolation compound comprises, for example, and high-molecular weight fatty ester class (for example fatty acid triglycercide); The fatty acid ester of unary alcohol; Aliphatics C ₁₈-C ₄₀Ketone (for example stearone); The alkylating aminotriazine class of N-such as three to six alkyl melamines or two are to tetraalkyl diammonium chloride triazines, the latter is that cyanuryl chloride and two or three moles of uncle or secondary amine that contain 1 to 24 carbon atom react the product that forms, propylene oxide, two stearic amides and single stearyl two basic metal (for example sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.

A kind of preferred foam inhibition system preferably contains the anti-alveolation compound of a kind of siloxanes, and it is in conjunction with containing following material:

(i) by the weight 50% to 99% of the anti-alveolation compound of siloxanes, preferred 75% to 95% polydimethylsiloxane; With

(ii) by the weight 1% to 50% of the anti-alveolation compound of siloxanes/silicon-dioxide, preferred 5% to 25% silicon-dioxide;

The amount that the anti-alveolation compound of wherein said silica/silicon oxygen alkane is impregnated in is 5% to 50%, preferred 10% to 40% by weight.

(b) a kind of compound dispersing agent, it most preferably contains the rake formula multipolymer of siloxane glycol class, and wherein the content of polyoxy alkylidene is 72-78%, and oxyethane is 1: 0.9 to 1: 1.1 to the ratio of propylene oxide; The content of dispersion agent is 0.5% to 10% by weight, preferred 1% to 10%; A kind of rake formula multipolymer of siloxane glycol class of particularly preferred this pattern is DCO544, can buy from DOW Corning company, and its trade name is DCO544.

(c) a kind of inert support fluid compound most preferably contains C ₁₆-C ₁₈Ethoxylated alcohol, the ethoxyquin degree is 5 to 50, and is preferred 8 to 15, content is 5% to 80% by weight, preferred 10% to 70%.

The foam inhibition system of a kind of highly preferred particulate state is described among the EP-A-0210731, it comprises the anti-alveolation compound of a kind of siloxanes and a kind of melting range at 50 ℃ to 85 ℃ organic support material, and this organic support material contains the monoesters of the lipid acid of glycerine and a kind of carbochain that contains 12 to 20 carbon atoms.EP-A-0210721 discloses the foam inhibition system of other preferred particulate state, and organic support material wherein is a kind of lipid acid or alcohol that contains 12 to 20 carbon atom carbochains, or their mixture, and fusing point is 45 ℃ to 80 ℃.

The clay softening system

Can contain a kind of clay softening system in particle and/or the detergent composition, it comprises a kind of clay mineral compound and alternatively a kind of clay flocculating agent.

Preferably a kind of terre verte compound of this clay mineral compound.Terre verte is disclosed United States Patent(USP) Nos. 3,862,058; 3,948,790; In 3,954,632 and 4,062,647; European patent Nos.EP-A-299,575 and EP-A-313,146 have narrated suitable organic polymer clay flocculating agent with the name of Procter and GambleCompany.

The polymeric dye transfer inhibitor

Particle but preferably in detergent composition can contain by weight 0.01% to 10%, preferred 0.05% to 0.5% polymeric dye transfer inhibitor.

This polymeric dye transfer inhibitor preferably is selected from polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinylpyrrolidonepolymers polymers or their combination.

A) polyamine N-oxide pllymers

Comprise unit at this polyamine N-oxide pllymers that is suitable for following structural formula:

Wherein P be polymerisable unit and

R is aliphatics, aromatic series, heterocycle or the alicyclic group of aliphatics, ethoxylation, or their arbitrary combination, and the nitrogen of N-O base can be connected on these groups or the N-O base is the part of these groups.

The N-O base can be represented with following general formula:

Or

R wherein ₁, R ₂And R ₃Be fat group, fragrance, heterocycle or alicyclic group or their combination, x or/and y or/and the z value is 0 or 1, and wherein the nitrogen of N-O base can be connected on these groups or the nitrogen of N-O base forms the part of these groups.The N-O group can be the part of polymerizable unit (P) or can be connected on the skeleton of polymkeric substance, or the combination of the two.

Wherein the suitable polyamine N-oxide of the part of N-O group formation polymerizable unit comprises such polyamine N-oxide, and wherein R is selected from fat, fragrance, alicyclic ring or heterocyclic group.The said polyamine N-oxide of one class comprises the group of such polyamine N-oxide, and wherein the nitrogen of N-O base forms the part of R group.Preferred polyamine N-oxide compound is the compound that those R wherein are heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.

Other suitable polyamine N-oxide is such polyamine N-oxide, and wherein the N-O group is connected on its polymerizable unit.Preferred these polyamine N-oxide of one class comprise the polyamine N-oxide with top general formula (I), wherein R is fragrance, heterocycle or alicyclic group, the nitrogen of N-O functional group is the part of said R group, and the example of this compounds has wherein that R is the polyamine oxide compound of heterogeneous ring compound such as pyridine, pyrroles, imidazoles and derivative thereof.

This polyamine N-oxide can almost extent of polymerization be obtained arbitrarily, as long as material has the ability of required water solubility and suspension dyestuff, extent of polymerization is not critical.Generally, molecular-weight average is 500 to 1,000, in 000 scope.

B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

What here be suitable for is that molecular-weight average is 5,000 to 50,000 N-vinyl imidazole and N-vinylpyrrolidone copolymers.The N-vinyl imidazole is 1 to 0.2 to the molar ratio of N-vinyl pyrrolidone in the preferred multipolymer.

C) Polyvinylpyrolidone (PVP)

It is 2,500 to 400,000 Polyvinylpyrolidone (PVP) (" PVP ") that the detergent composition here also can use molecular-weight average.Suitable Polyvinylpyrolidone (PVP) can have been bought from the ISP Corporation company and the Montreal, CAN of New York, continent, New York, name of product is a PVP K-15 (viscosity molecular weight 10,000) PVP K-30 (molecular-weight average 40,000), PVP K-60 (molecular-weight average 160,000) and PVP K-90 (molecular-weight average 360,000).PVP K-15 also can buy from ISP Corporation.Other suitable Polyvinylpyrolidone (PVP) can have been bought from BASF AG, comprises Sokalan HP165 and Sokalan HP12.

D) polyvinyl  oxazolidone

The detergent composition here also can use polyvinyl  oxazolidone as the polymeric dye transfer inhibitor.The molecular-weight average of said polyvinyl  oxazolidone is 2,500 to 400,000.

E) polyvinyl imidazol

The detergent composition here also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of said polyvinyl imidazol is preferably 2,500 to 400,000.

White dyes

The detergent composition here also alternatively contains about by weight 0.005% to 5% certain type wetting ability white dyes.

Comprise that at this useful wetting ability white dyes those have the compound of following structural formula:

R wherein ₁Be selected from anilino, N-2-double hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-double hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; M is that the salifiable positively charged ion of shape is such as sodium or potassium.

As R in following formula ₁Be anilino, R ₂Be the N-2-double hydroxyethyl, when M was positively charged ion such as sodium, this whitening agent was exactly 4,4 '-two [(4-anilino-6-(N-2-double hydroxyethyl)-S-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid and disodium salt.This concrete whitening agent species trade name when commercially available is Tinopal-UNPA-GX, is produced by Ciba-Geigy company.Tinopal-UNPA-GX is the preferred wetting ability white dyes of detergent composition that is used for here.

When in following formula, R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2 methylamino-, when M was positively charged ion a such as sodium, this whitening agent was exactly 4,4 '-two [(4-anilino-6 (N-2-hydroxyethyl-N-methylamino-)-S-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid disodium salt.This concrete whitening agent species trade name when commercially available is Tinopal 5BM-GX, is produced by Ciba-Geigy company.

When in following formula, R ₁Be anilino, R ₂Be morpholino, when M was positively charged ion a such as sodium, this whitening agent was exactly 4,4 '-two [(4-anilino-6-morpholino-S-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid, sodium salt.This concrete whitening agent species trade name when commercially available is Tinopal AMS-GX, is produced by Ciba-Geigy company.

The composition that other is selective

Other the selective composition that is fit to mix in particle of the present invention and/or the detergent composition comprises spices, colorant and filler salt, and sodium sulfate is a kind of preferred filling salt.

The pH of composition

Particle and/or final detergent composition are at least 10.0 with the pH value that records in 1% the solution in distilled water, and be preferred 10.0 to 12.5, and most preferably 10.5 to 12.0.

The form of composition

Containing grains of composition can have various physical form, the preferred particulates shape.This composition can be low-density particles detergent composition or so-called spissated granular detergent composition, be suitable for being added in the washing machine with the fabric load of making dirty by the distribution device that is installed in the washing machine drum, or by means of in the divider adding washing water, or freely add in the machine, preferably be added to the bottom of washing machine.

The mean particle size of the basic composition of particulate composition of the present invention can be at 0.1 millimeter to 5.0 millimeters, but preferable case be no more than 5% particle diameter greater than 1.7 millimeters, no more than 5% particle diameter is less than 0.15 millimeter simultaneously.

It is that some parts (5 parts typically) are calculated that the term mean particle size is defined as by with a series of Tyler sieves the composition sample being sieved at this.The parts by weight that obtain are to the pore size mapping of sieve.Mean particle size is got such pore size, promptly by weight can be by the sieve in this aperture in respect of 50% sample.

The tap density of granular detergent composition is generally at least 500 grams per liters, more preferably 650 grams per liter to 1200 grams per liters.Tap density is measured by simple funnel and cup device, this device comprises that a rigidity casts in suprabasil conical funnel, have a plate valve in its lower end, it can allow the content of funnel to be vented to be placed under the funnel with the axially aligned cylindrical bucket of funnel in.Funnel is high 130 millimeters, and the internal diameter of top and bottom respectively is 130 millimeters and 40 millimeters.It is installed like this, and the lower end that makes it is at 140 millimeters places of upper surface of substrate, 90 millimeters of cup total heights, and 87 millimeters of internal height, 84 millimeters of internal diameters, its nominal volume is 500 milliliters.

For measuring, topple over to make funnel be full of powder with hand, open plate valve and allow the excessive cup that is full of of powder.Take out the cup be full of from support, by with the straight flange instrument for example a top that cutter is passed through it to remove powder excessive in the cup.Flat full cup is weighed then, will claim to such an extent that the double in weight of powder promptly provides tap density in grams per liter.Can heavily cover measurement if desired.

Clothes washing method

The machine washing method here generally comprises therein oneself dissolving or disperseed handles black clothing in the wash water solution in the washing machine of significant quantity machine laundry detergent composition of the present invention.The detergent composition of significant quantity is meant in 5 to 65 liters of volume washing solns dissolving or is dispersed with the products of 40 grams to 300 grams, and is similar with the washing soln volume to the common typical products dosage that is used for usually the machine washing method.

The packing of composition

The commercial embodiments of bleaching composition can be packaged in any suitable containers, comprises the container that those are made with paper, cardboard, plastic material and any suitable veneer sheet.A kind of preferred packing embodiment is described among the european patent application No.94921505.7.

Employed abbreviation in following examples

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

LAS: line style C ₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

C45AS: C ₁₄-C ₁₅Linear alkyl sodium sulfate

C _XyE _zS: C _1x-C _1yThe product of branched sodium alkyl sulfate and the condensation of z moles of ethylene oxide

C45E7: C ₁₄-C ₁₅Be mainly the primary alconol of line style and the product of average 7 moles of ethylene oxide condensations

C25E3: C ₁₂-C ₁₅The product of branched primary alconol and average 3 moles of ethylene oxide condensations

C25E5: C ₁₂-C ₁₅The product of branched primary alconol and average 5 moles of ethylene oxide condensations

CEQ: R ₁COOCH ₂CH ₂N ⁺(CH ₃) ₃, R wherein ₁=C ₁₁-C ₁₃

QAS: R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH), R wherein ₂=C ₆-C ₁₄

Soap: by 80/20 butter and coconut oil blend institute deutero-linear alkyl carboxylic acid sodium

STS: toluenesulfonic acid sodium salt

SXS: sodium xylene sulfonate

SBS: benzene sulfonic acid sodium salt

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

TPKFA: C ₁₂-C ₁₄The full cut lipid acid of topping

STPP: anhydrous sodium tripolyphosphate

Zeolite A: formula is Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydrated sodium aluminosilicate of O, its primary granule magnitude range are 0.1 to 10 micron

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

Citric acid: Citric Acid, usp, Anhydrous Powder

Carbonate: anhydrous sodium carbonate, its granular size is between 200 μ m to 900 μ m

Supercarbonate: anhydrous sodium bicarbonate, its particle size dispersion is between 400 μ m to 1200 μ m

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

Sodium sulfate: anhydrous sodium sulphate

Citrate trianion: active 86.4% citrate trisodium dihydrate, its particle size dispersion is between 425 μ m to 850 μ m

MA/AA: toxilic acid/acrylic copolymer of 1: 4, molecular-weight average is about 70,000

CMC: Xylo-Mucine

QEA1: two ((C ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two ((C ₂H ₅O)-(C ₂H ₄O) _n), n=20 to 30 wherein

Proteolytic enzyme: active for the 4KNPU/ gram, by the protease of NOVO Industries A/S with trade name Savinase sale

Alcalase: active for the 3AU/ gram, by the protease of NOVO Industries A/S sale

Cellulase: active is the 1000CEVU/ gram, by the cellulolytic enzyme of NOVO Industries A/S with trade name Carezyme sale

Amylase: active for the 60KNU/ gram, by the amylolytic enzyme of NOVO Industries A/S with trade name Termamyl 60T sale

Lipase: active is the 100kLU/ gram, by the lipolytic enzyme of NOVO Industries A/S with trade name Lipolase sale

Restriction endonuclease (Endolase): the endoglucanase that activity is 3000 CEVU/ gram, sold by NOVO Industries A/S

PB4: the nominal formula is NaBO ₂3H ₂OH ₂O ₂Sodium perborate tetrahydrate

PB1: the nominal formula is NaBO ²H ²O ²Anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER

Percarbonate: the nominal formula is 2Na ₂CO ₃3H ₂O ₂SPC-D

NOBS: the nonanoly acyloxy benzene sulfonate that exists with sodium-salt form

NAC-OBS: (nonanoyl amino caproyl) the oxygen benzene sulfonate that exists with sodium-salt form

TAED: tetra acetyl ethylene diamine

DTPMP: by the diethylenetriamine five (methylene radical phosphoric acid salt) of Monsanto Company with trade name Dequest 2060 sales

EDDS: the sodium salt of quadrol two succinates

DTPMP: diethylenetriamine five (methylene phosphonic acid salt), sell with trade name Dequest2060 by Monsanto Company

The SYNTHETIC OPTICAL WHITNER of photoactivation: be encapsulated in the sulfonation phthalocyanine phthalocyanine zinc in the dextrin soluble polymer

Whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium

Whitening agent 2: 4,4 '-two (4-anilino-6-morpholino-1,3,5-triazines-2-yl) amino) Stilbene-2,2 '-the disulfonic acid disodium

HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid

PVNO: polyvinylpyridine N-oxide compound

PVPVI: the multipolymer of Polyvinylpyrolidone (PVP) and vinyl imidazole

SRP1: the end capped ester class of sulfo group benzoyl that has oxygen ethylidene oxygen and terephthaloyl skeleton

SRP2: the short block polymer of poly-(1, the 2 propylidene terephthalate) of diethoxyization

The siloxanes kilfoam: with siloxanes one oxyalkylene multipolymer is the polydimethylsiloxane Foam Control of dispersion agent, and said Foam Control is 10: 1 to 100: 1 to the ratio of said dispersion agent

Basicity: with the weight % equivalence of NaOH, available basicity release test method described herein records

All content are represented with the percentage ratio of composition weight in following examples:

Embodiment 1

Contain this particulate detergent formulations below having prepared according to the present invention.

	A		B	C	D
						Spray-dired particle
LAS	6.0		5.0	11.0	6.0
						TAS	2.0		-	-	2.0
Zeolite A	22.0		27.0		20.0
						STS	0.5		1.2	1.6	2.0
STPP	2.0		-	22.0	-
						Vitriol	9.0		6.0	13.0	-
MA/AA	2.0		4.0	6.0	4.0
						Silicate	7.0		-	3.0	-
CMC	1.0		1.0	0.5	0.6
						Whitening agent 1	0.2		0.2	0.2	0.2
The siloxanes kilfoam	1.0		0.1	0.1	0.05
						DTPMP	0.4		0.4	0.2	0.4
Spraying
						C45E7	-		-	-	5.0
C45E2	2.5		2.5	2.0	-
						C45E3	2.6		2.5	2.0	-
Spices	0.3		0.3	0.3	0.2
						The siloxanes kilfoam	0.3		0.3	0.3	-
The exsiccant additive
						Vitriol	3.0		3.0	5.0	10.0
Carbonate	6.0		13.0	15.0	14.0
						PB1	-		-	-	1.5
PB4	18.0		18.0	10.0	18.5
						TAED	3.0		2.0	-	2.0
NAC-OBS	-		2.0	4.0	-
						Proteolytic enzyme	1.0		1.0	1.0	1.0
Lipase	0.4		0.4	0.4	0.2
						Amylase	0.2		0.2	0.2	0.4
The photoactivation SYNTHETIC OPTICAL WHITNER	-		-	-	15ppm
						Other/accessory constituent is added to 100%

Embodiment 2

Prepared following detergent granules preparation according to the present invention.Wherein preparation N is particularly suitable for using under Japanese machine-washing condition.Preparation O-S then is particularly suitable for using under U.S.'s machine-washing condition.

	E		F	G		H	I	J
									Spray-dired particle
LAS	22.0		5.0	4.0		9.0	8.0	6.0
									C45AS	-		7.0	6.0		-	-	-
TAS	7.0		4.0	3.0		1.8	2.0	3.0
									STS	0.9		1.5	1.7		0.8	3.0	1.5
Zeolite A	6.0		16.0	14.0		19.0	16.0	14.0
									MA/AA	6.0		3.0	3.0		3.0	2.0	3.0
AA	-		3.0	3.0		-	-	-
									Vitriol	7.0		18.3	11.3		14.0	15.3	10.0
Silicate	5.0		1.0	1.0		-	1.0	-
									Carbonate	28.3		9.0	7.0		15.7	14.0	10.0
PEG 4000	0.5		1.5	1.5		-	-	-
									EDDS	2.0		-	-		0.1	0.2	0.3
HEDP	0.4		-	0.5		0.2	0.5	0.5
									QEA	-		-	0.8		-	0.8	0.5
Whitening agent 2	0.2		0.3	0.3		0.3	0.3	0.3
									Spraying
C25E9	1.0		-	-		-	-	-
									C45E7	-		2.0	2.0		3.5	2.0	2.0
Spices	1.0		0.3	0.3		1.0	0.3	0.3
									Agglomerate
TAS	0.5		-	-		-	1.0	0.9
									C45AS	-		5.0	5.0		-	5.0	5.0
LAS	-		2.0	2.0		-	2.0	2.0
									Zeolite A	-		7.5	7.5		-	7.5	7.5

Carbonate	-	4.0	4.0	-	4.0	4.0
							PEG 4000	-	0.5	0.5	-	-	-
Other (water etc.)	-	2.0	2.0	-	-	2.0
							The exsiccant additive
PB4	-	1.0	4.0	-	5.0	0.5
							TAED	6.0	2.0	-	2.0	1.6	2.5
Percarbonate	-	5.0	12.5	-	-	-
							Carbonate	-	5.3	1.8	14.0	4.0	8.0
NOBS	4.5	-	6.0	-	-	0.6
							Lipase	0.4	0.4	0.4	0.2	0.4	0.4
Cellulase	0.1	0.2	0.2	0.2	0.2	0.2
							Amylase	0.1	0.3	0.3	0.6	0.6	1.1
Proteolytic enzyme	1.0	0.5	0.5	1.5	1.0	01.2
							PVPVI	-	0.5	0.5	-	-	-
PVP	0.5	0.5	0.5	-	-	-
							PVNO	-	0.5	0.5	-	-	-
SRP1	-	0.5	0.5	-	-	-
							SKS-6	-	-	0.5	4.5	2.0	3.5
Citric acid	-	1.0	-	1.0	1.5	2.0
							QAS	-	-	1.0	1.0	1.0	1.5
QEA	1.0	-	-	1.0	-	-
							The siloxanes kilfoam	-	0.2	0.2	0.3	0.2	0.2
							Other/accessory constituent is added to 100%

Embodiment 3

The detergent formulations that does not contain SYNTHETIC OPTICAL WHITNER below having prepared according to the present invention, it is particularly useful when the coloured clothes of washing:

	K	L	M
				Spray-dired particle
Zeolite A	15.0	15.0	-
				Vitriol	0.0	5.0	-
LAS	3.0	3.0	-
				DTPMP	0.4	0.5	-
CMC	0.4	0.4	-
				MA/AA	4.0	4.0	-
TAS	3.0	2.0	-
				STS	2.5	-	1.2
SXS	-	2.0	-
				Agglomerate
C45AS	-	-	11.0
				LAS	6.0	5.0	-
Silicate	4.0	4.0	-
				Zeolite A	10.0	15.0	13.0
CMC	-	-	0.5
				MA/AA	-	-	2.0
Carbonate	9.0	7.0	7.0
				Spraying
Spices	0.3	0.3	0.5
				C45E7	4.0	4.0	4.0
C25E3	2.0	2.0	2.0
				The exsiccant additive
MA/AA	-	-	3.0
				NaSKS-6	-	-	12.0
Citrate trianion	10.0	-	8.0

Supercarbonate	7.0	3.0	5.0
				Carbonate	8.0	5.0	7.0
PVPVI/PVNO	0.5	0.5	0.5
				Alcalase	0.5	0.3	0.9
Lipase	0.4	0.4	0.4
				Amylase	0.6	0.6	0.6
Cellulase	0.6	0.6	0.6
				The siloxanes kilfoam	5.0	5.0	5.0
The exsiccant additive
				Vitriol	0.0	9.0	0.0
Other/accessory constituent is added to 100%	100.0	100.0	100.0
				Density (grams per liter)	700	700	700

Embodiment 4

Prepared following detergent granules preparation according to the present invention:

	N		O	O
					Spray-dired particle
Zeolite A	30.0		22.0	6.0
					Vitriol	19.0		5.0	7.0
MA/AA	3.0		3.0	6.0
					LAS	14.0		12.0	20.0
TAS	-		3.0	5.0
					STS	1.9		1.2	7.9
C45AS	8.0		-	-
					Silicate	-		1.0	5.0
Soap	-		-	2.0
					Whitening agent 1	0.2		0.2	0.2
Carbonate	8.0		16.0	20.0
					DTPMP	-		0.4	0.4
Spraying	-		1.0	5.0
					C45E7	1.0		1.0	1.0
The exsiccant additive
					PVPVI/PVNO	0.5		0.5	0.5
Proteolytic enzyme	1.0		1.0	1.0
					Lipase	0.4		0.4	0.4
Amylase	0.1		0.1	0.1
					Cellulase	0.1		0.1	0.1
NOBS	-		6.1	4.5
					PB1	1.0		5.0	6.0
Vitriol	-		6.0	-
					Other/accessory constituent is added to 100%

Embodiment 5

Prepared following granular detergent composition according to the present invention:

	Q		R
				Spray-dired particle
Zeolite A	20.0		18.0
				STPP	-		2.0
LAS	6.0		6.0
				TAS	2.0		3.0
C68AS	2.0		-
				Silicate	3.0		8.0
MA/AA	4.0		2.0
				CMC	0.6		0.6
Whitening agent 1	0.2		0.2
				DTPMP	0.4		0.4
STS	-		8.0
				SBS	2.0		-
Spraying
				C45E7	5.0		5.0
The siloxanes kilfoam	0.3		0.3
				Spices	0.2		0.2
The exsiccant additive
				Carbonate	14.0		9.0
PB1	1.5		2.0
				PB4	18.5		13.0
TAED	2.0		2.0
				The SYNTHETIC OPTICAL WHITNER of photoactivation	15ppm		15ppm
Proteolytic enzyme	1.0		1.0
				Lipase	0.2		0.2
Amylase	0.4		0.4
				Cellulase	0.1		0.1
Vitriol	10.0		20.0
				Other/accessory constituent is added to 100%
Density (grams per liter)	700		700

Embodiment 6

Prepared following detergent composition according to the present invention:

	S		T		U
						Spray-dired particle
STS	1.6		1.2		7.4
						C45AS	-		3.0		-
Zeolite A	15.0		15.0		15.0
						Vitriol	0.0		5.0		0.0
LAS	15.0		6.0		8.0
						TAS	1.0		-		3.0
DTPMP	0.4		0.2		0.4
						EDDS	-		0.4		0.2
CMC	0.4		0.4		0.4
						MA/AA	4.0		2.0		2.0
Agglomerate
						LAS	5.0		5.0		5.0
TAS	2.0		2.0		1.0
						Silicate	3.0		3.0		4.0
Zeolite A	8.0		8.0		8.0
						Carbonate	8.0		8.0		4.0
Spraying
						Spices	0.3		0.3		0.3
C45E7	2.0		2.0		2.0
						C25E3	2.0		-		-
The exsiccant additive
						Citrate trianion	5.0		-		2.0
Supercarbonate	-		3.0		-
						Carbonate	8.0		15.0		10.0
TAED	6.0		2.0		5.0
						PB1	14.0		7.0		10.0

PEO	-	-	0.2
				Wilkinite	-	-	10.0
Proteolytic enzyme	1.0	1.0	1.0
				Lipase	0.4	0.4	0.4
Amylase	0.6	0.6	0.6
				Cellulase	0.6	0.6	0.6
The siloxanes kilfoam	5.0	5.0	5.0
				The exsiccant additive
Sodium sulfate	0.0	3.0	0.0
				Other/accessory constituent is added to 100%	100.0	100.0	100.0
Density (grams per liter)	850	850	850

Claims (15)

1. detergent particles, it comprises:

A) a kind of anion sulfoacid salt surfactant, its content counts 0.01% to 20% by particulate weight;

B) a kind of hydrotropic agent, its content counts 0.01% to 45% by particulate weight;

Wherein the anion sulfoacid salt surfactant is 10: 1 to 2: 1 to hydrotropic weight ratio, and can have the phosphate component by particulate weight 0.0% to 30%.

2. according to the particle of claim 1, the content of anion sulfoacid salt surfactant wherein counts 5% to 15% by particle weight.

3. according to each particle in the claim of front, wherein hydrotropic content counts 0.5% to 2% by particle weight.

4. according to each particle in the claim of front, anion sulfoacid salt surfactant wherein is C ₁₀-C ₁₈Linear alkyl benzene sulfonate salt.

5. according to each particle in the claim of front, hydrotropic agent wherein is the salt of Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid or isopropyl sulfonic acid.

6. according to the particle of claim 5, hydrotropic agent wherein is a toluenesulfonic acid sodium salt.

7. according to each particle in the claim of front, wherein there is a kind of anion sulfate acid salt surfactant.

8. according to the particle of claim 7, anion sulfate acid salt surfactant wherein is a tallow alkyl vitriol.

9. according to each particle in the claim of front, wherein there are not cationic softening agent, cats product and/or nonionogenic tenside basically.

10. according to each particle in the claim of front, wherein there is not phosphate component basically.

11. a particulate method of making in the claim 1 to 6 each, it may further comprise the steps:

A) anion sulfoacid salt surfactant and hydrotropic agent are mixed with water and form a kind of particle that contains moisture;

B) drying step particle a).

12. according to the method for claim 10, wherein the particle drying of step b) is the particulate spraying drying.

13. according to particle any in the claim 1 to 10, particle wherein is a kind of spray-dired particle.

14. according to particle any in claim 1 to 10 or 13, wherein the particulate free water content is by weight less than 6%.

15. a granular detergent composition that comprises according to detergent particles any in claim 1 to 10 or 13, its content counts 5% to 85% by the weight of composition.