CN1354780A - Effervescence component - Google Patents

Abstract

The present invention relates to an effervescence composition comprising an acid source and a carbon dioxide source, wherein at least 85 % of said acid source has a particle size from 0.1 to 150 microns, preferably from 0.5 to 100 microns. The carbon dioxide source is preferably also of a small particle size. The effervescence composition is in particular useful in solid detergent compositions. The effervescence component is preferably in the form of a granule comprising at least part of the acid source and the at least part of the carbon dioxide source. The effervescence component can also be coated by a coating comprising an alkoxylated alcohol having an alkoxylation degree of at least 20.

Description

Effervescence component

Technical field

The present invention be applicable to need with a kind of easily and immediate mode be dissolved in the various compositions of water-bearing media.Present technique can be used for various fields as be used for family expenses, pharmaceutical preparation, the laundry detergent composition of aspect such as the articles for use that clean the teeth, food, washing by soaking agent composition, dish washing detergent compositions or other composition arbitrarily.More specifically, the present invention relates to be used for the granular detergent composition of clean fabric.

Background of the present invention

The problem that the used conventional granulates composition of human consumer occurs behind dilute with water usually is their relatively poor dissolvings or relatively poor distributivity.Tend to higher tap density particulate composition as detergent industry and aggravated this trend with the current trend of the granular detergent composition of activeconstituents with high level.Have 650 to 1100 kilograms/meter ³The granular detergent composition of high-bulk-density be attractive for the human consumer but dissolve in the water-bearing media unsatisfactorily.

Another difficult point of detergent composition is that they are difficult for flushing out from the ingredient capsule of washing machine.Similar problem appears when using these granular detergent compositions in the dosing device at washing machine drum.

Well-known is in powder composition, uses the lemon acid plus carbonate to improve the dissolving as pharmaceutical preparation and washing composition by the effervesce mode.

A possible problem that contains these compositions of particle acid plus carbonate is a package stability relatively poor when they are exposed to moisture, thereby causes effervescive to reduce.Therefore, the citric acid of big particle diameter is used in suggestion in as EP534525-A, it is said that it is stable when being exposed to moisture.

But the inventor finds that out of a clear sky the sour material of minimum particle diameter provides improved effervescency now.They find and pointed opposite of prior art curiously, can be used for various compositions and not cause the stability problem of effervescent system than the acid of small particle size, provide more efficient simultaneously and effervesce fast.They find that the acid source that adds minimum particle diameter not only causes improved distribution/dissolving (comparing with the acid of greater particle size), and obtain improved foaming faster, and this is very favorable for some application.When carbon dioxide source also has little particle diameter, obtain further improved effervesce performance and distribute more efficiently and/or dissolve and/or bubble.

Can height preferred acid and carbon dioxide source be mixture closely, preferably the form with dried effervescent granule exists.This has not only further improved the stability of described effervescent system, but also has improved effervesce efficient, causes thus more a spot ofly being used for desired effervesce, distribution/dissolving and/or blistered acid source.In addition, the inventor finds that the effervescent granule with greater particle size advantageously obtains more stable, better effervescent granule.

The inventor is surprised to find when the acid source that uses than small particle size, can obtain strong and homogeneous granules more, improves the effervesce performance thus.In addition, when the effervescent granule of needs compressions, when adopting, can reduce compression pressure than the acid source of small particle size and optional carbon dioxide source than small particle size.These particles dissolve quickly and improved effervesce are provided thus.In addition, perhaps, when described particle is prepared by agglomeration, find that it is favourable using the acid than small particle size, especially when tackiness agent is used to form agglomerate, discovery is compared with the material that uses greater particle size, and the performance characteristic of effervesce agglomerate is subjected to the influence of described tackiness agent less during the less acid source of fusion.

In addition, the inventor finds when comprising that the coating of specific alcohol alcoxylates is present on the described effervescence component, in the time of perhaps on its a kind of or various ingredients, it has not only strengthened the stability of effervescence component when being exposed to moisture, but also has increased the long duration foamy generation of high volume astoundingly.

The long-time foamy of high volume of the increase that the effervescence component by coating obtains generates also to have gives one of user the clearly advantage of signal in addition, and the detergent composition that promptly contains the effervescence component of described coating has dissolved and now or prepare to begin to clean soiled goods.It is particularly useful for hand washing and uses: it may be best introducing soiled goods in the cycles of washing when described detergent composition has dissolved.

Above-mentioned selected alcohol alcoxylates also can be in the last stages of cycles of washing as serving as suds suppressor in rinsing, and have dual role thus in cycles of washing.The specific alcohol alcoxylates that uses with this dual mode has desirable influence to the prescription space, make other optionally washing agent component have bigger space, because it helps avoid and is used to bubble and presses down two kinds of bubble independently necessity of detergent composition composition.

The present invention's general introduction

The invention provides a kind of effervescence component, comprise acid source and carbon dioxide source, wherein said acid source at least 75% has the 0.1-150 micron, more preferably 0.5 to 100 micron particle diameter.

In one embodiment, height preferably carbon dioxide source has the volume medium (volume median particle size) of 5-375 micron, preferred thus at least 60% has the particle diameter of 1-425 micron, the volume medium that perhaps more preferably has the 10-250 micron, preferred thus at least 60% has the particle diameter of 1-375 micron.In a preferred embodiment, carbon dioxide source has the particle diameter similar to acid source, preferred make at least 60% or even 75% carbon dioxide source have the 1-150 micron, the more preferably particle diameter of 1-100 micron.

In a highly preferred embodiment, acid source and carbon dioxide source are present in the intimate mixture each other together, preferably are present in the particle.

The inventor also provides a kind of preparation this particulate method, and this method may further comprise the steps:

-mix acid source and carbon dioxide source and optional tackiness agent forming mixture,

-subsequently described mixture is carried out granulation step, preferably this step comprises that compression and/or agglomeration step are to form compression and/or agglomerant mixture.

Preferred acid source is a particulate material, with before carbon dioxide source mixes, at first with its grinding to obtain acid source of the present invention.Carbon dioxide source also can obtain by the material that grinds greater particle size.

The present invention also comprises the composition that contains effervescence component.In a preferred embodiment, described composition is solid or water-free detergent composition, and it comprises laundry, pre-treatment and dish washing compositions, the solids composition of preferred particulates shape, sheet or strip.

In addition, the present invention comprises also and contains the detergent composition that is coated with effervescence component that wherein said coating comprises that extent of alkoxylation is at least 20 alcohol alcoxylates.

The present invention describes acid source in detail

The acid source of Shi Yonging can provide SOLID ORGANIC, mineral or mineral acid herein, and its source preferably exists with the form of its acid, salt or derivative or its mixture.Derivative specifically comprises the ester of acid.

Especially preferred organic acid.Can preferred described acid be single-, two-or three-protonic acid.These preferred acid comprise monocarboxylic acid or polycarboxylic acid, optimization citric acid, hexanodioic acid, pentanedioic acid, 3 cetoglutaric acid, citromalic acid, tartrate, toxilic acid, fumaric acid, oxysuccinic acid, Succinic Acid, propanedioic acid.These acid are preferably used with their sour form, and can preferably use their acid anhydrides, or the form of its mixture.Preferred acid source is apple acid anhydrides and maleic anhydride.Other preferred acid comprises sulfonic acid such as toluenesulphonic acids.

Surprisingly have now found that by using citric acid, tartrate, toxilic acid and/or oxysuccinic acid to obtain improved physics and/or chemical stability in the storage period that prolongs.In addition, find these materials, especially tartrate has improved dissolving, causes improved effervesce performance.

Described acid source and preferred acid are originally as the granulating compound; it is at least 75% years old; preferably at least 85% or even at least 90% or even at least 95% or even the particle diameter of at least 99% (volume) be 0.1-150 micron and more preferably 0.5-100 micron, and even can be preferably at least 65% or even at least 75% or even at least 85% particle diameter be 1.0-75 micron or even 1.0-55 micron or even 1.0-25 micron.

The following acid source and the particle diameter of carbon dioxide source can pass through any known method in this area, especially by laser light scattering or deftraction technology, measure as adopting Malvem 2600 or Sympatec Helos laser light scattering instrument (or defractometer).

Preferably the volume medium of acid source is 1-120 micron or even 5-75 micron or even 5-55 micron or even 5-30 micron herein.

The volume medium of acid source and carbon dioxide source can be measured by any known method in this area, and the mentioned laser light scattering instrument (program of compiling and editing is used to provide volume medium) of concrete herein employing is measured.

Preferably just before adding effervescence component, obtain acid source herein by the thick acid source material that grinds or the acid source more herein of milling has a bigger particle diameter.That is to say, find to produce some problems, therefore can advantageously store acid source and grind this material before use with thick form at storage aftertreatment fine grain size acid source herein.Carbon dioxide source

Another important feature of the present invention is a carbon dioxide source.When using herein, carbon dioxide source comprises when contacting with water and acid source reacts any materials that carbonic acid gas can be provided.This source especially comprises carbonate, supercarbonate and percarbonate or its mixture, particularly supercarbonate and/or carbonate.The carbonate of Shi Yonging comprises the carbonate and the supercarbonate of potassium, lithium, sodium etc. herein, wherein preferred yellow soda ash and salt of wormwood.The supercarbonate of Shi Yonging comprises as any alkali-metal supercarbonates such as lithium, sodium, potassium herein, wherein preferred sodium bicarbonate and saleratus.Can preferably supercarbonate and carbonate be used in combination or substitute the carbonate use, because it has bigger effective weight.But, can select carbonate or supercarbonate or its mixture in the dried effervescent granule according to the desired pH of the water-bearing media that has dissolved dried effervescent granule.For example need higher pH when (as greater than pH9.5) when water-bearing media, can preferably use the combination of carbonate or use carbonate and supercarbonate separately, wherein the content of carbonate is higher than the content of supercarbonate, usually the weight ratio of carbonate and supercarbonate is 0.1 to 10, more preferably 1-5 and most preferably 1-2.

Described carbon dioxide source preferably has the volume medium of 5-375 micron, thus preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% (volume) have the particle diameter of 1-425 micron.More preferably described carbon dioxide source has the volume medium of 10-250, thus preferably at least 60%, or even at least 70% or even at least 80% or even at least 90% (volume) have the particle diameter of 1-375 micron; Perhaps even the volume medium of preferred 10-200 micron, thus preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% (volume) have the particle diameter of 1-250 micron.

In a preferred embodiment, the particle diameter of carbon dioxide source is similar to described acid source, preferred make at least 60% or even 75% carbon dioxide source have the particle diameter of 1-150 micron, preferred thus described source has the volume medium of 1-120 micron, but more preferably at least 60% or even 75% source have the particle diameter of 1-100 micron, its volume medium is 5-75, perhaps more preferably at least 60% or even the particle diameter in 75% source be 1.0-75 micron or even for the 1.0-55 micron or even be the 1.0-25 micron.

The carbon dioxide source that can preferably have the requirement particle diameter is by grinding the material of greater particle size, and the optional material of selecting to have the requirement particle diameter by any suitable method subsequently obtains.Effervescent mixture/effervescent granule and production method thereof closely

Acid source and carbon dioxide source, or its at least a portion preferably is present in the intimate mixture each other together, for the present invention, this means that described acid source and carbon dioxide source are by uniform mixing.Therefore, in a highly preferred embodiment, to the small part acid source and at least the partial CO 2 source be not isolating independent particle.Highly preferred described acid source and carbon dioxide source are present in the effervescent granule, are preferably dried effervescent granule.

Described acid is preferably with 0.1% to 99% of total particle weight, preferred 3-75%, and more preferably 5%-60%, most preferably the level of 15-50% is present in intimate mixture or the effervescent granule.

Described carbon dioxide source is preferably with 0.1% to 99% of gross weight, preferred 30-95%, and more preferably 45%-85%, most preferably the level of 50-80% is present in intimate mixture or the effervescent granule.

" do " that to should be understood to described particle substantially anhydrous, promptly do not add entry or have the moisture of non-raw material itself.Usually water-content is lower than 5% of total intimate mixture or particle weight, preferably is lower than 3%, more preferably less than 1.5%.

Can preferably in described intimate mixture or effervescent granule, there be siccative, as the inorganic or organic salt of overdrying, anhydrous salt, the especially silicate of overdrying and silico-aluminate, anhydrous silicate and/or vitriol.

In order to be implemented in the best effervesce in the water-bearing media, the acid source in intimate mixture or the effervescent granule and the weight ratio of carbon dioxide source are preferably 0.1 to 10, and be preferred 0.5 to 2.5, more preferably 1-2.

Preferred effervescent granule is by comprising granulation step, and the method that preferably includes dry powder compression or pressure agglomeration step obtains.Though all adhesion mechanisms may occur in the pressure agglomeration, the bounding force between the i.e. acid of solid particulate, carbon dioxide source and the optional tackiness agent (if present) has vital role.This is because the pressure agglomeration, especially the high pressure agglomeration is a kind of important drying means that is formed novel entities (i.e. the effervescent granule of Ganing) by solid particulate (i.e. acid, supercarbonate, carbonate source and optional tackiness agent), thereby it increases definite bulk quality or the adhesion mechanism between volume and the described solid particulate of generation more or less by using external force, provide intensity to novel entities, promptly apply big external force solid particulate is combined densely.The inventor is surprised to find in the present invention, and reducing pressure can be enough to form the acid source that is doped with than small particle size, preferably with the stable particle of the carbon dioxide source than small particle size defined above.

Described effervescent granule can have any particle diameter, and preferred particle diameter depends on particulate application and component.

In a preferred embodiment, described effervescent granule has 500 microns to 1500 microns weight average particle diameter, preferred thus described particulate at least 70% or even at least 80% (weight) have the particle diameter of 350-2000 micron, perhaps even have a weight average particle diameter of 650-1180 micron, preferred thus described particulate at least 70% or even 80% (weight) have the particle diameter of 500-1500 micron, perhaps even have a weight average particle diameter of 710-1000 micron, preferred thus described particulate at least 70% or even 80% (weight) have the particle diameter of 600-1180 micron.Have been found that the effervescent granule (comprising the acid source of definition herein) with these particle size parameters not only provides improved dispersed/dissolved, can also provide improved foaming (comprise and bubbling faster and/or improved foam).

In another preferred embodiment, described effervescent granule preferably has the weight average particle diameter of 200-500 micron, preferred thus described particulate at least 70% has the particle diameter of 100-710 micron, perhaps even have the weight average particle diameter of 250-450 micron, preferred thus described particulate at least 70% has the particle diameter of 150-650 micron.Have been found that with above-mentioned to have big effervesce particulate detergent composition and compare, the effervescent granule (comprising the acid source of definition herein) with these particle size parameters can offer described detergent composition and better distribute and/or dissolving.

The weight average particle diameter of effervescent granule and detergent particles after this can be measured by any means known in the art herein, especially a series of sieves (common 5) screening of the mesh of the sample by making partic acid associated materials herein by having different diameter or aperture obtains mass part (have thus greater than, less than the particle diameter between the mesh size of the mesh model of used sieve size or used sieve model), measures described weight (weight fraction) thus.Can calculate the median size of each part, the weight percentage of every part is taken into account, can calculate the weight average particle diameter (as with the aperture mapping of weight fraction) of described material subsequently sieve.

Intimate mixture or effervescent granule can be chosen wantonly and comprise tackiness agent or binder blend.Can use any adhesive material known in the art.For example, highly the material of Shi Heing has and is higher than 40 ℃, but preferably is lower than the fusing point of 200 ℃ or 100 ℃.Generally speaking, the tackiness agent of Shi Yonging is known to those skilled in the art herein, comprises anion surfactant such as C ₆-C ₂₀Alkyl or alkylaryl sulphonate or vitriol, preferred C ₈-C ₂₀The homopolymer of alkylbenzene sulfonate, lipid acid, derivatived cellulose such as carboxymethyl cellulose and poly carboxylic acid or multipolymer or their salt, nonionogenic tenside, preferred C ₁₀-C ₂₀Fatty alcohol ethoxylate (every mol of alcohol contains the oxyethane of 5-100 mole), more preferably C ₁₅-C ₂₀Uncle's fatty alcohol ethoxylate (every mol of alcohol contains the 20-100 moles of ethylene oxide).In the middle of these materials, preferably contain the tallow fatty alcohol ethoxylate (TAE25) of every mol of alcohol 25 moles of ethylene oxide or the tallow fatty alcohol ethoxylate (TAE50) of every mol of alcohol 50 moles of ethylene oxide.It is that 12000 to 700000 Polyvinylpyrolidone (PVP) and molecular-weight average are 600 to 10000 polyoxyethylene glycol that other preferred adhesive comprises as molecular-weight average.Maleic anhydride and ethene, methylvinylether, methacrylic acid or acrylic acid multipolymer are other example of polymeric binder.Other tackiness agent also comprises C ₁₀-C ₂₀Single glyceryl ether and two glyceryl ethers and C ₁₀-C ₂₀Lipid acid.

Preferably effervescent granule contains a kind of liniment, and it can be selected from any one liniment known in the art.Preferred liniment is to be used for melt form particulate material, and described particle is solid under envrionment conditions, as polymer materials, nonionogenic tenside.These materials also can be used as tackiness agent described herein.The particulate liniment that also can preferably can be used for the solution form of the aqueous solution or organic solvent, it comprises organic and mineral acid or salt.In addition, also can upward be coated with by microparticle material being dispensed onto described particle (siccative as described here) to described particle.

Also can preferred described intimate mixture or particle comprise other component, as detergent active (when being used for detergent composition).Be preferably tensio-active agent (it also can serve as tackiness agent and/or liniment), bleaching component (especially bleaching activity thing or precursor), catalyzer or perhydro-salt, spices, whitening agent, washing assistant, enzyme.

Usually they contain and account for 70% of particle or mixture total weight amount at the most, and preferably at the most 50%, more preferably one or more tackiness agents of 35% and/or other actives at the most.

The present invention also comprises the method for preparing effervescent granule of the present invention, and described effervescent granule comprises acid source, carbon dioxide source and optional tackiness agent, and wherein said acid source, carbon dioxide source and optional tackiness agent are in intimate mixture.Present method preferably includes following steps:

-at first preferred acid source the material that passes through the greater particle size of grinding commercial offers obtains to have the acid source that defines particle diameter herein,

-mix thus obtained acid source, preferably the acid source that obtains of the acid source material of the greater particle size by grinding commercial offers and carbon dioxide source and optional tackiness agent and/or other component to be forming mixture,

-subsequently described mixture is sent into granulation step, preferably include extrude, nodularization (spheronisation), more preferably the compression or agglomeration step.

Optional other component (as liniment, it will be discussed in the back in more detail) can the adding in the particle that obtains.

" granulation step " is meant the gained mixture made the particle that requires size that has before this definition.

Preferred method used herein is roll compaction (roller compaction).In this method, acid source and carbon dioxide source and optional tackiness agent and other component are being compelled to send between two compressing rollers after the mixing, described compressing roller brings pressure to bear on the described mixture, and the rotation of roller is converted into described mixture the sheet/piece of compression like this.Sheet/piece with this compression carries out granulation subsequently.A kind of method of implementing it is to grind described/sheet or the agglomeration mixture is carried out granulation by ordinary method.Usually can adopt Flake Crusher FC 200 available from Hosokawa Bepex GmbH ^Implement to grind.The ultimate size desired according to effervescent granule can further sieve the material that ground.Screening to this dry effervescent granule can be as using the Alpine Airjet Screen of commercial offers ^Implement.

According to this method, with described effervesce raw material and optional tackiness agent (if present) preferably do not add water and/or moisture (except those water) from raw material itself thus condition under mix mutually and obtain dried free-pouring powdered mixture.Subsequently the free-pouring powdered mixture of doing of this binder particles (if present) that contains effervesce particle (being described acid source and carbon dioxide source) and choose wantonly is implemented granulation step, preferably include the pressure agglomeration step, it is a kind of dry method step, thereby wherein this free-pouring powdered mixture bears high external force described particle is closely combined, and makes the bulk quality densification of described particle thus and produce adhesion mechanism between solid effervesce particle and tackiness agent (if present).

Typical roll compaction machine used herein is as the Pharmapaktor L200/50P available from Hosokawa Bepex GmbH ^Be roller spacing, feeding rate, compression pressure and roller speed by the process variable in the pressure agglomeration step of roll compaction.Typical apparatus for feeding is a feed worm.The roller spacing is generally 0.5-10 centimetre, and preferred 3-7 centimetre, more preferably 4-6 centimetre.Squeeze is generally 20kN-120kN, preferred 30kN-100kN, and more preferably 40kN-80kN though lower pressure also is possible, and can preferably be used in the acid source of use fine grain size of the present invention.Usually roller speed is 1rpm-180rpm, preferably 2rpm-50rpm and more preferably 2rpm-35rpm.Usually feeding rate is 1rpm-100rpm, preferred 5rpm-70rpm, more preferably 8rpm-50rpm.The temperature of implementing compression is not crucial, is generally 0-40 ℃.

Can preferred described particle be lower than under 35% the dry air and prepare in humidity.The coating of effervescence component

Can be coated with by any liniment known in the art or its mixture by preferred described effervescence component.Preferred described coating comprises tensio-active agent and any other optional detergent component.At least 20% of the described coating wt of common described surfactant comprise is preferably greater than 75%, more preferably greater than 95% and even more preferably 100%.

The arbitrary surfaces promoting agent that tensio-active agent can be known in the art is preferably alcohol alcoxylates, more preferably has at least 20, and more preferably at least 40, even the more preferably alcohol alcoxylates of the average extent of alkoxylation of 50-80.The fusing point of described alcohol alcoxylates is generally at least 40 ℃, and preferably at least 50 ℃, more preferably 60 ℃-70 ℃.Preferred alkoxyl group is an oxyethyl group.

Alcohol alcoxylates preferably has the alcohol alcoxylates of the hydrocarbon chain of 12-18 carbon atom length derived from comprising the alkyl with preferred 12-18 carbon atom.Described hydrocarbon chain can be straight or branched and comprise all derivative forms that can be obtained by any conformation of 12-18 carbon atom.

By any means known in the art, preferably the method that is sprayed on the effervescence component of the coating of the melt form by will containing alcohol alcoxylates puts on coating on the effervescence component.This relates to usually and is at least 40 ℃ in temperature, preferably at least 50 ℃, more preferably 60 ℃-70 ℃ down fusing contain the coatings of alcohol alcoxylates.Described spray method can be an any means as known in the art, preferably coating is sprayed in the rotary mixing machine that contains the nuclear material by the hot melt spray gun, perhaps spraying of the adverse current by fluidized-bed or wurster type and flow coating machine, both all are sprayed to coating on the fluidized-bed that contains effervescence component.

The effervescence component that can be obtained by aforesaid method comprises surperficial coating, preferably makes described coating coat described effervescence component by this way, although described coating also can partly coat described effervescence component.Coating also can all or part of coating effervescence component any component, promptly described acid source and/or carbon dioxide source.

Preferably coating is contacted with effervescence component by any means known in the art.Be generally the formation intimate mixture, preferably make coating layer portion by this way or all coat effervescence component.Described coating is the 0.5%-25% of effervescence component gross weight, preferred 2%-10%.

The effervescence component of coating can obtain by relating to any means of mixing various components, and this method can be the part of compression or method of tableting, extrusion molding and agglomeration technique.The effervescence component of preferred coating prepares by the following method: a kind of melt of component mixed with another component, wherein simultaneously or form solid particulate subsequently, preferably by with the described melt of after fixing, preferably by reduction processing temperature formation solids.In the time will being doped into the effervescence component of coating more than a kind of component, preferably described melt is mixed with the pre-composition of various components, thus described pre-composition with described melt-mixing before the intimate mixture of the various components of pre-mixing before obtaining to add described melt.Above-mentioned various component is a kind of specific alcohol alcoxylates, acid source, carbon dioxide source, any other optional detergent component or its arbitrary combination.

Described effervescence component can be formed for a part automatic and/or detergent composition that hand washing is used with optional arbitrarily detergent component.

Particularly, the effervescence component that comprises the coating of specific alcohol alcoxylates can be used to produce foam and also can serve as suds suppressor in the last stages of cycles of washing at the allocated phase of cycles of washing.The last stages of cycles of washing behind allocated phase 5 minutes at least.Detergent composition

In a preferred embodiment, effervescence component herein or effervescent granule are included in and need distribute and be dissolved in the water in the composition of (especially in the short period of time and/or in cold water and/or under the lower effervescent granule/material of total content).

The level that preferably exists of described effervescence component makes that the level that exists of acid source is the 0.5%-40% of detergent component weight, more preferably 1%-30% or even be 2%-25% or even 4%-20% (weight); With make that the level that preferably exists of carbon dioxide source is the 1%-60% of detergent composition weight, more preferably 2%-50% or even 4%-35% or even 6%-30% (weight).

Especially effervescence component is herein mixed cleaning compositions such as laundry detergent composition and pretreatment compositions, hard-surface cleaning compositions and dish washing detergent compositions.Especially non-aqueous liquid composition and solids composition, particularly particulate composition, tablet, extrudate and medicated roll are that this place is considered.

Described composition can contain as the acid source of isolating grain fraction and carbon dioxide source.Described composition preferably contains the effervescence component of effervescent granule form.All acid in can preferred described composition include in the effervescent granule of doing.Perhaps, can comprise effervescent granule and do acid and/or the dried carbon dioxide source that adds that adds by preferred described composition.

In a preferred embodiment, solid detergent composition herein comprises washing composition basis particle, and its at least a portion comprises at least a effervescence component (preferred particulates form).Particle preferred weight average particle diameter in washing composition basis is 350 microns to 4 millimeters subsequently, more preferably 500 microns to 2.5 millimeters or even be 710 microns to 2 millimeters.

Preferred effervescence component of the present invention is present in the detergent particles that comprises some component, described component may cause distribution or problems of dissolution or need faster dissolving, as tensio-active agent, especially nonionogenic tenside and or the mixture (particularly silico-aluminate washing assistant and anion surfactant) of anion surfactant and detergent active such as bleach-activating agent and tensio-active agent and washing assistant.

This washing composition basis particle can and can comprise any detergent component by any means preparation.Preferably washing composition basis particle prepare by following method: the different detergent particles (preferably by agglomeration, spraying drying or extruding pelletization) that will contain different detergent component mixtures mixes, subsequently choose wantonly under the adding tackiness agent compress, agglomeration, nodularization or make ball or extrude.Therefore can preferably herein effervescent granule and other detergent granules component be mixed with tackiness agent, implement granulation step such as agglomeration, nodularization subsequently or make ball.

Have been found that when effervescence component of the present invention is present in the particle of greater particle size obtaining to bubble is able to improved detergent composition.Therefore, by in detergent particles, adding effervescence component of the present invention (effervescence component that comprises particle form described herein), the invention provides a kind of in order to improve the blistered method of detergent composition, the weight average particle diameter of described detergent particles is 500 microns to 1500 microns, the particle diameter of preferred described particulate at least 70% is the 350-2000 micron thus, perhaps even have 650 microns-1180 microns weight average particle diameter, the particle diameter of preferred described particulate at least 70% is the 500-1500 micron thus.

Find that also the detergent composition that obtains has more high efficiency distribution and/or dissolving when effervescence component of the present invention is present in the less size particles.Therefore, by in detergent particles, adding according to each effervescence component among the claim 1-13, the invention provides a kind of in order to improve the distribution and/or the dissolved method of detergent composition, the weight average particle diameter of described detergent particles is 200 microns to 500 microns, the particle diameter of preferred described particulate at least 70% is the 100-710 micron thus, perhaps in addition its weight average particle diameter be 250 microns-450 microns, the particle diameter of preferred described particulate at least 70% is the 150-650 micron thus.

Particulate composition of the present invention can be prepared into has different stacking densities, is preferably the 300-1200 grams per liter, preferred 500-1100 grams per liter.These compositions can be by the whole bag of tricks known in the art, comprise do mix, spraying drying, agglomeration and granulation and combination thereof prepare.

In a preferred embodiment, described composition comprises the 0.1%-99% that accounts for composition total weight, and is preferred 2% to 50%, perhaps even 3% to 25% effervescence component or particle.

In a preferred embodiment, preferred described composition comprises some particles, wherein at least 60%, and more preferably the weight average particle diameter of at least 80% (weight) is 600 microns-1400 microns, preferred 700 microns-1100 microns or even be the 750-1000 micron.Can preferred described composition comprise less than 20% or even less than 10% or even less than the particle diameter of 5% (weight) less than 300 microns, perhaps in addition less than 425 microns or even less than 600 microns various grain fractions; Also can preferred described composition comprise less than 20% or even less than 10% or even less than the particle diameter of 5% (composition weight) greater than 1700 microns, perhaps even greater than 1400 microns or even greater than 1180 microns various grain fractions.

Described composition can be by any means preparation known in the art, and described method comprises agglomeration and/or spraying drying, above some component can mix as described here or be sprayed to thus.Can preferably prepare composition by mixing all or part particle, these particles comprise by the preparation of agglomeration or spraying drying those and even comprise effervescence combination herein, and add tackiness agent subsequently and mix or the described particle of agglomeration and tackiness agent to form preferred agglomerate detergent granules.They can have desired particle diameter or they can sieve the particle that obtains the size that requires.

Composition of the present invention also can contain other detergent component.The definite character and the adding level thereof of these other components will depend on the physical form of composition or component, and the definite character of using its washing operation.

In the time of in being present in detergent composition, but also can preferably only there be hydrated inorganic salt less than 25% blending of detergent composition weight, form with individual particles exists thus, but perhaps exists in total composition even less than the inorganic salt of 25% hydration of detergent composition weight.Can preferably there be the inorganic peroxy SYNTHETIC OPTICAL WHITNER, preferably has percarbonate thus.

In a preferred embodiment, can be preferably herein detergent composition contain one or more anion surfactants and silico-aluminate washing assistant, preferably only a spot of thus silico-aluminate washing assistant and anion surfactant in intimate mixture, promptly the total amount of anion surfactant less than 50% or even less than 30% and the total amount of silico-aluminate less than 50% or even less than 30%; Even can preferably in intimate mixture, there be anion surfactant and silico-aluminate washing assistant substantially.Therefore, can contain at least two kinds of independently particles that comprise anion surfactant or silico-aluminate by preferred described composition." intimate mixture " is meant that two or more components compositions are in component or the particle substantially equably for the present invention.Promptly have been found that solvability and/or the distributivity of having improved described composition thus.

In another embodiment of the invention, it is low-level that but preferred composition only contains, for example less than composition weight 10% or even less than 5% silico-aluminate washing assistant, preferred composition contains the washing assistant of high resolution thus, as Trisodium Citrate or citric acid, carbonate and/or crystal layered silicate.

Also but preferred composition contains the agglomerate as a builder system or a builder system part, this agglomerate contains the crystalline layered silicate (preferred NaSKS-6) of 0.5%-80% (weight) and the tensio-active agent (preferred anionic tensio-active agent) of 10%-70% (weight), thus can be preferably less than 10% free-water of agglomerate weight, the more preferably anion surfactant of the crystal layered silicate of 30%-60% (weight) and 20%-50% (weight).

Effervescence component of the present invention can contain one or more other detergent components as described here, and detergent composition preferably contains one or more and is selected from following component herein: tensio-active agent

According to the present invention and herein the component of composition preferably contains one or more tensio-active agents that are selected from negatively charged ion, nonionic, positively charged ion, both sexes, both sexes and zwitterionics and composition thereof.

The general list of the type of these negatively charged ion, nonionic, both sexes and zwitterionics and material is authorized the U.S.P.3 that gives Laughlin and Heuring on December 30th, 1975, and 929,678 provide.Other example provides in " Surface Active Agents and Detergents " (I and II volume, Schwartz, Perry and Berch).The cats product that is fit to is authorized the U.S.P.4 that gives Murphy on March 31st, 1981, list in 259,217.When existing, both sexes, both sexes and zwitterionics are used in combination with one or more negatively charged ion and/or nonionogenic tenside usually.Anion surfactant

Preferably contain other anion surfactant according to component of the present invention and/or detergent composition herein.Basically the anion surfactant that is used for the decontamination purpose arbitrarily can be included in described detergent composition.They can comprise anion sulfate acid, sulfonic acid, carboxylic acid and sarkosine tensio-active agent various salt (comprise as sodium, potassium, ammonium and substituted ammonium salt as single-, two-and triethanolamine salt).Preferred anionic vitriol and sulfosalt surfactant.

The level that exists of preferred anionic tensio-active agent is 0.1%-60%, more preferably 1-40%, most preferably 5%-30% (weight).

Highly preferred tensio-active agent comprises sulfonate and sulfate surfactant, and preferred straight or branched alkylbenzene sulfonate and alkyl ethoxyquin vitriol described herein preferably combines with cats product described herein.

Other anion surfactant comprises isethionate such as acyl isethionic salt, N-acyl taurine salt, methylamino esilate, alkyl succinate and the sulfosuccinate of fatty acid amide, monoesters (the especially saturated and unsaturated C of sulfo-succinic acid ₁₂-C ₁₈Monoesters), the diester of sulfo-succinic acid (especially saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate, resinous acid and hydrogenated resin acid also be fit to, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in or come from butter.The anion sulfate acid salt surfactant

The anion sulfate tensio-active agent of Shi Yonging comprises primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oleoyl glycerine vitriol, alkylphenol ethylene oxide ether sulfate, the C of straight chain and side chain herein ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of the vitriol of glucosamine sulfate and alkyl polysaccharide such as alkyl polyglucoside (compound of nonionic non-sulfuric acid salt described herein).

The preferred alkyl sulfate surfactant is selected from straight chain and side chain uncle C ₁₀-C ₁₈Alkyl-sulphate, more preferably C ₁₁-C ₁₅Branched-chain alkyl vitriol and C ₁₂-C ₁₄Straight-chain alkyl sulfate.

Preferred alkyl ethoxy sulfate tensio-active agent is selected from C ₁₀-C ₁₈Alkyl-sulphate (each molecule carries out ethoxylation with the oxyethane of 0.5-20 mole).More preferably described alkyl ethoxy sulfate surfactant is C ₁₁-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate (each molecule 0.5-7, preferred 1-5 moles of ethylene oxide is carried out ethoxylation).

A preferred especially aspect of the present invention adopts the mixture of preferred alkyl-sulphate and/or sulfonate and alkyl ethoxy sulfate surfactant.These mixtures have been disclosed among the PCT number of patent application WO93/18124.The anion sulfoacid salt surfactant

The anionic sulphonate tensio-active agent of Shi Yonging comprises C herein ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary alkyl sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oleoyl glycerol sulfonate and composition thereof.The anionic carboxylic acid salt surfactant

The anionic carboxylate tensio-active agent that is fit to comprises alkyl ethoxy carboxylate, many oxyethyl groups of alkyl multi-carboxylate's tensio-active agent and soap (' alkyl carboxylate (carboxyls) '), the secondary soap of especially described herein some (secondary soap).

The alkyl ethoxy carboxylate that is fit to comprises formula RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Those compounds, R is C in the formula ₆-C ₁₈Alkyl, x are 0-10, and ethoxylate distributes and to make that x is that the amount of 0 material is a positively charged ion less than 20% (by weight) and M.The alkyl polyethoxye multi-carboxylate tensio-active agent that is fit to comprises that those have RO-(CHR ₁-CHR ₂-O)-R ₃Material, R is C in the formula ₆-C ₁₈Alkyl, x are 1-25, R ₁And R ₂Be selected from hydrogen, methyl acid group, Succinic Acid group, carboxyl Succinic Acid group and composition thereof, R ₃Be selected from hydrogen, have the replacement of 1-8 carbon atom or do not replace hydrocarbon and composition thereof.

The soap class tensio-active agent that is fit to comprises and contains the unitary secondary soap surfactant of the carboxyl that links to each other with secondary carbon.The preferred secondary soap surfactant that is used for herein is a water-soluble substances, and it is selected from 2-methyl isophthalic acid-undeeanoic 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 included in the suds suppressor.The basic metal sarcosinate surfactant

Other anion surfactant that is fit to is formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, R is C in the formula ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ion.Preferred example is the sodium-salt form of myristyl and oleoyl methyl sarkosine.Oxyalkylated nonionogenic tenside

Basically oxyalkylated arbitrarily nonionogenic tenside all is applicable to this.Preferred ethoxylation and propenoxylated nonionogenic tenside.

The preferred alkoxylated tensio-active agent can be selected from the condenses of nonionic condenses, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, nonionic ethoxylate/propoxylated glycerine and propylene glycol of alkylphenol and the condensation product of nonionic ethoxylate and propylene oxide/ethylenediamine adduct.Nonionic alcohol alcoxylates tensio-active agent

Fatty alcohol and 1-25 mole alkylene oxide, especially the condensation product of oxyethane and/or propylene oxide is applicable to this.The alkyl chain of fatty alcohol can be straight or branched, uncle or secondary alkyl chain, and contain 6-22 carbon atom usually.Especially preferably have the alcohol of alkyl of 8-20 carbon atom and the condensation product of every mol of alcohol 2-10 moles of ethylene oxide.The nonionic polyhydroxy fatty acid amide surfactant

The polyhydroxy fatty acid amide that is applicable to this has formula R ²CONR ¹Z, R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁-C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is the polyhydroxy alkyl with the straight-chain alkyl chain that directly links to each other with at least 3 hydroxyls, or its alkoxy derivative (preferred ethoxylation or propoxylation).Z is preferably derived by reducing sugar in reductive amination process; More preferably Z is glycityl.The nonionic fatty acid amide surfactant

The fatty acid amide surfactant that is fit to comprises having formula R ⁶CON (R ⁷) ₂Those materials, R in the formula ⁶For containing 7-21, the alkyl of preferred 9-17 carbon atom, each R ⁷Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, x is 1-3 in the formula.The nonionic alkyl polysaccharide surfactant

The alkyl polysaccharide of Shi Yonging is disclosed in and authorized the United States Patent (USP) 4 that gives Llenado on January 21st, 1986 herein, 565,647, described alkyl polysaccharide has the hydrophobic grouping of 6-30 carbon atom and contains polysaccharide such as many glycosides (polyglucoside) of the hydrophilic radical of 1.3-10 sugar unit.

Preferred alkyl polyglycoside has formula R ²O (C _nH _2nO) _t(glycosyl) _x, R in the formula ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T is 0-10, and x is 1.3-8.Glycosyl is preferably derived from glucose.Amphoterics

The amphoterics of Shi Yonging comprises amine oxide surfactant and alkyl both sexes carboxylic acid herein.

The amine oxide that is fit to comprises having formula R ³(OR ⁴) _xNO (R ⁵) ₂Those compounds, R in the formula ³Be selected from alkyl, hydroxyalkyl, amido propyl group and the alkylbenzene group or its mixture that contain 8-26 carbon atom; R ⁴Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; R ⁵The alkyl or the hydroxyalkyl of respectively doing for oneself and containing 1-3, or contain the polyethylene oxide group of 1-3 ethylene oxide group.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈Amidoalkyl dimethyl oxidation amine.

The suitable example of alkyl both sexes carboxylic acid is by Miranol, Inc., Dayton, the Miranol that NJ produces ^TMC2M Conc.Zwitterionics

Zwitterionics also can add in the detergent composition of the present invention.These tensio-active agents can generalized description be the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the example that is used for zwitterionics herein.

The trimethyl-glycine that is fit to is for having formula R (R ') ₂N ⁺R ²COO ^-Compound, R is C in the formula ₆-C ₁₈Alkyl, R ¹Be generally C separately ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C _12-18Dimethyl Ammonium capronate and C _10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.Complexing trimethyl-glycine surface also is applicable to herein.Cats product

The cats product of Shi Yonging comprises quaternary ammonium surfactant herein.Preferred quaternary ammonium surfactant is single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl in the formula.Also preferred monoalkoxyization and bis-alkoxy amine tensio-active agent.

Can be used for herein detergent composition or the another kind of suitable cats product of its component be the cationic ester tensio-active agent.Described cationic ester tensio-active agent comprises at least one ester (compound of key and at least one positively charged ion charged group promptly-COO-) for what (preferably water dispersive) had a surfactant properties.

The cationic ester tensio-active agent (comprising the cholinesterase tensio-active agent) that is fit to has been disclosed in as U.S. Patent number 4228042,4239660 and 4260529.

One preferred aspect, ester bond and positively charged ion charged group are spaced apart base separately mutually in surfactant molecule, described spacer is by containing at least 3 atoms (i.e. the chain length of three atoms), preferred 3-8 atom, more preferably 3-5 atom, most preferably the chain of 3 atoms is formed.The atom that forms spacer is selected from carbon, nitrogen and Sauerstoffatom and arbitrary combination thereof, and condition is only to link to each other with carbon on the chain at any nitrogen on the described chain and Sauerstoffatom.Therefore do not comprise have as-O-O-(being superoxide) ,-N-N-and-spacer of N-O-key, and comprise having as-CH ₂-O-CH ₂-and-CH ₂-NH-CH ₂The spacer of-key.One preferred aspect, the spacer chain includes only carbon atom, optimum select chain is a hydrocarbyl chain.Cation mono-alkoxylated amines tensio-active agent

Highly preferred herein cation mono-alkoxylated amines tensio-active agent preferably has following general formula I,

R in the formula ¹Have an appointment 6 to about 18 carbon atoms for containing, preferred 6 to about 16 carbon atoms, most preferably from about 6 alkyl or alkenyl parts to about 14 carbon atoms; R ²And R ³Independently of one another for to contain 1 alkyl to about 3 carbon atoms, preferable methyl, most preferably R ²And R ³Be methyl; R ⁴Be selected from hydrogen (preferably), methyl and ethyl; X ^-For thereby negatively charged ion such as chlorine negative ion, bromine negative ion, methylsulfate, sulfate radical etc. provide electric neutrality; A is an alkoxyl group, especially oxyethyl group, propoxy-or butoxy; P is 0 to about 30, preferred 2 to about 15, most preferably 2 to about 8.

ApR among the preferred formula I ⁴The p=1 of group and be hydroxyalkyl, carbonatoms is no more than 6, thus-nitrogen-atoms that the OH group is no more than 3 carbon atom and quaternary ammonium separates.Especially preferred ApR ⁴Group is-CH ₂CH ₂OH ,-CH ₂CH ₂CH ₂OH ,-CH2CH (CH ₃) OH and-CH (CH ₃) CH ₂OH, especially preferred-CH ₂CH ₂OH.Preferred R ¹Group is a straight chained alkyl.The straight chain R that preferably has 8-14 carbon atom ¹Group.

The another kind of highly preferred cation mono-alkoxylated amines tensio-active agent that is used for herein has following formula R in the formula ¹Be C ₁₀-C ₁₈Alkyl and combination thereof, especially C ₁₀-C ₁₄Alkyl, preferred C ₁₀-C ₁₂Alkyl, thus X for arbitrarily easily negatively charged ion provide charge balance, preferred chlorine negative ion or bromine negative ion.

The compound that it should be noted that the front type comprises those wherein oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy, isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃) O] unit (i-Pr) or positive propoxy unit (Pr), or EO and/or Pr and/or the unitary combination metathetical of i-Pr compound.

The preferred levels of cation mono-alkoxylated amines tensio-active agent is 0.1%-20%, more preferably 0.2%-7%, most preferably 0.3%-3.0% (weight).Positively charged ion is two-the alkoxylated amines tensio-active agent

Preferred cationic bis-alkoxy amine tensio-active agent has general formula I I, R in the formula ¹Have an appointment 8 to about 18 carbon atoms for containing, preferred 10 to about 16 carbon atoms, most preferably from about 10 alkyl or alkenyl parts to about 14 carbon atoms; R ²For containing the alkyl of 1-3 carbon atom, preferable methyl; R ³And R ⁴Can independent variation and be selected from hydrogen (preferably), methyl and ethyl, X-is negatively charged ion such as chlorine negative ion, bromine negative ion, methylsulfate, sulfate radical etc., is enough to provide electric neutrality.A and A ' can independent variation and are selected from C separately ₁-C ₄Alkoxyl group, especially oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and combination thereof; P is 1 to about 30, preferred 1 to about 4, and q is 1 to about 30, preferred 1 to about 4, and most preferably p and q are 1.

The highly preferred positively charged ion bis-alkoxy amine tensio-active agent that is used for herein has following formula,

R in the formula ¹Be C ₁₀-C ₁₈Alkyl and combination thereof, preferred C ₁₀, C ₁₂, C ₁₄Alkyl and combination thereof.Thereby X for arbitrarily easily negatively charged ion provide charge balance, preferred chlorine negative ion.With reference to the general structure of above-mentioned positively charged ion bis-alkoxy amine, because in preferred compound, R ¹Derived from (cocounut oil) C ₁₂-C ₁₄Moieties lipid acid, so R ²Be methyl, ApR ³And A ' qR ⁴The monosubstituted ethoxy of respectively doing for oneself.

Other positively charged ion bis-alkoxy amine tensio-active agent that is used for herein comprises the compound with following formula,

R in the formula ¹Be C ₁₀-C ₁₈Alkyl, preferred C ₁₀-C ₁₄Alkyl, independently p is 1 to about 3, q is 1 to about 3, R ²Be C ₁-C ₃Alkyl, preferable methyl, X is a negatively charged ion, especially chlorine negative ion or bromine negative ion.

Other compound of aforementioned type comprises those oxyethyl group (CH wherein ₂CH ₂O) unit (EO) is by butoxy, isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃) O] unit (i-Pr) or positive propoxy (Pr), or EO and/or Pr and/or the unitary combination metathetical of i-Pr compound.Bleach-activating agent

Component of the present invention and/or detergent composition herein preferably contain bleach-activating agent, preferably contain the organic peroxide acid bleach precursor.Can comprise at least two kinds of peroxyacid bleach precursors by preferred described composition, the hydrophobic peroxyacid bleach precursor of preferred at least a definition herein and at least a hydrophilic peroxyacid bleach precursor of definition herein.Reaction in by described precursor and hydrogen peroxide cource generates organic peroxide acid subsequently.

Bleach-activating agent also can selectively perhaps comprise preformed peroxyacid bleach in addition.

Preferred bleach-activating agent is present in the grain fraction of component herein or composition.Can be preferably as independently, the blended particle exists.Perhaps, bleach-activating agent or its part may reside in the basic detergent particles.

Preferred at least a bleach-activating agent (preferred peroxyacid bleach precursor) is present in the grain fraction, and the weight average particle diameter of described grain fraction is 600 microns to 1400 microns, preferred 700 microns to 1100 microns.More preferably all activators are present in one or more grain fractions with specific weight average particle diameter.

Thus, can be preferably at least 80%, preferred at least 90% or even at least 95% or even basically 100% the component that comprises described bleach-activating agent or the particle diameter of various components be 300 microns to 1700 microns, preferred 425 microns to 1400 microns.

Hydrophobic peroxyacid bleach precursor preferably includes has oxygen-compound of benzene sulfonate group, preferred NOBS, DOBS, LOBS and/or NACA-OBS described herein.

Hydrophilic peroxyacid bleach precursor preferably includes TAED described herein.Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that generates peroxy acid in crossing hydrolysis (perhydrolysis) reaction with hydroperoxidation.Usually peroxyacid bleach precursor can be expressed as

L is a leavings group in the formula, and X can be any functional group basically, and the structure of the peroxy acid that generates in crossing hydrolysis is like this

For the present invention, hydrophobic peroxyacid bleach precursor generates the peroxy acid of following formula, and wherein X contains the group of at least 6 carbon atoms and the peroxyacid bleach that hydrophilic peroxyacid bleach precursor generates following formula, and wherein X is the group that contains 1-5 carbon atom.

The preferred adding level of peroxyacid bleach precursor compound is 0.5%-30% (weight), more preferably 1%-15% (%), most preferably 1.5%-10% (weight).Hydrophilic and ratio hydrophobic bleach agent precursor (when existing) are preferably 10: 1-1: 10, more preferably 5: 1-1: 5 or even 3: 1-1: 3.

The peroxyacid bleach precursor compound that is fit to contains one or more N-or O-carboxyl groups usually, can extensively select its precursor-type.The type that is fit to comprises acid anhydrides, ester, imide, lactan and the acylated derivatives of imidazoles and oxime.The example that belongs to the useful materials of these types is disclosed among the GB-A-1586789.The ester that is fit to be disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.Leavings group

Leavings group (after this representing with the L group) must have enough activity to the hydrolysis reaction of crossing that carries out in optimal time section (as cycles of washing).But if the L activity is too strong, this activator will be difficult to stably be used for bleaching composition.

Preferred L group is selected from: And composition thereof, R in the formula ¹Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R ³For containing the alkyl chain of 1-8 carbon atom, R ⁴Be H or R ³Y is H or solubilizing group.R ¹, R ³And R ⁴Any can be replaced by following any functional group basically, these functional groups comprise as alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.

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

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids in crossing hydrolysis.Preferred this class precursor provides peracetic acid in crossing hydrolysis reaction.

The alkyl peroxycarboxylic acid precursors compound of preferred imide type comprises N, N, N ¹, N ¹Tetra-acetylated Alkylenediamine, wherein alkylidene group contains those compounds that 1-6 carbon atom, particularly alkylidene group contain 1,2 and 6 carbon atom.Tetra acetyl ethylene diamine (TAED) especially is preferably used as hydrophilic peroxyacid bleach precursor.

Other preferred alkyl peroxycarboxylic acid precursors comprises 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 of the acid amides replacement that herein is suitable for comprises those compounds with following general formula:

R in the formula ¹For having about 1 aryl or alkaryl, R to about 14 carbon atoms ²For containing alkylidene group, arylidene and the alkyl arylene of 1 to 14 carbon atom of having an appointment, R ⁵For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom, L can be any leavings group basically.R ¹Preferably contain 6 to 12 carbon atoms of having an appointment.R ²Preferably contain 4 to 8 carbon atoms of having an appointment.R ¹Can or comprise side chain, substituting group or both alkylaryls for straight or branched alkyl, substituted aryl, and can be from synthetic source and natural source (comprising as tallow).The variant of similar structures also is fit to R ²R ²Can comprise alkyl, aryl, wherein said R ²Also can comprise halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Be preferably H or methyl.R ¹And R ⁵Total should not contain more than 18 carbonatomss.The bleach activating immunomodulator compounds that such acid amides replaces is described in EP-A-0170386.Preferred R ¹And R ⁵Form ring structure with nitrogen and carbon atom.

The preferred example of such bleach precursor comprises the peroxyacid precursor compound that acid amides replaces; these compounds are selected from (6-decoyl amido-caproyl) oxygen base benzene sulfonate, (6-caprinoyl amido-caproyl) oxygen base benzene sulfonate, highly preferred (6-nonanoyl amido caproyl) oxygen base benzene sulfonate and composition thereof (being described in EP-A-0170386).Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid in crossing hydrolysis.The O-acidylate peroxybenzoic acid precursors compound that is fit to comprises and replacing and unsubstituted benzoyloxy benzene sulfonate, sorbyl alcohol, glucose and all sugared benzoylation products that adopts the benzoylation reagent; and those compounds of imide type, comprise the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.The imidazole type peroxybenzoic acid precursors that is fit to comprises N-benzoyl imidazoles and N-benzoyl benzoglyoxaline.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.The positively charged ion peroxyacid precursor

Positively charged ion peroxyacid precursor compound generates the positively charged ion peroxy acid in crossing hydrolysis.

Usually partly form the positively charged ion peroxyacid precursor by the peroxy acid that replaces the peroxyacid precursor compound that is fit to positively charged functional group (as ammonium or alkane ammonium, preferred second ammonium or first ammonium group).The positively charged ion peroxyacid precursor usually in solid detergent composition the form with salt with suitable negatively charged ion such as halogen anion exist.

The peroxyacid precursor compound that replaces of positively charged ion can be peroxybenzoic acid or its substitutive derivative, precursor compound (as previously mentioned) like this.Perhaps, the peroxyacid precursor compound can be the alkyl peroxy acids precursor (as described in after this) that alkyl peroxycarboxylic acid precursors compound or acid amides replace.

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

The example of preferred cation peroxyacid precursor is described in GB Patent Application No. 9407944.9 and Application No. 08/298903,08/298650,08/298904 and 08/298906.

The positively charged ion peroxyacid precursor that is fit to comprises alkyl or the tetra-acetylated glucose benzoyl peroxide of benzoyloxy benzene sulfonate, N-acidylate hexanolactam and single benzoyl that any ammonium or alkylammonium replace.The preferred cationic peroxyacid precursor of N-acidylate hexanolactam class comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.Benzoxazine (benzoxazin) organic peroxy acid precursor

Be disclosed in as EP-A-332,294 and EP-A-482, the precursor compound of 807 benzo oxazinyl also is fit to, and especially has those compounds of following formula,

R in the formula ¹Be H, alkyl, alkaryl, aryl or aralkyl.Preformed organic peroxide acid

According to the present invention and/or the component of detergent composition herein can contain (except or as the substitute of organic peroxide acid bleach precursor compound) preformed organic peroxide acid, usually its level is 1%-15% (weight), more preferably 1%-10% (weight).

The preferred organic peroxy acid compound of one class is the compound that acid amides replaces, and it has following general formula,

R in the formula ¹Be alkyl, aryl or the alkaryl with 1-14 carbon atom, R ²Be alkylidene group, arylidene and the alkyl arylene that contains 1-14 carbon atom, R ⁵For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy acid compound that this class acid amides replaces is described in EP-A-0170386.

Other organic peroxide acid comprises diacyl and four acyl peroxides, especially diperoxy dodecandioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.Single-and two cross nonane diacids, list-and two mistake brassylic acids and N-O-phthalic amido peroxide caproic acid also be applicable to this.The perhydride source

Inorganic perhydrate salts is preferred peroxide source.The level that exists of preferred these salt is the 0.01%-50% (weight) of described composition or component, more preferably 0.5%-30% (weight).

Inorganic perhydrate salts comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salts is generally an alkali metal salt.Inorganic perhydrate salts can be used as not have and adds the crystalline solid forms of protection and included.But for some perhydrate salt, the coated form of described material is adopted in the preferred enforcement of these particulate compositions, and the better package stability of perhydrate salt in the granular product is provided like this.The coating that is fit to comprises inorganic salt such as alkalimetal silicate, carbonate or borate or its mixture, perhaps organic materials such as wax, oil or fatty soap.

Sodium peroxoborate is a kind of preferred perhydrate salt, and can mark formula (norninalformula) NaBO ₂H ₂O ₂Monohydrate or NaBO ₂H ₂O ₂.3H ₂The form of the tetrahydrate of O exists.

Alkali metal percarbonate, especially SPC-D is preferred herein perhydrate.SPC-D is a kind of addition compound, its corresponding 2Na ₂CO ₃.3H ₂O ₂, and form that can crystalline solid obtains commercial offers.

The peroxide Potassium peroxysulfate is that another kind is used for the inorganic perhydrate salts of detergent composition herein.Dyestuff

A kind of preferred ingredients of composition is dyestuff and dye granule or spot (speckles) herein, and they are responsive for bleaching.Dyestuff used herein can be the aqueous solution or the non-aqueous solution of dyestuff or dyestuff.Can preferred described dyestuff be the aqueous solution that comprises dyestuff; obtain the suitable detergent particles or the dyeing of spot with any level; the level of the preferred dye solution that obtains like this is up to 2% (weight) of dye granule described herein, or more preferably up to 0.5% (weight).Described dyestuff also can mix with nonaqueous carrier material such as on-aqueous liquid material (comprising nonionogenic tenside).

Described dyestuff is optional also to comprise other component such as organic jointing material, and they also can be non-water liquid.

Dyestuff can be the dyestuff that is fit to arbitrarily.The object lesson that is fit to dyestuff comprises E104-food yellow 13 (quinoline yellow), E110-food yellow 3 (sunset yellow FCF), E131-food blue 5 (patent blue V), Ultra Marine blue (trade(brand)name), E133-food blue 2 (brilliant blue FCF), E140-natural green 3 (chlorophyll and CHLOROPHYLLINE), E141 and Pigmentgreen 7 (chlorination CuPc).Preferred dyestuff can be Monastral Blue BV paste (trade(brand)name) and/or Pigmasol Green (trade(brand)name).

Painted detergent particles or effervescence component preferably contain at the most 10% or more preferably at the most 2% or even the dyed particles or the component of 1% (weight) at the most.Spices

Component of the present invention or herein the another kind of preferred ingredients of composition be spices or flavor compositions.Can use any flavor compositions herein.Described spices also can be encapsulated.

Preferred spices contains at least a low-molecular-weight volatile constituent such as molecular weight is the component of 150-450 or preferred 350.

Preferred described perfume composition comprises oxygen-containing functional group.Preferred functional group is aldehyde, ketone, alcohol or ether functional group or its combination.Heavy metal ion chelating agent

According to the present invention and/or the component of detergent composition herein preferably contain heavy metal ion chelating agent as optional components.Heavy metal ion chelating agent is meant the component of serving as heavy metal ion chelating agent herein.These components also can have the sequestering power of calcium and magnesium, but preferably they to having selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

The common amount of heavy metal ion chelating agent is the 0.005%-10% of described composition or composition weight, preferred 0.1%-5%, more preferably 0.25%-7.5%, most preferably 0.3%-2%.

The heavy metal ion chelating agent of Shi Yonging includes organic phosphonates such as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo propylidene phosphonate herein.

In the above in the compound, preferred heavy metal ion chelating agent is diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexanediamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1,1-diphosphonate, 1,1-hydroxyl hexane di 2 ethylhexyl phosphonic acid and 1,1-hydroxyl ethane dimethylene phosphonic acids.

The suitable heavy metal ion chelating agent of other of Shi Yonging comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid such as second diamino tetraacethyl, quadrol two Succinic Acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine two Succinic Acid or its any salt herein.

The heavy metal ion chelating agent that is fit to of other of Shi Yonging is iminodiacetic acid derivatives such as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid (being described in EP-A-317,542 and EP-A-399,133) herein.Be described in EP-A-516,102 iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl sulfonic acid sequestrant also are applicable to this.Be described in EP-A-509, Beta-alanine-N of 382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic Succinic Acid sequestrant also are fit to.

EP-A-476,257 have described the sequestrant based on amino that is fit to.EP-A-510,331 have described by collagen protein, Keratin sulfate or the casein derived and next sequestrant that is fit to.EP-A-528,859 have described the alkyl imino oxalic acid sequestrant that is fit to.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is fit to.G-NH2-N, N '-two Succinic Acid (GADS), quadrol-N-N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N-N '-two Succinic Acid (HPDDS) also are fit to.

Especially preferred diethylene triaminepentaacetic acid(DTPA), quadrol-N, N '-two Succinic Acid (EDDS) and 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or its an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, or its mixture.

Particularly, it is may be to SYNTHETIC OPTICAL WHITNER responsive and be applicable in the composition of the present invention to contain the sequestrant of amino or amido.Enzyme

The another kind of highly preferred composition that is used for component herein or composition is the enzyme of one or more interpolations.

The preferred enzyme material that adds comprises lipase, keratanase, amylase, neutrality and Sumizyme MP, cellulase, endolase, esterase, polygalacturonase, Sumylact L and the peroxidase that is routinely added to the commercial offers in the detergent composition.The enzyme that is fit to is at United States Patent (USP) 3,519, discusses in 570 and 3,533,139.

The proteolytic enzyme that preferred commercially available protein enzyme comprises the proteolytic enzyme sold with the trade(brand)name of Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), sold with the trade(brand)name of Maxatase, Maxacal and Maxapem by Gist-Brocades, by Genencor International sell proteolytic enzyme and those proteolytic enzyme of selling with the trade(brand)name of Opticlean and Optimase by Solvay Enzymes.The proteolytic enzyme that can add the present composition can join in the composition of the present invention with the level of the organized enzyme of the 0.0001%-4% of described composition weight.

Preferred amylase comprises the α-Dian Fenmei that obtains as the specific bacterial strain by Bacillus licheniformis (B licheniformis), its more detailed content be described in GB-1,269,839 (Novo).Preferred commodity starch enzyme comprise as sell with the trade(brand)name of Rapidase by Gist-Brocades those, by Novo Industries A/S with Termamyl, those amylase that the trade(brand)name of Duramyl and BAN is sold.Highly preferred amylase can be for being described in those amylase of PCT/US 9703635 and WO95/26397 and WO96/23873.

Amylase can add in the composition of the present invention with the organized enzyme level of 0.0001%-2% (weight).

Lipolytic enzyme can be with 0.0001%-2% (weight), preferred 0.001%-1% (weight), and most preferably the level of the active lipolytic enzyme of 0.001%-0.5% (weight) exists.

Lipase can be to come from fungi or bacterium, by as by Humicola sp, Thermomyces sp. or Pseudomonas sp, bacterial strain production obtains.Also be applicable to this from the chemistry of these bacterial strains or the lipase of gene modification mutant.Preferred lipase is derived from pseudomonas pseudoalcaligenes (Pseudomonas pseudoalcaligenes), and it is described in the European patent EP-B-0218272 of mandate.

Another kind of herein preferred lipase is by cloning from the gene of Humicola lanuginosa and express acquisition (being described in European patent application EP-A-0258 068) in Aspergillus oryza (host), it is by Novo Industri A/S, Bagsvaerd, Denmark obtains commercial offers with the trade(brand)name of Lipolase.This lipase also is described in and authorized the United States Patent (USP) 4,810,414 give Huge-Jensen etc. on March 7th, 1989.White dyes

Component herein or composition also preferably contain the hydrophilic white dyes (as mentioned above) of some type of the 0.005%-5% that has an appointment (weight).

The hydrophilic white dyes of Shi Yonging comprises that those have the compound of following structural formula herein,

R in the formula ₁Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholinyl, chlorine and amino; M is salt-forming cation such as sodium or potassium.

In following formula, work as R ₁Be anilino, R ₂Be N-2-pair-hydroxyethyl, when M was positively charged ion such as sodium, described whitening agent was 4,4 '-two [(4-anilino-6-(N-2-couple-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid and disodium salt.This concrete whitening agent is sold with the trade(brand)name of Tinopal-UNPA-GX by Ciba-GeigyCorporation.Tinopal-CBS-X and Tinopal-UNPA-GX are the preferred hydrophilic white dyess that are suitable for of detergent composition herein.

In following formula, work as R ₁Be anilino, R ₂When being positively charged ion such as sodium for N-2-hydroxyethyl-N-2-methylamino-and M, described whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl-N-methylamino)-s-triazine-2-yl)-amino] 2, and 2 '-Stilbene disulfonic acid disodium salt.This concrete whitening agent is sold with the trade(brand)name of Tinopal-5BM-GX by Ciba-Geigy Corporation.

In following formula, work as R ₁Be anilino, R ₂When being positively charged ion such as sodium for morpholinyl and M, described whitening agent is 4,4 '-two [(4-anilino-6-morpholinyl-s-triazine-2-yl) amino] 2,2 '-Stilbene disulfonic acid sodium salt.This concrete whitening agent is sold with the trade(brand)name of Tinopal-DMS-X and Tinopal AMS-GX by Ciba-Geigy Corporation.Optical white

Optical white is the preferred ingredient of composition or component herein.Preferred herein optical white comprises the compound with porphines or porphyrin structure.

Porphines and porphyrin are used as synonym in the literature, but the simplest porphyrin that the representative of conventional porphines does not replace; Its mesoporphyrin is a subclass of porphines.The porphines that the application quotes will comprise porphyrin.

The porphines structure optimization comprises metallic element or positively charged ion, preferred Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn.

Can preferred described photobleaching compound or component be selected from following substituting group and replaced: alkyl, as methyl, ethyl, propyl group, the tertiary butyl and aromatic ring system such as pyridyl, pyridyl-N-oxide compound, phenyl, naphthyl and anthryl part.

Photobleaching compound or component can have solubilization radical as substituting group.Perhaps, or in addition optical white can contain can the described photobleaching compound of solubilising polymeric constituent, as PVP, PVNP, PVI or its multipolymer or its mixture.

Highly preferred photobleaching compound is the compound with phthalocyanine structure, and it preferably has aforesaid metallic element or positively charged ion.

Metal phthalocyanine and their derivative have Fig. 1 and/or structure shown in Figure 2, and wherein the position of atom adopts ordinary method to encode on the phthalocyanine structure.

Described phthalocyanine can for as phthalocyanine structure at 1-4,6,8-11,13,15-18,20,22-25 is substituted on one or more positions of 27 atoms.The water soluble detergency promoter compound

Component or composition preferably contain the water soluble detergency promoter compound herein, its usually the amount in detergent composition be 1%-80% (weight), preferred 10%-60% (weight), most preferably 15%-40% (weight).

Detergent composition of the present invention preferably includes phosphatic washing assistant material.Preferably having level is 0.5%-60%, more preferably 5%-50%, more preferably 8%-40%.

Phosphatic washing assistant material preferably includes tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

The water soluble detergency promoter compound that is fit to comprises water-soluble mono build polycarboxylate or their sour form, homopolymerization or copolymerization polycarboxylic acid or their salt (wherein polycarboxylic acid contain be no more than at least two carboxyls that two carbon atoms are separated from each other), borate and aforementioned mixture arbitrarily.

Although owing to the common preferred monomers type of the reason of price and performance polycarboxylate, described carboxylate salt or polycarboxylate washing assistant can be haplotype or oligomeric.

The carboxylate salt that contains a carboxyl that is fit to comprises the water-soluble salt of lactic acid, oxyacetic acid (glycolic acid) and ether derivant thereof.The polycarboxylate that contains two carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of Succinic Acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The polycarboxylate or their acid-specific that contain three carboxyls comprise that water-soluble citrate, aconitate (aconitrate) and citraconate and succinate derivative are as being described in British Patent No. 1,379,241 carboxymethyl oxygen succinate, be described in British Patent No. 1,389,732 lactoyl oxygen succinate (lactoxysuccinates) and be described in the amino-succinic acid salt of Netherlands patent applications 7205873 and oxygen multielement carboxylate salt material as being described in British Patent No. 1,387,447 2-oxa--1,1,3-tricarballylic acid salt.The polycarboxylic acid that most preferably contains three carboxyls is a citric acid, and preferably having level is 0.1%-15%, more preferably 0.5%-8% (weight).

The polycarboxylate that contains four carboxyls comprises and is disclosed in British Patent No. 1,261,829 oxygen connection succinate (oxydisuccinates), 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent polycarboxylate of sulfo group and comprise and be disclosed in British Patent No. 1,398,421 and 1,398,422 and the sulfosuccinate derivant of U.S. Patent number 3,936,448 and be described in British Patent No. 1,439,000 sulfonation pyrolysis Citrate trianion.Preferred polycarboxylate contains the hydroxycarboxylate of three carboxyls, more preferably Citrate trianion at the most for each molecule.

Female acid of haplotype or oligomeric polycarboxylate sequestrant or their mixture and their salt such as citric acid or Citrate trianion/citric acid mixture are also considered to be used in the builder component.

The borate washing assistant and contain washing composition store or wash conditions under can to generate the washing assistant that boratory borate forms material be the water soluble detergency promoter that is applicable to this.

The example that is fit to of water-soluble phosphate washing assistant is alkali-metal tri-polyphosphate, trisodium phosphate, potassium and ammonium, and trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, the polymerization degree is about 6 to 21 Sodium polymetaphosphate/sodium polyphosphate and phytate.Be partly dissolved or insoluble washing-aid compound

According to component of the present invention or herein composition can contain and be partly dissolved or insoluble washing-aid compound, its usually the level that exists in detergent composition be 0.5%-60% (weight), preferred 5%-50% (weight), most preferably 8%-40% (weight).

The main example of water-insoluble washing assistant comprises sodium silicoaluminate.As mentioned above, in one embodiment of the invention, can preferably have only a spot of silico-aluminate washing assistant to exist.

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

Described aluminosilicate zeolite can be natural materials, but is preferably synthetic materials.It is Zeolite A that synthetic crystalline silica-aluminate ion-exchange material can derive from the trade mark, Zeolite B, Zeolite P, Zeolite X, commodity of Zeolite HS and composition thereof.Zeolite A has formula Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] .xH ₂X is 20-30 in the O formula, especially 27.Zeolite X has formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] .276H ₂O.

Another kind of preferred aluminosilicate zeolite is a zeolite MAP builder.The level that exists of zeolite MAP can be 1%-80%, more preferably 15%-40% (weight).

Zeolite MAP is described in EP 384070A (Unilever).It is defined as the silicoaluminate an alkali metal salt of zeolite P type, and silica alumina ratio is not more than 1.33, and preferable range is 0.9-1.33, and more preferably scope is 0.9-1.2.

Especially relevant is to have to be not more than 1.15, more specifically for being not more than the zeolite MAP of 1.07 silica alumina ratio.

One preferred aspect, the particle diameter of zeolite MAP washing auxiliary detergent is (with median particle diameter d ₅₀Expression) is 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferably is the 2.5-5.0 micron.

d ₅₀The diameter of the particle of value representation 50% (weight) is worth less than this.Described particle diameter can specifically be measured as the micro-mensuration of employing scanning electronic microscope or by laser particle size analyzer by routine analysis technology described herein.Establish d ₅₀Other method of value is disclosed in EP384070A.Organic polymer

Organic polymer is preferred other component herein, and preferably exists with the form of the component of any grain fraction, and wherein they can be used for grain fraction is bonded together mutually.Organic polymer herein is meant any basically polymerizable organic compound of the dispersion agent, anti redeposition agent or the soil-suspending agent that are used as detergent composition usually, it comprises any one high molecular organic polymer of describing as clay flocculating agent herein, comprises according to quaternized (quaternised) ethoxylation of the present invention (gathering) amine clay-decontamination/anti redeposition agent.

Usually the level that adds the organic polymer of detergent composition of the present invention is the 0.01%-30% of described composition or composition weight, preferred 0.1%-15%, most preferably 0.5%-10%.

The example of organic polymer comprises water-soluble organic homopolymerization or copolymerization polycarboxylic acid or their salt, and wherein said polycarboxylic acid comprises and is no more than two separated at least two carboxyls of carbon atom.The polymkeric substance of latter type is disclosed in GB-A-1, and 596,756.The example of these salt is the multipolymer with the polyacrylic ester of MWt of 1000-5000 and they and maleic anhydride, and the molecular weight of these multipolymers is 2000-100,000, especially 40, and 000-80,000.

Polyamino compounds is applicable to this, they comprise as be disclosed in EP-A-305282, EP-A-305283 and EP-A-351629 by aspartate-derived and those materials that come.

Contain and be selected from the monomeric terpolymer of toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, especially molecular-weight average is 5,000-10, and those multipolymers of 000 also are applicable to this.

Being suitable for adding herein, other organic polymer of detergent composition comprises derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.

Other organic polymer that is suitable for is a polyoxyethylene glycol, and especially molecular weight is 1000-10000, more preferably 2000-8000, most preferably from about those polyoxyethylene glycol of 4000.

Highly preferred herein polymeric component is the United States Patent (USP) 5,415,807 according to the United States Patent (USP) 4,968,451 of Scheibel etc. and Gosselink etc., especially according to the cotton goods and the non-cotton goods soil release polymers of Application No. 60/051517.

The another kind of organic compound of the preferably clay dispersion agent/anti redeposition agent that herein uses can be the ethoxylation positively charged ion monoamine and the diamines of following formula, X is a non-ionic group in the formula, is selected from H, C ₁-C ₄Alkyl or hydroxy alkyl ester or ether and combination thereof, a is 0-20, preferred 0-4 (as ethylidene, propylidene, hexa-methylene), b is 1 or 0; For positively charged ion monoamine (b=0), n is at least 16, and scope is 20-35 usually; For cationic diamine (b=1), it is about 12 that n is at least, and scope is about 12 to about 42 usually.

Other dispersion agent used herein/deposition agent is described in EP-B-011965 and United States Patent (USP) 4,659,802 and United States Patent (USP) 4,664,848 again.Press down foam system

When the preparation machine cleaning composition, component and detergent composition can contain and press down foam system herein, and there is level in it is the 0.01%-15% of described composition or composition weight, preferred 0.02%-10%, most preferably 0.05%-3%.

The foam that presses down that is applicable to this is mainly to contain any known defoaming compounds, comprises as silicone defoamer and 2-alkyl alcanol defoaming compounds.

Defoaming compounds herein is meant that any can be used in as suppressing produces the foamy compound of (especially under the situation of stirred solution) or the mixture of these compounds by detergent composition solution.

The especially preferred defoaming compounds that is used for herein is the silicone defoaming compounds that comprises the silicone component that herein is defined as to any defoaming compounds.These silicone defoaming compounds also contain silica component usually.General term " silicone " used herein and industrial comprises the various higher molecular weight polymer that contain siloxane unit and dissimilar alkyl.Preferred silicone defoaming compounds is a siloxanes, the polydimethylsiloxane that especially has the trimethylsilyl end-blocked block unit.

Other defoaming compounds that is fit to comprises mono carboxylic lipid acid and soluble salt thereof.These materials are described in and authorize the United States Patent (USP) 2,954,347 that gives Wayne St.John September 27 nineteen sixty.Usually have 10-24 carbon atom as the mono carboxylic lipid acid of suds suppressor and the hydrocarbon chain of salt thereof, preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt such as sodium, potassium and lithium salts and ammonium salt and alkanol ammonium salts.

Other defoaming compounds that is fit to comprises as the fatty acid ester of high-molecular weight fatty ester (as fatty acid glyceryl ester), monovalent alcohol, aliphatic C ₁₈-C ₄₀To tetraalkyl diamines chlorination triazine, they are cyanuryl chlorides and contain two moles of 1-24 carbon atom or three moles of uncles or secondary amine, propylene oxide, two stearic amide and single stearyl two basic metal (as sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester to ketone (as stearone) N-alkylation aminotriazine as three to six alkyl melamines or two.

The preferred foam system that presses down comprises:

(a) defoaming compounds, preferred silicone defoaming compounds, silicone defoaming compounds most preferably, it comprises following combination,

(i) polydimethylsiloxane, its level are the 50%-99% of silicone defoaming compounds weight, preferred 75%-95%; With

(ii) silicon-dioxide, its level is the 1%-50% of silicone/silicon-dioxide defoaming compounds weight, preferred 5%-25%;

The adding level of wherein said silica/silicon ketone defoaming compounds is 5%-50%, preferred 10%-40% (weight);

(b) compound dispersing agent most preferably comprises rake shape (rake) multipolymer of silicone dibasic alcohol, and the amount of polyoxyalkylene is 72-78%, and oxyethane is 1: 0.9 to 1: 1.1 with the ratio of propylene oxide, and its level is 0.5-10%, preferred 1%-10% (weight); Especially preferred this class silicone dibasic alcohol rake shape multipolymer is DCO544, available from the commodity of the DCO544 by name of DOW Corning;

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

Highly preferred granular suds suppressing system is described in EP-A-0210731 and comprises the silicone defoaming compounds and melting range is 50 ℃-85 ℃ a organic support material, wherein said organic support material comprises glycerine and has the monoesters of the lipid acid of 12-20 carbon atom, or its mixture, fusing point is 45 ℃-80 ℃.

Other highly preferred foam system that presses down comprises polydimethylsiloxane or silicone mixture, as polydimethylsiloxane, silico-aluminate and polycarboxylic acid polymkeric substance such as laic and acrylic acid multipolymer.The polymeric dye migration inhibitor

Component herein and/or composition also can comprise 0.01%-10%, the polymeric dye migration inhibitor of preferred 0.05%-0.5% (weight).

The polymeric dye migration inhibitor is preferably selected from polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinylpyrrolidonepolymers polymers or its combination, and these polymkeric substance can be cross-linked polymers thus.The polymerization soil releasing agent

Polymerization soil releasing agent (after this being called " SRA ") can be chosen wantonly and be used for component of the present invention or composition.If use, generally include 0.01%-10.0%, be generally 0.1%-5%, the SRA of preferred 0.2%-3.0% (weight).

Preferred SRA has hydrophilic segment and hydrophobic part usually, hydrophilic segment makes the surface hydrophilic of hydrophobic fiber such as polyester and nylon, hydrophobic part is deposited on above the hydrophobic fiber and keeps adhering on it in finishing washing and rinse cycle, serves as the anchor of hydrophilic segment thus.This makes the dirt of handling with SRA be easier to be eliminated in the subsequent wash program.

Preferred SRA comprises low polyterephthalate, generally by adopting at least a transesterification reaction/oligomerization of metal catalyst such as pure titanium (IV) to prepare usually.These esters can adopt the preparation of other monomer, these monomers can one, two, three, four or more a plurality of position add ester structure, not have to form tight crosslinked overall texture certainly.

The SRA that is fit to comprises that sulfonated products that contains the terephthaloyl and the basic linear ester oligopolymer of the oligomer ester main chain of oxyalkylene oxygen repeating unit and the allyl deriv sulfonation end-blocking that links to each other with the main chain covalency partly (as are described in the United States Patent (USP) 4 that J.J.Scheibel and E.P.Gosselink are given in mandate on November 6 nineteen ninety; 968,451).These ester oligomers can be prepared by following method: (a) ethoxylated allyl; (b) in secondary transesterification reaction/oligomerization program, make (a) product and dimethyl terephthalate (DMT) (" DMT ") and 1,2-propylene glycol (" PG ") reaction; (c) in water, make the reaction of (b) product and sodium metabisulfite.Other SRA comprises and authorized the U.S.4 give people such as Gosselink on December 8th, 1987,711, nonionic in 730 end capped 1,2-propylidene/polyoxyethylene terephthalate polyester, for example those materials of producing by transesterify/oligomerization of poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other example of SRA comprises: on January 26th, 1988 was authorized the end capped oligomer ester of part or all of negatively charged ion of the United States Patent (USP) 4,721,580 that gives people such as Gosselink, as ethylene glycol (" EG "), PG, DMT and 3, and 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Authorized the U.S.4 that gives Gosselink on October 27th, 1987,702, the end capped block polyester oligopolymer of nonionic in 857, as by DMT, methyl (Me)-end capped PEG and EG and/or PG, or DMT, EG and/or PG, the block oligomers that the PEG of methyl blocking and dimethyl-5-sulfoisophthalic acid sodium is produced; And on October 31st, 1989 authorize and to give Maldonado; people's such as Gosselink U.S.4; 877; negatively charged ion in 896; especially the end capped terephthalate of sulfo group aroyl; the latter is used to do washing and the typical SRA of fabric-conditioning product, and example is as by a sulfosalicylic acid list sodium salt, PG and DMT, and is optional but preferably further comprise the ester composition of PEG (as the PEG 3400) preparation of adding.

SRA also comprises: the simple segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, can be referring to authorizing the U.S.3 that gives Hays on May 25th, 1976,959, authorized the U.S.3 that gives Basadur on July 8th, 230 and 1975,893,929; Derivatived cellulose is as the hydroxy ethers cellulose polymer compound that provides with METHOCEL from Dow; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is referring to authorizing the U.S.4 that gives people such as Nicol, 000,093 on December 28th, 1976; And methyl cellulose ether, the unitary average substitution degree of wherein every dextrose anhydrous (methyl) is about 1.6 to about 2.3, is about 80 to about 120 centipoises at the soltion viscosity of 2% aqueous solution that records for 20 times.These materials obtain supply with METOLOSE SM100 and METOLOSESM200, and they are the trade(brand)names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK production.

The SRA of other type comprises: (I) adopt the vulcabond coupling agent to be connected to the structural nonionic terephthalate of polyester, and referring to people's such as Violland U.S.4,201,824 and people's such as Lagasse U.S.4,240,918; (II) have the SRA of carboxylicesters end group, by with 1,2, thereby the 4-benzenetricarboxylic anhydride adds among the known SRA and end capped hydroxyl is converted into 1,2, the preparation of 4-benzenetricarboxylic acid ester.With regard to suitable selecting catalyst, 1,2, the 4-benzenetricarboxylic anhydride is by 1,2, the ester of the isolated carboxylic acid of 4-benzenetricarboxylic anhydride, rather than form bonding with polymer ends by opening anhydride bond.Nonionic or anionic SRA can be used as raw material, condition be they have can esterification hydroxyl end groups.Referring to people's such as Tung U.S.4,525,524.Other type comprises: (III) the negatively charged ion terephthalic acid ester group SRA variant of carbamate connection, and referring to people's such as Violland U.S.4201,824.Other optional components

Other optional components that is suitable for being included in the present composition comprises colorant and filling salt (filler salt), and sodium sulfate is preferred filling salt.

Highly preferred composition contains 2% organic acid to about 10% (weight) of having an appointment, optimization citric acid.Also can be preferably and neutralizing agent, buffer reagent, phase modifier (phase regulants), hydrotropic agent, enzyme stabilizers, polyacid, foaming regulator, opalizer, antioxidant, sterilant and the dyestuff of carbonate, a small amount of (as being less than about 20% (weight)) (as authorizing the United States Patent (USP) 4 that gives people such as Barrat in 1981,285, those materials described in 841 add this paper with for referencial use at this) exist together.The chloro SYNTHETIC OPTICAL WHITNER

Described detergent composition can contain the chloro SYNTHETIC OPTICAL WHITNER as other component.But because detergent composition of the present invention is solid, most liquid chloro SYNTHETIC OPTICAL WHITNER will be not suitable for these detergent composition and have only particle or powder chloro SYNTHETIC OPTICAL WHITNER is fit to.

Perhaps, described detergent composition can be mixed with the chloro bleach-compatible, guarantee that thus the chloro SYNTHETIC OPTICAL WHITNER can be added in the detergent composition by the user in the beginning of washing process or process.

The chloro SYNTHETIC OPTICAL WHITNER can form hypochlorite in the aqueous solution.The chemical expression of hypochlorite ion is OCl ^-

These SYNTHETIC OPTICAL WHITNER that generate hypochlorite in the aqueous solution comprise basic metal and alkaline-earth metal hypochlorite, the adduct of hypochlorite, chloramines, chlorimide, N-(2-ethapon) methane amide and chlorimides.The object lesson of this compounds comprises clorox, potassium hypochlorite, single alkali formula Losantin, two basic magnesium hypochlorites, Efficacious Disinfeitant dodecahydrate, potassium dichloroisocyanurate, Surchlor GR 60, Surchlor GR 60 dihydrate, trichlorocyanuric acid, 1,3-two chloro-5,5-T10, N-Clofenamide, chloramine-T, dichloramine-T, chloramine B and dichloramine B.The preferred SYNTHETIC OPTICAL WHITNER that is used for composition of the present invention is clorox, potassium hypochlorite or its mixture.Preferred chloro SYNTHETIC OPTICAL WHITNER can be Triclosan (trade(brand)name).

The SYNTHETIC OPTICAL WHITNER of most of above-mentioned generation hypochlorites can solid or conc forms obtain supply and when preparation composition of the present invention, be dissolved in water.Some of above-mentioned materials obtain supply with the form of the aqueous solution.The clothes washing method

Machine laundry method herein is usually included in the washing machine with wherein dissolving and disperseing the machine-wash water-based washing soln processing of detergent composition of the present invention of significant quantity to stain clothing.The detergent composition of significant quantity is meant 10 grams is dissolved in or is scattered in 5 to 65 liters of washing solns to 300 gram products that this significant quantity is typical product dosage and the washing soln volume that is generally used for conventional machine washing method laundry.Preferred washing machine can be so-called low filling washing machine (low-fill machines).

Aspect a preferred use, described composition is mixed with is suitable for hard-surface cleaning or hand washing.Another preferred aspect described detergent composition be pre-treatment or soak composition, be used for pre-treatment or immersion and contain spot and color spot fabric.The abbreviation LAS straight chain C of in effervescence component and detergent composition embodiment, using _11-13Sodium alkyl benzene sulfonate LAS (I) straight or branched C _11-13Alkyl benzene sulphonate (ABS) potassium TAS tallow alkyl sodium sulfate C _XyAS C _1x-C _1ySodium alkyl sulfate C ₄₆SAS C ₁₄-C ₁₆Secondary (2,3) sodium alkyl sulfate C _XyE _zS C _1x-C _1yThe condensation C of sodium alkyl sulfate and z moles of ethylene oxide _XyE _zC _1x-C _1yThe condensation QAS R of main straight chain primary alcohol and average z moles of ethylene oxide ².N ⁺(CH ₃) ₂(C ₂H ₄OH), R ²=C ₁₂-C ₁₄QAS1 R ².N ⁺(CH ₃) ₂(C ₂H ₄OH), R ²=C ₈-C ₁₁APA C ₈-C ₁₀Amido propyl group dimethylamine soap is derived from the straight chain alkane of 80/20 mixture of butter and fatty acid distribution of coconut oil

Yl carboxylic acid sodium STS 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 ₁₂-C ₁₄The 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, particle diameter

Be 0.1-10 micron (expressing weight) NaSKS-6 formula d-Na based on anhydride ₂Si ₂O ₅Crystal layered silicate citric acid I Citric Acid, usp, Anhydrous Powder, 80% particle diameter is 40 microns-70 microns, volume

Median particle diameter is 55 microns anhydrous or monohydrate potassiums of citric acid II, 80% particle diameter be 15 microns-40 little

Rice, volume medium is 25 microns anhydrous oxysuccinic acid of oxysuccinic acid, 80% particle diameter is 50 microns to 100 microns, body

Long-pending median particle diameter is 75 microns toxilic acid Maleic Acid, Anhydrouss, and 80% particle diameter is 5 microns to 30 microns, volume

Median particle diameter is 15 microns anhydrous tartrate of tartrate, and 80% particle diameter is 25 microns to 75 microns, body

Long-pending median particle diameter is 50 microns carbonate I anhydrous sodium carbonates, the particle grain size of 80% (volume) be 50 microns extremely

150 microns, volume medium is 100 microns carbonate II anhydrous sodium carbonates, the particle grain size of 80% (volume) be 35 microns extremely

75 microns, volume medium is 55 microns supercarbonate II anhydrous sodium bicarbonates, and the particle grain size of 80% (volume) is 100 little

Rice is to 200 microns, and volume medium is 150 microns supercarbonate I anhydrous sodium bicarbonates, and the particle grain size of 80% (volume) is 15 microns

To 40 microns, volume medium is 25 microns silicate amorphous sodium silicate (SiO ₂: Na ₂O=2.0: 1) vitriol anhydrous sodium sulphate sal epsom anhydrous magnesium sulfate Citrate trianion two hydration trisodium citrates, activity is 86.4%, size distribution is 425

Toxilic acid/acrylic copolymer of 1: 4 of-850 microns MA/AA of micron, molecular-weight average is about 70,000MA/AA (1) toxilic acid/acrylic copolymer of 4: 6, molecular-weight average is about 10, the 000AA molecular-weight average is 4, the plain ether polymerization degree of 500 polyacrylic acid sodium polymer CMC sodium carboxyme-thylcellulose fibre is 650 methyl cellulose ether, available from Shin Etsu

Chemicals protease protein lytic enzyme, the organized enzyme with 3.3% (weight) is by NOVO

Industries A/S sells proteolytic enzyme I proteolytic ferment with the trade(brand)name of Savinase, and the organized enzyme with 4% (weight) is described in WO

95/10591, sell the Alcalase proteolytic ferment by Genencor Int.Inc., the organized enzyme with 5.3% (weight) is by NOVO

Industries A/S sells the cellulase cellulolytic enzyme, the organized enzyme with 0.23% (weight), by

NOVO Industries A/S sells the amylase amylolytic enzyme with the trade(brand)name of Carezyme, and the organized enzyme with 1.6% (weight) is by NOVO

Industries A/S sells the lipase fat hydrolase with the trade(brand)name of Termamy 120T, and the organized enzyme with 2.0% (weight) is by NOVO

Industries A/S sells lipase (1) fat hydrolase with the trade(brand)name of Lipolase, and the organized enzyme with 2.0% (weight) is by NOVO

Industries A/S sells the Endolase endoglucanase with the trade(brand)name of Lipolase Ultra, and the organized enzyme with 1.5% (weight) is by NOVO

Industried A/S sells PB4 and contains mark formula NaBO ₂.3H ₂The sodium perborate tetrahydrate of O

Grain, described particulate weight average particle diameter is 950 microns, 85% particle

Particle diameter be that 850 microns to 950 microns PB1 contain mark formula NaBO ₂.H ₂O ₂The anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER

Grain, described particulate weight average particle diameter is 800 microns, 85% particle

Particle diameter be that 750 microns to 950 microns percarbonate contain mark formula 2Na ₂CO ₃.3H ₂O ₂The particle of SPC-D, described

The particulate weight average particle diameter is 850 microns, 5% or particle diameter still less less than

600 microns, 2% or particle diameter still less contain the nonanoly acyloxy benzene sulfonate of sodium-salt form, particulate weight average grain greater than 1180 microns NOBS

The footpath is the particle that 750 microns-900 microns NAC-OBS contain (6-nonanoyl amido caproyl) oxygen base benzene sulfonate,

The weight average particle diameter of grain is the particle that 825 microns-875 microns TAED I contain tetra acetyl ethylene diamine, described particulate weight average particle diameter

Be 700 microns to 1000 microns TAED II tetra acetyl ethylene diamines; particle diameter is 150 microns to 600 microns DTPA diethylene triaminepentaacetic acid(DTPA) DTPMP diethylenetriamine five (methylene phosphonic acid salt), by Monsanto with

The trade(brand)name of Dequest 2060 is sold light activating agent and is encapsulated in sulfonation phthalocyanine phthalocyanine zinc light activating agent in SYNTHETIC OPTICAL WHITNER (1) the dextrin soluble polymer and is encapsulated in aluminum phthalocyanine whitening agent 14 in SYNTHETIC OPTICAL WHITNER (2) the dextrin soluble polymer, 4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 24,4 '-two (4-anilino-6-morpholine also-1.3.5-triazine-2-yl) amino) Stilbene-

2:2 '-disulfonic acid disodium EDDS quadrol-N, N '-two Succinic Acid, sodium-salt form (S, S) isomer HEDP 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid PEG _xPolyoxyethylene glycol, molecular weight is that x (is generally 4,000) PEO polyethylene oxide, molecular-weight average is 50,000TEPAE tetren ethoxylate PVI polyvinyl imidosole, and molecular-weight average is 20, the 000PVP polyvinylpyrrolidonepolymers polymers, molecular-weight average is 60,000PVNO polyvinylpyridine N-oxide polymer, and molecular-weight average is

50, the multipolymer of 000PVPVI Polyvinylpyrolidone (PVP) and vinyl imidazole, average mark

The son amount is 20, the two ((C of 000QEA ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃)

Two ((C ₂H ₅O) (C ₂H ₄O)) _n, wherein n is that the short block of the end capped polyester SRP2 of 20-30SRP1 negatively charged ion diethoxyization poly-(terephthalic acid 1,2 propylene glycol ester) is poly-

Compound PEI polymine, molecular-weight average are 1800, and average ethoxyquin degree is

7 ethylene oxy residues of each nitrogen silicone defoamer siloxanes-oxyalkylene multipolymer is as the polydimethyl silica of dispersion agent

The alkane Foam Control, the ratio of described Foam Control and described dispersion agent

Be 10: 1-100: the water base single styrene latex mixture of 1 opalizer, by BASF

Aktiengesellschaft sells among the alabaster wax effervescent granule effervescent granule I-XII any with the trade(brand)name of Lytron 621

Following effervescent granule I-XII is according to particle of the present invention (calculating percentages of ingredients with effervescent granule weight).The component that described particle can pass through to mix described component and the described component of agglomeration or pass through compressed mixed prepares, and the latter is for preparing the preferred method of particle I, IV and VIII.

Particle	??I	??II	??III	??IV	??V	??VI	??VII	??VIII	??IX	??X	??XI	??XII
													Citric acid I	??60		??35			??20				??20
Citric acid II		??40						??20	??30			??30
													Oxysuccinic acid I				??50		??20					??40
Oxysuccinic acid II					??30
													Tartrate (Tarteric acid)							??50
Toxilic acid								??30
													Carbonate I	?40			??20		??40			??30	??30	??20
Carbonate II		??20	??30		??30		??35	?30				??20
													Supercarbonate I		??20
Supercarbonate II				??30				??20			??20
													LAS		??10			??20				??20
Nonionic *										??30	??20	??30
													AS						??10				??20
TAED			??20									??5
													Siccative #			??2				??5					??10

NACOBS					??20
													NOBS									??20
CMC			??5									??5
													Percarbonate							??10
Whitening agent			??3
													PEG4000		??10	??5			??10

# (overdrying or anhydrous salt/zeolite or overdrying zeolite)

* nonionic ethoxylated alcohol tensio-active agent, average degree of ethoxylation is 3-9, pure alkyl chain has 12-18 carbon atom.

Embodiment 1

All levels of the following examples are all in the weight of described composition,

Table I

Following composition is a composition of the present invention

	A	B	C	D	E	F	G	H	I
										Spray-dried granules
LAS	10.0	10.0	15.0	5.0	5.0	10.0	-	-	-
										TAS	-	1.0	-				-	-	-
MBAS	-	-		5.0	5.0		-	-	-
										C 45AS	-	-	1.0		2.0	?2.0	-	-	?-
C 45AE 3S	-	-		1.0			-	-	-
										QAS			1.0	1.0			-	-	-
DTPA, HEDP and/or EDDS	0.3	0.3	0.5	0.3			-	-	-
										MgSO 4	0.5	0.5	0.1	-			-	-	-
Trisodium Citrate	-	-	-	3.0	5.0		-	-	-
										Yellow soda ash	10.0	7.0	15.0			10.0	-	-	-
Sodium sulfate	5.0	5.0	-	-	5.0	3.0	-	-	-
										Water glass 1.6R	-	-	-	-	2.0		-	-	-
Zeolite?A	16.0	18.0	20.0	20.0	-	-	-	-	-
										SKS-6	-	-	-	3.0	5.0	-	-	-	-
MA/AA or AA	1.0	2.0	11.0	-	-	2.0	-	-	-

PEG4000	-	2.0	-	1.0	-	1.0	-	-	-
										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	-	-	-
Effervescent granule I, III, IV or VIII	10	7.0	-	-	-	-	-	-	-
										Agglomerate
LAS			-	-	-	-	2.0	2.0	-
										MBAS			-	-	-	-	-	-	?1.0
C 45AS			-	-	-	-	2.0	-	-
										AE 3			-	-	-	-	-	1.0	0.5
Carbonate			-	-	4.0	1.0	1.0	1.0	-
										Trisodium Citrate			-	-	-	-	-	-	5.0
CFAA					-	-	-	-	-
										Citric acid			-	-	-	4.0	-	1.0	1.0
QEA			-	-	-	2.0	2.0	1.0	-
										SRP			-	-	-	1.0	1.0	0.2	-
Zeolite?A			-	-	-	15.0	26.0	15.0	16.0
										Water glass			-	-	-	-	-	-	-
PEG	-	-	-	-	-	-	4.0	-	-
Builder agglomerates
										SKS-6	6.0	-	-	-	6.0	3.0	-	7.0	10.0
LAS	4.0	5.0	-	-	5.0	3.0	-	10.0	12.0
Do the particle that adds
										Component
Effervescent granule	-	4.0	10.0	4.0	25	8.0	12.0	2.0	4.0
										QEA	-	-	-	0.2	0.5	-	-	-	-
NACAOBS	3.0	-	-	4.5	-	-	-	2.5	-
										NOBS	1.0	3.0	3.0	-	-	-	-	-	5.0
TAED?I	2.5	-	-	1.5	2.5	6.5	-	1.5	-
										MBAS	-	-	-	8.0	-	-	?8.0	-	?4.0

LAS (sheet)	10.0	10.0	-	-	-	-	-	8.0	-
										Citric acid II	-	-	-
Spraying drying
										Whitening agent	0.2	0.2	0.3	0.1	0.2	0.1	-	0.6	0.3
Dyestuff	-	-	-	0.3	0.05	0.1	-	-	-
										AE7	-	-	-	-	-	0.5	-	0.7	-
Spices	1.0	0.5	1.1	0.8	0.3	0.5	0.3	0.5	-
Do and add
										Citrate trianion	-	-	20.0	4.0	-	5.0	15.0	-	5.0
Percarbonate	15.0	3.0	6.0	10.0	-	-	24.0	18.0	5.0
										Perborate	-	-	-	-	6.0	18.0	-	-	-
Optical white	0.02	0.02	0.02	0.1	0.05	-	0.3	-	0.03
										Enzyme (cellulase, amylase, proteolytic enzyme, lipase)	1.3	0.3	0.5	0.5	0.8	2.0	0.5	0.16	0.2
Carbonate	0.0	10.0	?-	-	?-	5.0	8.0	10.0	5.0
										Spices (packing)	-	0.5	0.5	-	0.3	-	0.2	-	-
Suds suppressor	1.0	0.6	0.3	-	0.10	0.5	1.0	0.3	1.2
										Soap	0.5	0.2	0.3	3.0	0.5	-	-	0.3	-
Citric acid (I or crude product)	-	-	-	6.0	6.0	-	-	-	5.0
										Dyeing carbonate (blue, green)	0.5	0.5	1.0	2.0	-	0.5	0.5	0.5	1.0
SKS-6	-	-	-	4.0	-	-	-	6.0	?-
										Filler to 100%

Table II

Following composition is a composition of the present invention.

	A	B	C	D	E	F	G	H	I
										Spray-dried granules
LAS or LAS (I)	10.0	?10.0	?16.0	?5.0	?5.0	?10.0	-	-	?-

TAS	-	1.0	-				-	-	-
										MBAS	-	-	-	5.0	5.0		-	-	-
C 45AS	-	-	1.0		2.0	2.0	-	-	-
										C 45AE 3S	-	-	-	1.0			-	-	-
QAS	-	-	1.0	1.0			-	-	-
										DTPA, HEDP and/or EDDS	0.3	0.3	0.3	0.3			-	-	-
MgSO 4	0.5	0.4	0.1	-			-	-	-
										Trisodium Citrate	10.0	12.0	17.0	3.0	5.0		-	-	-
Yellow soda ash	15.0	8.0	15.0			10.0	-	-	-
										Sodium sulfate	5.0	5.0	-	-	5.0	3.0	-	-	-
Water glass 1.6R	-	-	-	-	2.0		-	-	-
										Zeolite?A	-	-	-	2.0	-	-	-	-	-
SKS-6	-	-	-	3.0	5.0	-	-	-	-
										MA/AA or AA	1.0	2.0	10.0	-	-	2.0	-	-	-
PEG4000	-	2.0	-	1.0	-	1.0	-	-	-
										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	-	-	-
Effervescent granule I, III, IV, VII or VIII	?5	?12	?-	-	-	-	-	-	-
										Agglomerate
LAS	-	-	-	-	-	-	2.0	2.0	-
										MBAS	-	-	-	-	-	-	-	-	1.0
C 45AS	-	-	-	-	-	-	2.0	-	-
										AE 3	-	-	-	-	-	-	-	1.0	0.5
Carbonate	-	-	-	-	4.0	1.0	1.0	1.0	-
										Trisodium Citrate	-	-	-	-	-	-	-	-	5.0
CFAA	-	-	-	-	-	-	-	-	-
										Citric acid	-	-	-	-	-	4.0	-	1.0	1.0
QEA	-	-	-	-	-	2.0	2.0	1.0	-
										SRP	-	-	-	-	-	1.0	1.0	0.2	-

Zeolite?A	-	-	-	-	-	15.0	26.0	15.0	16.0
										Water glass	-	-	-	-	-	-	-	-	-
PEG	-	-	-	-	-	-	4.0	-	-
										TAED?II							3.0		1.5
Builder agglomerates
										SKS-6	6.0	5.0	-	-	6.0	3.0	-	7.0	10.0
LAS	4.0	5.0	-	-	5.0	3.0	-	10.0	12.0
Do the grain fraction of adding
										Effervescent granule	-	10.0	4.0	5	15	8.0	2.0	20	4.0
NACAOBS	3.0	-	-	1.5	-	-	-	5.5	-
										NOBS/LOBS/ DOBS	-	3.0	3.0	-	-	-	-	-	5.0
TAED?I	2.5	-	?-	1.5	2.5	6.5	-	1.5	-
										MBAS	-	-	-	8.0	-	-	8.0	-	4.0
LAS (sheet)	-	-	-	-	-	-	-	8.0	-
Spraying drying
										Whitening agent	0.2	0.2	0.3	0.1	0.2	0.1	-	0.6	-
Dyestuff	-	-	-	0.3	0.05	0.1	-	-	-
										AE7	-	-	-	-	-	0.5	-	0.7	-
Spices	-	-	-	0.8	-	0.5	0.8	0.5	1.0
Dried additive
										QEA	-	-	-	0.2	0.5	-	-	-	-
Citrate trianion	4.0	-	3.0	4.0	-	5.0	15.0	-	5.0
										Percarbonate	15.0	3.0	6.0	10.0	-	-	12.0	18.0	5.0
Perborate	-	-	-	-	6.0	18.0	-	-	-
										Optical white	0.02	0.02	0.02	0.1	0.05	-	0.3	-	0.03
Enzyme (cellulase, amylase, proteolytic enzyme, lipase)	1.5	0.3	0.5	0.5	0.8	2.0	0.5	0.16	0.2

Carbonate II	-	-	-	-	-	5.0	?8.0	10.0	5.0
										Spices (packing)	0.6	0.5	0.5	-	0.3	0.5	?0.2	0.1	0.6
Suds suppressor	1.0	0.6	0.3	-	0.10	0.5	?1.0	0.3	1.2
										Soap	0.5	0.2	0.3	3.0	0.5	-	-	0.3	-
Citric acid II	-	-	-	-	-	-	-	5.0	5.0
										Dyeing carbonate (blue, green)	0.5	0.5	？	2.0	-	0.5	0.5	0.5	1.0
SKS-6	-	-	-	4.0	-	-	-	6.0	-
										Filler to 100%

Table III

Be according to high-density of the present invention and the detergent formulation that contains SYNTHETIC OPTICAL WHITNER below.

	???A	???B	???C
				The blowing powder
???????????????????ZeoliteA	???-	???-	???15.0
				Sodium sulfate	???0.0	???5.0	???0.0
????????????????????????LAS	???3.0	???-	???3.0
				??????????????????????C45AS	???3.0	???2.0	???4.0
????????????????????????QAS	???-	???-	???1.5
				??????????????????????DTPMP	???0.4	???0.4	???0.4
????????????????????????CMC	???0.4	???0.4	???0.4
				??????????????????????MA/AA	???4.0	???2.0	???2.0
Effervescent granule I or VIII	???7.0	???-	???-
				???????????????????????TAED	????-	???-	???3.0
Agglomerate
				Effervescent granule I, III, VIII or IX	???7.0	???-	???7.0
????????????????????????QAS	???1.0	???-	???-
				????????????????????????LAS	???-	???11.0	???7.0
????????????????????????TAS	???2.0	???2.0	???1.0
				Silicate	???3.0	???-	???4.0
??????????????????Zeolite?A	???8.0	???8.0	???8.0
				Carbonate	???8.0	???8.0	???4.0

Agglomerate
				NaSKS-6 (I) or (II)	???15.0	???12.0	???5.0
??????????????????????????LAS	???8.0	???7.0	???4.0
				???????????????????????????AS	???5.0	???-	???-
Spraying
				Spices	???0.3	???0.3	???0.3
????????????????????????C 25E 3	???2.0	???-	???2.0
				Whitening agent	???0.1	???0.4
Optical white	???0.03	???0.05	???-
				Dried additive	???-	???-	???-
??????????????????????????QEA	???1.0	???0.5	???0.5
				Citric acid I	???5.0	???-	???2.0
Supercarbonate I	???-	???3.0	???-
				Carbonate II	???8.0	???15.0	???10.0
??????????????????????NAC?OBS	???6.0	???-	???5.0
				Mn catalyst	???-	???-	???0.3
???????????????????????TAED?I	???-	???3.0	???-
				?????????????????????????NOBS	???-	???2.0	???-
Percarbonate	???14.0	???7.0	???10.0
				Polyethylene oxide, molecular weight 5,000,000	???-	???-	???0.2
Wilkinite	???-	???-	???10.0
				Effervescent granule	???-	???5.5	???7.5
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
Silicone defoamer	???5.0	???5.0	???5.0
				Dried additive
Sodium sulfate	???0.0	???3.0	???0.0
				Equal amount (moisture and impurity)	???100.0	???100.0	???100.0
Density (grams per liter)	???850	???850	???850

Embodiment 2 coating effervescence components

The tallow alcohol ethylene oxide condensate (TAE) of tallow alcohol and 50-80 moles of ethylene oxide (TAE 50/80) condensation is melted down at 70 ℃.4.750 kilograms of effervescence components (64% citric acid and 36% yellow soda ash compression form) are placed drum tumbler (Eirich) and start mixing tank but do not make rotation.This will stimulate the mixing at a slow speed of " inflation particle ".Placing 250 gram fused TAE 50/80 with atomizing air is the heating container that links to each other of 80 ℃ Devilbliss spray gun (surrounding water jacket～80 ℃).Obtain the TAE 50/80 of gross weight 5% like this.The unlatching tumbling mixer rotates and fused TAE 50/80 is sprayed on the mobile effervescence component, thereby adheres to the surface of effervescence component by this way, effectively is coated with described effervescence component.In case all fused TAE 50/80 are sprayed onto on the effervescence component, allow tumbling mixer rotate until TAE 50/80 effervesce surface hardening (promptly until solidifying).Thereby the effervescence component that TAE 50/80 is coated with sieves under 1180 microns and removes any agglomerant particle subsequently.This is the particle XIII of described embodiment.

Claims (20)

CLAIMS 1. An effervescent component comprising an acid source and a carbon dioxide source, wherein at least 75% of said acid source has a particle size of 0.1-150 microns, preferably 0.5-100 microns. 2. The effervescent composition according to claim 1, wherein the carbon dioxide source has a volume median particle size of 5-375 microns, whereby preferably at least 60% of the particles have a particle size of 1-425 microns, or even preferably 10-250 Micron volume median particle size, whereby preferably at least 60% of the particles have a diameter of 1-375 microns, or even have a volume median particle size of 1-120 microns, whereby preferably at least 60% of the particles have a diameter of 1-150 Micron. 3. The component according to any one of the preceding claims, wherein the acid source comprises sulphonic acid or mono- or polycarboxylic acids or mixtures thereof, preferably citric acid, adipic acid, glutaric acid in anhydrous and/or hydrated form , 3 cetoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid and/or malonic acid and/or toluenesulfonic acid, preferably citric acid, malic acid, maleic acid or tartaric acid or a mixture thereof. 4. A component according to claim 1, whereby said effervescent component, or one or more of said acid source or carbon dioxide source, is prepared by an alkoxylated alcohol containing an average degree of alkoxylation of at least 20 coating applied. 5. A component according to any one of the preceding claims, whereby the carbon dioxide source comprises sodium carbonate or bicarbonate or a mixture thereof. 6. An effervescent composition according to any one of the preceding claims, said acid source and said carbon dioxide source being present in intimate admixture with each other. 7. The effervescent composition according to claim 6, wherein said acid source and said carbon dioxide source are present in granules, preferably said granules have a weight average particle size of 500 microns to 1500 microns, whereby preferably said granules have At least 70% of the particles have a particle size of 350 to 2000 microns, or even have a weight average particle size of 650 to 1180 microns, whereby preferably at least 70% of the particles have a particle size of 500 to 1500 microns. 8. An effervescent granule according to claim 6, wherein said acid source and said carbon dioxide source are present in a granule having a weight average particle size of 200 microns to 500 microns, whereby preferably at least 70% of said granules have a particle size 100-710 microns, or even have a weight average particle size of 250-450 microns, whereby preferably at least 70% of the particles have a particle size of 150-650 microns. 9. Granules according to any one of claims 7 or 8 comprising, by weight of the total granules, 30%-95%, preferably 45%-85%, most preferably 50%-80% of a source of carbon dioxide and 3%-75% , preferably 5%-60% or more preferably 15%-50% of the acid source. 10. A granule according to any one of claims 7-9 comprising up to 50% by weight of the total granule of one or more binders, detergent actives, preferably surfactants and/or bleaching agents or its mixture. 11. Granules according to claim 10, wherein the binder is selected from the group consisting of cellulose derivatives; homopolymers and copolymers of carboxymethylcellulose and polycarboxylic acids and their salts; C ₆ -C ₂₀ alkyl groups and alkylaryl sulfonates and sulfates; C ₁₀ -C ₂₀ fatty alcohol ethoxylates with 5-100 moles of ethylene oxide per mole of alcohol; fatty acids; polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000; Polyethylene glycols with an average molecular weight of 600 to 10,000; copolymers of maleic anhydride with ethylene, methyl vinyl ether, methacrylic acid or acrylic acid; C ₁₀ -C ₂₀ mono- and diglycerides; C ₁₀ -C ₂₀ fatty acids and mixtures thereof and preferably C ₈ -C ₂₀ alkylbenzene sulfonates. 12. A method of preparing particles according to any one of claims 7-11, wherein said method comprises the steps of: - grinding a crude acid source to obtain an acid source having at least 75% of a particle size of 0.1-150 microns, preferably 0.5-100 microns, - mixing said source of crude acid and said source of carbon dioxide and optionally binders and/or other actives to form a mixture, - subsequently subjecting said mixture to a granulation step, preferably said granulation step comprises a compression step and/or an agglomeration step. 13. A method according to claim 11 or 12, wherein the granulation step comprises a roller compaction step, wherein the resulting mixture is forced between compression rollers under pressure, after which the resulting compressed mixture is granulated into effervescent granules and Optionally sieve. 14. A detergent composition comprising an effervescent component characterized in that said effervescent component is coated with a coating comprising an alkoxylated alcohol having an average degree of alkoxylation of at least 20. 15. A detergent composition according to claim 14, comprising a coated effervescent component obtained by a process comprising the steps of: (a) forming a molten alkoxylated alcohol; (b) contacting the molten alkoxylated alcohol with an effervescent component. 16. A detergent composition according to claim 14 or 15, whereby said coating is present at a level of from 0.5% to 25% by weight of said effervescent component. 17. A detergent composition, preferably in the form of a non-aqueous liquid, a granular composition, a tablet or a stick, comprising an effervescent component according to any one of the preceding claims, preferably in the form of Levels are from 2% to 50%, more preferably from 3% to 25%, most preferably from 4% to 15%, by weight of the detergent composition. 18. A granular detergent composition according to claim 17, wherein at least one effervescent component, preferably in granular form, is comprised in at least one detergent base particle, said base particle preferably having a weight average particle size of 350 microns to 4 mm, more preferably 500 microns to 2.5 mm or even 710 microns to 2 mm. 19. A method of providing improved sudsing of a detergent composition by adding an effervescent component according to any one of claims 1 to 12 to detergent granules, the weight average particle diameter of said detergent granules being 500 microns to 1500 microns, whereby preferably at least 70% of said particles have a particle diameter of 350 to 2000 microns, or even have a weight average particle diameter of 650 to 1180 microns, whereby preferably at least 70% of said particles have a particle diameter of 500-1500 microns. 20. By adding an effervescent component according to any one of claims 1 to 11 in detergent granules to provide improved distribution and/or dissolution of detergent compositions, the weight average particle diameter of said detergent granules from 200 microns to 500 microns, whereby preferably at least 70% of the particles have a particle size of 100-710 microns, or even have a weight average particle diameter of from 250 microns to 450 microns, whereby preferably at least 70% of the particles The particle size is 150-650 microns.