CN1415007A

CN1415007A - Detergent compositions

Info

Publication number: CN1415007A
Application number: CN00817829.1A
Authority: CN
Inventors: A·多维伊; A·P·多德斯
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd; Procter and Gamble Co
Priority date: 1999-10-28
Filing date: 2000-10-23
Publication date: 2003-04-30
Also published as: EP1228177A2; GB9925472D0; GB2355721A; CA2386131A1; JP2003513151A; WO2001030949A3; AR026264A1; BR0015151A; AU1102601A; MXPA02004212A; WO2001030949A2

Abstract

A detergent composition which dispenses and dissolves well in aqueous solution and having good storage stability is described. The composition comprises a reactive particle which preferably comprises first and second reactants which are respectively, acid and alkali-sources and which release gas on contact with water, in which the particle number ratio of the first reactant to the second reactant (that is the ratio of number of particles of the first reactant to the second reactant) in the reactive particle is at least 50:1. The reactive particles themselves are also claimed.

Description

Detergent composition

Invention field

The present invention relates to comprise the stable granular component of two kinds of reactants, two reactants with fluid, react each other when especially liquid such as water contact, wherein before this reaction took place in hope, each particle can contact this type of fluid in storage.The present invention relates to provide this type of granular component of stable form, so that the reaction between two kinds of reactants can not take place basically, until till when wish taking place.The invention still further relates to the composition that contains this type of granular component.

The present invention be more particularly directed to the effervescent granules material, it promotes dissolving fast to be incorporated in the composition, and the latter needs to be dissolved in the water-bearing media easily and apace.This technology can be applied in various fields, as cleaning combination, especially does washing and washes the dishes and use detergent composition, and these compositions can be granular forms or can further process shape in blocks.The present invention be more particularly directed to cloth-washing detergent uses.

Background of invention

The dissolving and the assignment problem of difference are well-known in the detergent applications.This problem is owing to produce the more washing composition of high-bulk-density in recent years, as is higher than 600g/l, with satisfy the human consumer to less product and packaging volume and less waste promptly the needs of more highly active cleaning combination those trend and become more outstanding.This problem is complexity because use detergent formulation, and this is filled a prescription not based on the processable phosphate builders, is difficult for molten surrogate and be based on, and the latter can overcome any environmental problem relevant with phosphate builders.In addition, need more to promote the washing composition snap-out release in the washing water to lack, to provide maximum cleaning performance in the wash(ing)cycle of energy efficient, wherein detergent solution can reduce to minimum with the duration of contact of the object that needs washing.Many solutions have been suggested dissolving and the assignment problem of attempting avoiding difference.

This class solution is the foaming system of using in washing composition.For example, the detergent composition that comprises foaming ingredient is described among the WO98/04687.In WO98/04671, the foaming system that is used for washing composition is disclosed, wherein in improving the dissolved effort, mix to obtain anhydrous basically whipability particulate matter with stablizer at the bronsted lowry acids and bases bronsted lowry foaming reactant that contacts the meeting generated reactive gas with water, it has efficient when using in washing step.Similarly, WO98/35011 also discloses the particulate matter that comprises sodium bicarbonate and organic acid reaction thing, and they one react and form particle with binding agent.EP-A-918087 has described to join and has comprised supercarbonate and polycarboxylic complementary lotion-aid particle thing in the detergent composition, and it forms by roll-in and does not comprise free water content.Yet the requirement of good final use whipability is the requirement of conflict mutually when good storage stability being provided and contacting with washing lotion; Can prevent or be reduced in the effectiveness under the wash conditions when using stablizer that water is contacted with the foaming reactant, make respective reaction speed slow down, therefore bubble and dissolve synergism and can undesirably reduce.So still need to be used for the foaming generation system that this type of is used, when having good storage stability and contact with water in use, it can dissolve apace, discharge foam thus.

Summary of the invention

The inventor finds, by being chosen in the granularity of reactant in the whipability particulate matter carefully, can obtaining improved astoundingly package stability and the best in use and render a service.

Therefore, according to the present invention, the reactive behavior that comprises two kinds of granular reactants particulate material is provided, two kinds of granular reactants one react when promoting that with reaction fluid contacts, and the ratio of first reactant and the granule number of second reactant (i.e. the ratio of first reactant and the numbers of particles of second reactant) is at least 50: 1.Preferably, second reactant is at least 2: 1 with the ratio of the median particle of first reactant.Therefore, though can use the relatively large granularity reactant of larger amt, preferably use the relative reactant of larger amt than small grain size.

A large amount of having been found that than the binding substances of the relatively large granularity component of small grain size reactant and lesser amt relatively can obtain wonderful result, promptly the first and second reactant fusion are being formed in the reactive behavior particulate process, reactant than volume particle size is used as " nuclear ", and it is enclosed in the reactive behavior particle effectively by second component.Therefore, second component provides barrier layer, make to promote the fluid of the reaction between two reactants can not penetrate barrier layer (it stops moisture to enter interface between two kinds of reactants as obstacle), like this between first and second reactants instead would not be promoted and also package stability has obtained surprisingly, improve significantly.

Of the present invention preferred aspect, particle is an effervescent granules, wherein separately at least a of first and second reactants is respectively alkali source and acid source, and fluid is liquid, i.e. water or other aqueous components.Yet, for skilled reader, be clear that very much, this principle is more widely applicable for the improvement stability of any other reactant, and these reactants touch the fluid (being liquid or gas) that can promote their reactions each other, before wishing the required application conditions of contacting with fluid.

The invention still further relates to the detergent composition that comprises this type of effervescent granules material.

The invention still further relates to washing methods, the detergent composition that wherein comprises the effervescent granules material contacts with water so that detergent composition is dissolved in the water fast, and the water that comprises the dissolved detergent composition then is used to wash the article of contamination.The invention particularly relates to the washing of the household goods of making dirty, particularly wash the dishes and/or laundry applications.The present invention is used in particular for clothes washing method.

Detailed Description Of The Invention

The reactive behavior particle

The reactive behavior particle comprises two kinds of granular reactants, and they react understanding one when contact with the third component (be generally reaction promote liquid).Reaction promotes that liquid can be needed the third reactant of reaction between first and second reactants, or it can comprise reaction medium, this medium can make the third reactant be penetrated into and make in the reactive behavior particle to react and be carried out, or this medium can promote that in the contact between first and second reactants first and second kinds of reactions between the component being become may or obtain promoting.When fluid be liquid and especially when fluid is water the present invention be useful especially, this fluid can contact with the reactive behavior particle in gas phase or liquid phase.Especially, the reactive behavior particle comprises effervescent granules, wherein first and second kinds of reactants with the generation foam that reacts to each other after water contacts.Therefore, in this embodiment, separately each of first and second kinds of reactants comprises acid source and at least a alkali source that comprises.

The ratio of first kind of reactant and the granule number of second kind of reactant (i.e. the ratio of first kind of reactant and the number of particles of second kind of reactant) is at least 50: 1, preferably at least 100: 1, more preferably at least 500: 1, or even at least 1000: 1 and most preferably at least 5000: 1 or even at least 10000: 1.

In addition, second kind of reactant is at least 2: 1 with the ratio of the median particle of first kind of reactant, preferably at least 8: 1, more preferably at least 15: 1, or at least 20: 1 or even at least 30: 1.Preferably the fabric width of each reactant granularity (span) is to be not more than 3, more preferably no more than 2, most preferably is not more than 1.5.

Phrase used herein " median particle " is meant the geometry mass median particle diameter of one group of discrete particle being measured by the granulometry technology based on quality of any standard (preferably passing through dry screening).The phrase of size-grade distribution used herein " geometric standard deviation " or " fabric width " are meant the geometric widths to the log-normal function of the best-fit of above-mentioned granularity data, and it is that diameter by 84.13 hundredths of cumulative distribution is divided by the ratio (D of the diameter of the 50th hundredths _84.13/ D ₅₀) obtain; Referring to people such as Gotoh, Powder Technology Handbook, 6-11 page or leaf, Marcel Dekker 1997.

Preferably, the particulate mean particle size is about 500 microns to about 1500 microns, more preferably about 600 microns to about 1200 microns and most preferably about 700 microns to about 1000 microns.Size-grade distribution is to be defined by geometric standard deviation or " fabric width " relatively more closely, deflects away from targeted particle size so that be unlikely too many particle.Therefore, geometric standard deviation preferably about 1 to about 2, more preferably about 1.0 is to about 1.7, even more preferably about 1.0 to about 1.4 and most preferably about 1.0 to about 1.2.

Especially for the effervescent granules of preparation example as using in family expenses cleaning or industry cleaning application, the median particle of second kind of reactant is preferably greater than 100 microns, more preferably greater than 200 microns with most preferably greater than 300 microns.The granularity of first reactant preferably is lower than 50 microns, more preferably less than 25 microns with most preferably be lower than 10 microns.When the reactive behavior particle was effervescent granules, first reactant comprised acid source or alkali source, but preferably comprised alkali source, and second reactant preferably comprises acid source.

First reactant is preferably with the 0.1-99wt% of total particle, preferred 3-80wt%, more preferably 10-75wt% and most preferably the amount of 15-70wt% be present in the reactive behavior particle.

Second reactant is preferably with the 0.1-99wt% of total effervescent granules, preferred 20-95wt%, more preferably 30-85wt% and most preferably the amount of 35-75wt% be present in the reactive behavior particle.For best reaction is arranged, the weight ratio of first and second reactants is preferably calculated according to stoichiometry basically in the reactive behavior particle, so that equimolar basically reaction active groups is arranged.Therefore, the mol ratio of the reaction active groups of first reactant and second reactant preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3, even more preferably 3: 2 to 2: 3 and most preferably 9: 10 to 10: 9.

Suitable acid source comprises solid organic acid, mineral acid or mineral acid, their salt or derivative or their mixture.Preferably, acid is singly-, two-or three-protonic acid.This type of acid comprises monocarboxylic acid or poly carboxylic acid, optimization citric acid wherein, hexanodioic acid, pentanedioic acid, 3-chetoglutaric acid, citromalic acid, tartrate, toxilic acid, fumaric acid, oxysuccinic acid, succsinic acid, propanedioic acid.This type of acid is preferably used with their acid form.Derivative also comprises the ester of acid.Preferred acid comprises citric acid and oxysuccinic acid.Special optimization citric acid.

Any alkali source can be used in the reactive behavior particle.The carbonate alkali source is particularly preferred, for example comprises carbonate, supercarbonate, sesquicarbonate and percarbonate, particularly supercarbonate and/or carbonate.Preferred carbonate used herein comprises carbonate and supercarbonate, and it should be being present in the effervescent granules with the form of acid source reaction.So usually, alkali source should be water miscible, or has very thin granularity, so that can take place easily when effervescent granules contacts with water with the reaction of acid source.The salt of basic metal or alkaline-earth metal is suitable.The salt of water-soluble salt such as potassium, lithium, sodium etc. is preferred, and wherein the carbonate of sodium and potassium is particularly preferred.Suitable supercarbonate used herein comprises the supercarbonate of any basic metal such as lithium, sodium, potassium etc., and wherein the supercarbonate of sodium and potassium is preferred.Supercarbonate than carbonate more preferably because it has higher weight efficiency, promptly supercarbonate is the CO bigger than carbonate under equivalent weight ₂" reserve bank ".Yet, detergent formulation general requirement meeting causes the more alkaline pH that caused by carbonate, more useful overall detergent mixture is provided, and therefore the selection of carbonate or supercarbonate or their mixture can be depending on desirable pH in the water-bearing media that has dissolved the detergent composition that comprises this effervescent granules therein in the effervescent granules material.For example, when hope has higher pH when (for example being higher than pH9.5) in water-bearing media, preferably use the binding substances of carbonate or use carbonate and supercarbonate separately, wherein the amount of carbonate is higher than the amount of supercarbonate, typically the weight ratio according to carbonate and supercarbonate is 0.1 to 10, more preferably 1 to 5 and most preferably 1 to 2.In one aspect of the invention, when detergent composition comprised supercarbonate separately as alkali source, preferably this effervescent granules comprised the citric acid greater than 6wt% in addition, and the latter is optional to be mixed with other acid source component.

Preferably, the reactant particle is anhydrous basically, so that whole moisture content is lower than (comprising that bonded water is that crystal water and unconjugated water are free water content) 0.5wt% of effervescent granules.When this promotes fluid to be water in reaction, or when water can promote to react contacting of promotion fluid and reactant, be particularly preferred.More particularly, when effervescent granules comprised acid source and alkali source simultaneously, the acid source that preferably is used to form effervescent granules at least had the 0.1wt% of being lower than, more preferably less than 0.05wt% with most preferably be lower than the total moisture content of 0.01wt%.More preferably, alkali source also has the 0.1wt% of being lower than, more preferably less than 0.05wt% with most preferably be lower than the total moisture content of 0.01wt%.

Preferably, the granularity that the effervescent granules material has makes that median particle is 0.001 millimeter to 7 millimeters, preferably is lower than 2 millimeters.

Preferably 500g/l is to 1200g/l for the tap density of effervescent granules, and more preferably 700g/l is to 1100g/l.

The optional supplementary component that comprises of reactive behavior particle.Usually, the effervescent granules material package contains the particle of the supplementary component that is not higher than 50wt%, preferably is not higher than 35wt% and more preferably no higher than 20% or 10%.Particularly preferably be and have highly active particle, it comprises no more than 5wt% or not even more than the supplementary component except that those help gas generation/release component of 2wt%.When the reactive behavior particle is when being used for the effervescent granules of detergent composition, any or its mixture below suitable supplementary component can comprise in the simple detergent ingredients of describing.Specially suitable is that tensio-active agent or organic or inorganic help and wash component, preferred water miscible those, as described below those.

Optional binding agent or the coating of comprising of reactive behavior particle of the present invention.Suitable bonding or coating material are the mixtures that is selected from one or more in the known binding agent and coating in the prior art field.Especially, suitable binding agent comprises anion surfactant such as C ₆-C ₂₀Alkyl or alkylaryl sulphonate or vitriol, preferred C ₈-C ₂₀Alkylbenzene sulfonate, derivatived cellulose such as carboxymethyl cellulose and homopolymerization-or copolymerization-poly carboxylic acid or their salt, nonionogenic tenside, preferred every mol of alcohol contains the C of 5-100mol oxyethane ₁₀-C ₂₀Alcohol ethoxylate and more preferably every mol of alcohol contain the C of 20-100mol oxyethane ₁₅-C ₂₀Primary alcohol ethoxylate.In the middle of these, every mol of alcohol with 25mol oxyethane in addition the tallow alcohol (TAE25) of ethoxylation or every mol of alcohol with 50mol oxyethane in addition the tallow alcohol (TAE50) of ethoxylation be preferred.Other preferred binding agent comprises polymer materials, as has the polyvinylpyrrolidone of 12,000 to 700,000 molecular-weight average and have the polyoxyethylene glycol of 600 to 10,000 molecular-weight average.Maleic anhydride and ethene, methylvinylether, other example that methacrylic acid or acrylic acid multipolymer are polymeric binder.Other binding agent further comprises C ₁₀-C ₂₀Single-and two-glyceryl ether and C ₁₀-C ₂₀Lipid acid.C is arranged in embodiment of the present invention of binding agent in hope ₈-C ₂₀Alkylbenzene sulfonate is particularly preferred.

The reactive behavior particle of Shi Yonging allows this mixture carry out granulation step formation particulate material then and prepares preferably by reactant composition being mixed with any supplementary component to produce homogenizing mixture in the present invention.Can use any prilling process, yet in order to keep the high reactivity level in finished product reactive behavior particle, granulation is carried out under situation about any free water content not being incorporated into basically in the mixture preferably.Common is coalescent, extrudes, and pill, compression method all are suitable.Yet preferred agglomeration step comprises that the pressure agglomeration step forms the reunion mixture, then carries out granulation step if necessary, and aggregate is made into the reactive behavior particle in this step, as is used for the effervescent granules of detergent composition of the present invention.

In the coalescent method of preferred pressure, the substantially dry mixture that comprises reactant and any selective supplementary component is bearing high external force, particle closely is close together, thereby with (bulk mass) densification of particulate quality and between each component of mixture, produce bonding mechanism.Really, the coalescent coalescence mechanism that caused of pressure, be characterised in that and between the primary stage solids effervescent granules, have intergranular cohesive action and be a kind of structure, many their characteristics still can be recognized and keep to effervescent granules in this structure, for example has the ability of next release of carbon dioxide that reacts at water.

Being used for the relevant density of the present invention's reactive behavior particulate preferred method with manufacturing increases with institute's applied pressure and is closely related.Typically, carry out pressure coalescent before, from comprising the density that bubbling raw material is the mixture of acid plus carbonate source and optional binding agent, tap density is brought up to 200g/l at the most, preferred 10g/l is to 150g/l.

The coalescent different methods of being classified by the size of the power that applies that uses of pressure carries out.Preferred method used herein is a roll compaction.In this method, reactant, preferred acid source and alkali source and any selective supplementary component apply reactive force between two compressing rollers after being mixed together, this roller is exerted pressure to mixture so that the rotation of roller is transformed into mixture the sheet/thin slice of compacting.Broken then reactive behavior particle, the i.e. effervescent granules of forming of the sheet/thin slice of compacting.

Typical roll squeezer used herein is the Pharmapaktor L200/50P  that for example is purchased from Hosokawa Bepex GmbH.Via the process variable of the pressure agglomeration step of roll compaction is distance, feeding rate, compaction pressure and roller rotating speed between roller.Typical feeding unit is a feed worm.0.5-10 centimetre typically of distance between roller, preferred 3-7 centimetre, more preferably 4-6 centimetre.Pressing force typically between 20kN and 120kN, preferred 30-100kN, more preferably 50-100kN.Typically, the roller rotating speed is 1-180rpm, preferably 2-50rpm and more preferably 2-35rpm.Typically, feeding rate is 1-100rpm, preferably 5-70rpm and more preferably 8-50rpm.The temperature of compressing is not crucial, is generally 0-40 ℃.

Sheet/thin slice of being produced by the coalescent method of pressure can be broken into effervescent granules with any appropriate method that forms particulate material by the size minimizing with sheet/thin slice, for example by sheet/flaking, weak point are cut or the production desired length that ruptures, if necessary, by making particulate material become circle or spherical pellets that circle promptly obtains to meet the defined diameter in front someway.In preferred embodiments, a kind of mode of flinders/thin slice is that sheet/thin slice with compacting grinds after the roll compaction step.Grinding typically uses the small thin slices crusher FC200  available from Hosokawa Bepex GmbH to carry out.

According to the needed granularity of effervescent granules material, the material of grinding can further sieve.Sieving of foaming pellet can be carried out with the Alpine Airjet Screen  that for example is purchased.

Water is that reaction promotes in the fluidic reactive behavior particulate preferred method producing wherein, when they are made into the reactive behavior particle, handling under the condition of control so that when reactant forms the reactive behavior particle, reduce the amount of the moisture that can contact each reactant.The inventor has been found that even the moisture of trace also can influence the reactive behavior particulate stability of being produced unfriendly.Especially, when the reaction between first and second reactants was self-accelerating reaction, for example when the reaction between two reactants produced water as by product, this was a particularly important.This factor seems, and a very important object lesson is that the particle that will produce is an effervescent granules, and it forms from two kinds of reactants, is respectively acid source and alkali source, is especially respectively for example organic acid (for example citric acid) and carbonate source.

Therefore, in such preferred method, first and second kinds of reactants are made into reactive behavior particle such as effervescent granules in the overdrying condition, and wherein atmospheric moisture is than littler in the processing environment.This is usually by using dehumidizer to realize.Preferably, relative humidity (RH) is lower than 40%, more preferably less than 30% with most preferably be lower than 20%.Preferably, in addition, at least a and preferred two kinds in the reactant provide to be prepared into reactive behavior particle of the present invention with the overdrying form." overdrying " is meant that reactant provides in one way, this mode is exsiccant (promptly whole basically free water contents is removed), still anhydrous basically in addition (like this, combination water, as crystal water or be incorporated in structural other water of reactant at least some be removed).Therefore, preferably, when first and second kinds of reactants contact with each other, preferred a kind of and more preferably the total moisture content that has of two kinds of reactants (comprise free-water and crystal water, it can be in drying oven measure down at 120 ℃ in dry 2 hours) for being not more than 0-1wt%, more preferably no more than 0.05wt% with most preferably be not more than 0.01wt%.

The detergent composition that comprises effervescent granules

According to the present invention, also provide the detergent composition that comprises detergent base and above-mentioned effervescent granules.This detergent base can be any common detergent composition.Yet generally speaking, it comprises preformed detergent base component, and the latter comprises tensio-active agent and optional additional detergent composition.Preferably when contacting with effervescent granules, the eRH of base-material (equilibrium relative humidity) is not more than 25%, more preferably no more than 20% or not even greater than 15% or 12% or even 10%.ERH is the description of product according to manufacturers, as illustrated method in the RotronicHygroskop application specifications 2/E Spi/S of mark date 3.1.83, uses the Rotronic that calibrated ^TMHygroskop DT, the defined saturated salt solution of the tested humidity range of use covering is measured.Whole measurements is to carry out under 25 ℃.

Of the present invention preferred aspect, at least a component has been carried out overdrying and promptly has been dried to a kind of like this level in detergent base, makes the water that is incorporated on one or more detergent ingredients in this detergent base component or optional additional detergent composition be removed.

The detergent base component

Detergent base comprises the detergent base component usually.This type of component comprises the prefabricated particulate matter of powder, particle, sheet form or other solid form, and it comprises tensio-active agent and optional additional detergent composition.

Tensio-active agent can be a negatively charged ion, nonionic, and positively charged ion, amphipathic, zwitter-ion or their mixture.Preferred detergent base component comprises negatively charged ion, nonionic and/or cats product.Especially, the base ingredient that comprises anion surfactant is useful especially.Suitable tensio-active agent is discussed in more detail below.The surfactant content of preformed base ingredient is the 5-80wt% of this base ingredient preferably.Be higher than 10 or even to be higher than 30% amount of surfactant be preferred.Be lower than 70% or even to be lower than 50% amount of surfactant be preferred.

The detergent base component also comprises solid material usually, and it can be filler such as vitriol (especially sodium sulfate), but more preferably comprises at least a detergent ingredients, especially washing assistant or basic component, or the mixture of this type of component.Suitable examples comprises phosphoric acid salt, aluminosilicate, crystalline layered silicate, yellow soda ash or unbodied silicate.These materials are described in greater detail below.For example, these components can be higher than 5wt% to account for the content that is pre-formed base ingredient separately or with form of mixtures, preferably be higher than 10wt% or even the amount that is higher than 20wt% exist.Particularly preferred builder component is yellow soda ash and/or zeolite.Zeolite A and zeolite MAP all are suitable.

Preformed base ingredient preferably also comprises organic washing-assisting detergent, as poly carboxylic acid and/or salt such as citric acid, tartrate, oxysuccinic acid, succsinic acid and their salt or polymeric polycarboxylic acid ester (salt) as polymkeric substance or its multipolymer based on vinylformic acid or toxilic acid.Usually to account for the 15wt% that is lower than of base ingredient, the amount that preferably is lower than 10wt% is present in the base ingredient this type of component.

Other preferred composition is a sequestrant in preformed base ingredient, as phosphonic acid ester sequestrant NTA, and DTPA and succinic acid derivative sequestrant, as described below.These components preferably with account for base ingredient be lower than 5wt% or even the amount that is lower than 2wt% be present in the preformed granular component.

Detergent base can comprise one or more preformed detergent base components.Suitable be pre-formed component and can pass through spraying drying, coalescent, pill is extruded or is compressed and forms, and all methods that are used for the fusion detergent ingredients are that the prior art field is known.The particularly preferred base ingredient that is pre-formed is powder, agglomerated thing and the extrudate that obtains from spray-drying process.Spray-drying powder is useful especially.According at least one low shear-mixed step, for example the detergent base component that (for example coalescent by fluidized-bed) makes in fluidized-bed also is preferred.

The suitable spray-drying process that is used to form this preformed detergent base component for example is described among EP-A-763594 or the EP-A-437888.The appropriate method that is used to form the detergent base component that belongs to agglomerated thing is described in for example WO93/25378, and EP-A-367339 is among EP-A-420317 or the EP-A-506184.Suitable medium to low shear mixer can be (Ploughshare) moderate-speed mixers of Lodige KM (trade mark) for example, or by Fukae, the mixing tank that DraesSchugi makes or only come the mixing tank of the similar brand of blended to low shearing with medium.Lodige KM (ploughshare) moderate-speed mixers as the preferred mixing tank that uses among the present invention comprises a horizontal hollow stationary cylinder, and it has the rotating shaft that install at the center, and several plow-shape blades are distributed on the axle.Preferably, axle is with about 15-140rpm, and more preferably approximately the speed of 80-120rpm is rotated.Grind or pulverize and can finish by cutting knife, cutting knife is generally dimensionally less than turning axle, and it is preferably approximately being operated under the 3600rpm.Kin other mixing tank that is suitable in this method comprises Lodige Ploughshare ^TMMixing tank and Drais  K-T160 mixing tank.Usually, in the method for the invention, shearing action is not more than the shearing that is produced by Lodige KM mixing tank, and the tip speed of plough is lower than 10m/s, or even is lower than 8m/s or even lower.

Preferably, the mean residence time of various initial detergent ingredients is preferably about 0.1-15 minute in low speed or moderate-speed mixers, and most preferably the residence time is about 0.5-5 minute.The density of the washing composition agglomerated thing that is obtained by this way, is at desired level.

Other suitable blender that is used for the present invention is low or extremely low shear mixer, as rotating cylinder coalescer, rotary drum coalescer, disc type coalescer and fluidized-bed coalescer.

The fluidized-bed coalescer is particularly preferred.Typical fluidized-bed coalescer is to arrive under the airflow on surface speed of 4m/s 0.4, operates under malleation or negative pressure.Inlet air temperature is normally-10 or 5 ℃ up to 250 ℃.Yet inlet air temperature is usually less than 200 ℃, or even is lower than 150 ℃.Suitable method for example is described among WO98/58046 or the WO99/03964.The appropriate method that is used for being formed by extrusion molding the detergent base component is described in for example WO91/02047.

Detergent base can comprise that only a kind of aforesaid preformed component or it can comprise the mixture of component, the for example mixture of the mixture of different spray-drying powders or different agglomerated things etc., or the mixture of the binding substances of agglomerated thing as previously discussed, spray-drying powder and/or extrudate etc.

Particularly preferred detergent base component is a spray-drying powder.

The additional detergent composition

As mentioned above, detergent base comprises tensio-active agent, and can comprise one or more additional detergent compositions.This can comprise detergent raw material or preformed particulate matter, and the latter is processed to form solid particulate matter by other composition with at least a detergent ingredients and show activity or non-activity in washing composition to prepare.When granular component was detergent raw material, any granulated detergent composition was suitable.These can be solid surfactant or soap, or the water-soluble or dispersible polymeric material of water, enzyme, bleaching component such as bleach-activating agent or bleaching salt such as peroxy salt.Tensio-active agent and additional detergent composition discuss in more detail hereinafter.Below any in the listed composition can be used as independent solid particulate matter or add as preformed particulate matter or via the detergent base component.These additional detergent compositions must be incorporated in the detergent base, if desired, then carry out drying step.Final detergent base preferably has and is lower than 30% eRH.

Detergent ingredients

Tensio-active agent

The suitable surfactant that is used for the present invention is these tensio-active agents of negatively charged ion, nonionic, both sexes and zwitter-ion type, at the U.S.P3 that is issued to Laughlin and Heuring of on December 30th, 1975 bulletin, lists in 929,678.Other example is given among " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Suitable cationic surfactants be listed in the U.S.P4 that on March 31st, 1981 was issued to Murphy, in 259,217.

Preferably, detergent composition of the present invention and comprise this type of grains of composition and contain additional anion surfactant.Basically, any anion surfactant that is used for washing purpose can both be included in this detergent composition.These comprise the anion sulfate acid root, sulfonate radical, the salt of carboxylate radical and sarkosine root tensio-active agent (for example comprise sodium, potassium, ammonium and substituted ammonium salt as single-, two-and the trolamine salt).Anion sulfate and sulfosalt surfactant are preferred.

Anion surfactant can be lower than 25wt% or even the amount that is lower than 20wt% be present in the detergent base component, but in comprising the final detergent composition of particulate, preferably with 0.1-60%, more preferably 1-40%, most preferably the amount of 5-30% exists.

Other anion surfactant comprises anionic carboxylic acid salt surfactant such as alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate and soap (" alkyl carboxyls "), as from 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, the aqueous solution salt of selecting in the water-soluble salt of the sad and 2-amyl group-1-enanthic acid of 2-butyl-1-.Some soap is also included as suds suppressor.Other suitable anion surfactant is that general formula is R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl and M are alkalimetal ions.Other anion surfactant comprises isethionate; as acyl-hydroxyethyl sulfonate, N-acyl taurine salt, the fatty acid amide of methyl tauride; alkyl succinate and sulfosuccinate, the monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂-C ₁₈Monoesters), the diester of sulfosuccinate (especially saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resin Acid and hydrogenated resin acids also are suitable, as rosin, and staybelite, and Resin Acid and hydrogenated resin acids are present in the butter or from butter and derive.

Here the anion sulfate tensio-active agent of Shi Yonging comprises straight chain and side chain primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol ethylene oxide ether sulfate, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine vitriol and alkyl polysaccharide is as the vitriol (nonionic non-sulfuric acid salt compound is described in herein) of alkyl polyglucoside.Preferably, 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.Preferably, alkyl ethoxy sulfate surfactant is selected from per molecule carries out ethoxylation with 0.5-20mol oxyethane C ₁₀-C ₁₈Alkyl-sulphate.More preferably, alkyl ethoxy sulfate surfactant is a per molecule with the oxyethane of 0.5-7, the preferred 1-5mol C of ethoxylation in addition ₁₁-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate.

The preferred surfactants binding substances is preferred alkyl-sulphate and/or sulfonate and alkyl ethoxy sulfate surfactant, chooses the mixture with cats product wantonly.This type of mixture has been disclosed among the PCT patent application No.WO93/18124.

Be adapted at anionic sulphonate type tensio-active agent used herein and comprise C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary sulfonated alkane, C ₆-C ₂₄Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, the salt of fatty oil acylglycerol sulfonate and their any mixture.

Basically any alkoxy-based non-ionic surface active agent or mixture here all are suitable.Ethoxylation and propoxylation nonionic surface active agent are preferred.

The preferred alkoxylated tensio-active agent can be selected from the nonionic condenses of alkylphenol, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, with the initial nonionic ethoxylate/propoxylation condenses of propylene glycol with the initial nonionic ethoxylation condensation product of propylene oxide/ethylenediamine adduct.

Fatty alcohol and 1-25mol epoxy alkane, especially the condensation product of oxyethane and/or propylene oxide is particularly suitable for here using.Particularly preferably be the condensation product of straight or branched uncle with the alkyl that contains 6-22 carbon atom or secondary alcohol and 2-10mol oxyethane/mol of alcohol formation.

Being adapted at polyhydroxy fatty acid amide used herein is to have formula R ²CONR ¹Those of Z, wherein: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-, or their mixture, preferred C ₁-C ₄Alkyl; R ²Be C ₅-C ₃₁Alkyl; Z has to have at least 3 hydroxyls to be directly connected in the polyhydroxy alkyl of the line style hydrocarbon chain on the chain, or their alkoxy derivative (preferred ethoxylation or propoxylation).Z preferably derives from reducing sugar in reductive amination process; More preferably Z is glycidyl (glycityl).

Suitable alkyl polysaccharide used herein is disclosed in the US patent 4 of bulletin on January 21st, 1986, among 565,647 (Llenado), has the hydrophobic grouping that contains 6-30 carbon atom, and the polysaccharide with the hydrophilic group that contains 1.3 to 10 sugar units, for example poly glucoside.Preferred alkyl poly glucoside has following formula:

R ²O (C _nH _2nO) _t(glycosyl) x

R wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T be 0 to 10 and x be 1.3 to 8.Glycosyl is preferably from the glucose deutero-.

Suitable amphoterics used herein comprises amine oxide surfactant and alkyl both sexes carboxylic acid.Suitable amine oxide comprises having general formula R ³(OR ⁴) xN ⁰(R ⁵) ₂Those compounds, R wherein ³Be selected from the alkyl that contains 8-26 carbon atom, hydroxyalkyl, amido propyl and alkyl phenyl, or their mixture; R ⁴Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; With each R ⁵Be alkyl or the hydroxyalkyl that contains 1-3 carbon atom, or contain the polyethylene oxide group of 1-3 ethylene oxide group.C preferably ₁₀-C ₁₈Alkyl dimethyl amine oxide, and C _10-18Amido alkyl dimethyl amine oxide compound.

Zwitterionics can also be incorporated in the detergent composition of the present invention.These tensio-active agents can loosely be described as the derivative of secondary and tertiary amine, the derivative of the heterocycle second month in a season and tertiary amine, or the derivative ， quaternary phosphine of quaternary ammonium or uncle's sulfonium compound.Betaines such as C _12-18Dimethylammonio (ammonio) hexanoate and C _10-18Amide group propane (or ethane) dimethyl (or diethyl) trimethyl-glycine and sultaine tensio-active agent are the exemplary zwitterionicss that here uses.

Suitable cationic surfactants used herein comprises quaternary ammonium surfactant.Preferably, quaternary ammonium surfactant is single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant wherein remain the N position by methyl, and hydroxyethyl or hydroxypropyl replace.Preferred monoalkoxyization and bis-alkoxy amine tensio-active agent in addition.

Cationic ester surfactant such as cholinesterase tensio-active agent (for example being disclosed in US patent No4228042,4239660 and 4260529) they also are suitable, as preferably having the cation mono alkoxylate amine surfactant of general formula I:

R wherein ¹Be C _10-18Alkyl and their mixture, especially C ₁₀-C ₁₄Alkyl, preferred C ₁₀And C ₁₂Alkyl, and X provides any suitable anion of charge balance, preferred chlorine or bromine ion.

The amount of cation mono alkoxylate amine surfactant in detergent composition of the present invention generally is 0.1-20 weight %, preferred 0.2-7 weight %, most preferably 0.3-3.0 weight %.

Positively charged ion bis-alkoxy amine surfactant as Also be useful, R wherein ¹Be C ₁₀-C ₁₈Alkyl and their mixture, preferred C ₁₀, C ₁₂, C ₁₄Alkyl and their mixture.X provides any suitable anion of charge balance, preferred chlorion.

Bleach-activating agent

Detergent composition of the present invention preferably comprises bleach-activating agent, preferably includes organic peroxyacid bleach precursor.Preferably, said composition comprises at least two kinds of peroxyacid bleach precursors, preferred at least a hydrophobicity peroxyacid bleach precursor and at least a wetting ability peroxyacid bleach precursor, as defined herein.The generation of organic peroxide acid can realize by the situ reaction of precursor and hydrogen peroxide cource.Bleach-activating agent selectively or in addition also comprises preformed peroxyacid bleach.Preferably, bleach-activating agent is to exist as particle independent, blending.

Preferably, any bleach-activating agent is present in and has 600 microns to 1400 microns, in the granular component of preferred 700 microns to 1100 microns mean particle size (by weight).Preferably, at least 80%, preferred at least 90% or even at least 95% or even 100% component or the component that comprises this bleach-activating agent have 300 microns to 1700 microns, preferred 425 microns to 1400 microns granularity basically.Preferred hydrophobicity peroxyacid bleach precursor preferably comprises and has the oxygen base-compound of Phenylsulfonic acid foundation group, preferred NOBS, DOBS, LOBS and/or NACA-OBS.Preferred wetting ability peroxyacid bleach precursor preferably includes TAED.

Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that produces peroxy acid in crossing oxygen hydrolysis reaction with hydroperoxidation.Usually peroxyacid bleach precursor can be expressed as X-C (O)-L, and wherein L is that leavings group and X are any functional group basically, so that the structure of the peroxy acid that is produced after crossing oxygen hydrolysis is

For the purposes of the present invention, the hydrophobicity peroxyacid bleach precursor produces the peroxy acid of above general formula, wherein X is the group that comprises at least 6 carbon atoms, and the wetting ability peroxyacid bleach precursor produces the peroxyacid bleach of above general formula, and wherein X is the group that comprises 1-5 carbon atom.Leavings group hereinafter is called the L group, enough reactive behavioies must be arranged so that allowed oxygen hydrolysis reaction take place in Best Times scope (for example wash(ing)cycle).Yet if L has too high reactive behavior, this activator is difficult to stable, makes to be used for bleaching composition.Preferred L group is selected from: With

With With their mixture, wherein R ¹Be the alkyl that contains 1-14 carbon atom, aryl, or alkaryl, R ³Be the alkyl chain that contains 1-8 carbon atom, R ⁴Be H or R ³And Y is H or solubilizing group.R ¹, R ³And R ⁴In any one can be replaced by any functional group basically, comprising for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkylammonium.

Preferred solubilizing group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be the alkyl chain that contains 1-4 carbon atom, M provides deliquescent negatively charged ion for bleach-activating agent provides deliquescent positively charged ion and X for activator of bleaching agent.Preferably, M is a basic metal, the ammonium cation of ammonium or replacement, and wherein sodium and potassium are most preferred, and X is a halogen, hydroxide radical, methylsulfate or acetic acid anion.

The peroxyacid bleach precursor compound is preferably with 0.5-30wt%, more preferably 1-15wt%, and most preferably the amount of 1.5-10wt% is incorporated in the final detergent composition.When existing, the ratio of wetting ability and hydrophobicity bleach precursor preferably 10: 1 to 1: 10, more preferably 5: 1 to 1: 5 or even 3: 1 to 1: 3.Suitable peroxyacid bleach precursor compound typically contains one or more N-or O-acyl group, and this precursor is selected from large-scale classification.Suitable classification comprises acid anhydrides, ester, imide, the acylated derivatives of lactan and imidazoles and oxime.The example of the useful matter in these classifications is disclosed among the GB-A-1586789.Suitable ester is disclosed in GB-A-836988, and 864798,1147871,2143231 and EP-A-0170386.

Alkyl percarboxylic acids bleach precursor has formed percarboxylic acids after crossing oxygen hydrolysis.The preferred precursor of this type provides peracetic acid in crossing oxygen hydrolysis.The alkyl peroxycarboxylic acid precursors compound of preferred imide-type comprises N, N, and N ', N '-tetra-acetylatedization Alkylenediamine, wherein alkylidene group contains 1-6 carbon atom, and especially wherein alkylidene group contains those compounds of 1,2 and 6 carbon atom.Tetra acetyl ethylene diamine (TAED) is especially preferably as the wetting ability peroxyacid bleach precursor.Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (iso-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.

The alkyl peroxy acids precursor compound that acid amides replaces among the present invention is suitable, and it comprises those with following general formula:

Or

R wherein ¹Be to have about 1 aryl or alkaryl, R to about 14 carbon atoms ²Be the alkylidene group that contains 1-14 carbon atom, arylidene, and alkarylene, and R ⁵Be H or the alkyl that contains 1-10 carbon atom, aryl or alkaryl and 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 be the aryl or the alkaryl of straight or branched alkyl, replacement, contain branch, substituting group or both, and derive from synthetic source or natural source (comprising for example tallow).Similarly structural changes is for R ²Allow.R ²Can comprise alkyl, aryl, wherein this R ²Also can contain halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Should not contain and surpass 18 carbon atoms altogether.The bleach activating immunomodulator compounds that the acid amides of this type replaces is described among the EP-A-0170386.Preferably, R ¹And R ⁵Form ring texture with nitrogen and carbon atom.

The preferred embodiment of the bleach precursor of this type comprises the peroxyacid precursor compound that acid amides replaces; be selected from (6-decoyl amido-caproyl) oxygen base benzene sulfonate; (6-caprinoyl amido-caproyl) oxygen base benzene sulfonate; (6-nonanoyl amido caproyl) oxygen base benzene sulfonate very preferably; with their mixture, as described in the EP-A-0170386.

The cationic peroxyacid precursor compound that the peroxybenzoic acid precursors compound (for example be disclosed in EP-A-332294 and EP-A-482807 in) of peroxybenzoic acid is provided when crossing oxygen hydrolysis benzoxazine organic peroxy acid precursor and produces the positively charged ion peroxy acid when crossing oxygen hydrolysis also is suitable.

The positively charged ion peroxyacid precursor is described in United States Patent (USP) 4,904,406; 4,75 1,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,09 3,022; 5,106,528; Britain 1,382,594; EP475,512,458,396 and 284,292; And JP87-318, in 332.The example of preferred cation peroxyacid precursor is described in UK Patent Application No.9407944.9 and US patent application 08/298903,08/298650,08/298904 and 08/298906.

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

Except containing organic peroxide acid bleach precursor compound, or replace this compound, particle of the present invention or composition contain preformed organic peroxide acid, and typical amount is 0.1-15wt%, more preferably 1-10wt%.The preferred classes of organic peroxy acid compound is the compound that acid amides replaces, described in EP-A-0170386.Other organic peroxide acid comprises diacyl and four acyl peroxides, especially dodecane diperoxy carboxylic acid, tetradecane diperoxy carboxylic acid and n-Hexadecane diperoxy carboxylic acid.Single-and two-peroxide nonane diacid, single-and diperoxy undecane dicarboxylic acid and N-O-phthalic amido peroxide caproic acid also be suitable.

Peroxide source

Inorganic perhydrate salts is the preferred source thing of superoxide.Preferred these salt are with the 0.01-50wt% with respect to said composition, and more preferably the amount of 0.5-30wt% exists.

The example of inorganic perhydrate salts comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Usually these materials are to prepare by crystallization or bed process.Inorganic perhydrate salts normally is an an alkali metal salt.Inorganic perhydrate salts can be used as crystalline solid and is included, and need not additional protection.Yet, for some perhydrate salt, the form that the preferred practice scheme of this type of granular composition utilizes certain material to apply, this material provides better package stability for the perhydrate salt in the granulated product.Suitable coating comprises inorganic salt such as alkalimetal silicate, carbonate or borate or their mixture, or organic materials such as wax, oil, or fatty soap.Sodium peroxoborate is a preferred perhydrate salt and can to present nominal general formula be NaBO ₂H ₂O ₂Mono-hydrate or tetrahydrate NaBO ₂H ₂O ₂3H ₂The form of O.Alkali metal percarbonate, especially SPC-D is the preferred perhydrate of the present invention.SPC-D is to have corresponding to 2Na ₂CO ₃3H ₂O ₂The addition compound of molecular formula, and can be used as crystalline solid and be purchased.The peroxy Potassium peroxysulfate is the another kind of inorganic perhydrate salts that is used for detergent composition.

Sequestrant

Sequestrant used herein is meant the detergent ingredients that is used for the chelating heavy metal ion.These components also can have calcium and magnesium sequestering power, but preferably, they have shown the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.Sequestrant is present in the detergent base component and/or the dry additional detergent composition that adds of conduct usually, so that they are with the 0.005-10 weight % with respect to said composition or component, preferred 0.1-5 weight %, more preferably 0.25-7.5 weight % and most preferably the total amount of 0.3-2 weight % be present in the final detergent composition.

Suitable sequestrant includes organic phosphonates, as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt, preferred diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexanediamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene-1, the 1-diphosphonate, 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid and 1,1-hydroxyl ethane dimethylene phosphonic acids.

Other suitable sequestrant used herein comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or any their salt and iminodiacetic acid derivatives such as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid are described in EP-A-317, in 542 and EP-A-399,133.Be described in EP-A516, iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant in 102 here also are suitable.Be described in EP-A-509, the Beta-alanine-N in 382, N '-oxalic acid, aspartic acid-N, N '-oxalic acid, single acetate of aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable.EP-A-476,257 describe suitable amino-type sequestering agent.EP-A-510,331 describe from collagen, Keratin sulfate or casein derived suitable sequestering agent.EP-A-528,859 describe suitable alkyl imino oxalic acid sequestering agent.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2,4-tricarboxylic acid also are suitable.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is suitable.Especially preferred is diethylene triaminepentaacetic acid(DTPA), quadrol N, N '-disuccinic acid (EDDS) and 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or their basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or their mixture.Especially, the sequestrant that comprises amino or amido be bleaching responsive and in composition of the present invention, be suitable.

Water miscible washing-aid compound

Detergent composition preferably contains water miscible washing-aid compound here, typically with 1-80 weight %, and preferred 10-60 weight %, most preferably the amount of 15-40 weight % is present in this detergent composition.

A kind of preferred detergent composition of the present invention comprises phosphatic builder material, preferably with 0.5-60 weight %, and more preferably 5-50 weight %, more preferably the amount of 8-40 weight % exists.The suitable example of water miscible phosphate builders is an alkali metal tripolyphosphates, the pyrophosphate salt of sodium, potassium and ammonium, the pyrophosphate salt of sodium and potassium and ammonium, (just) phosphoric acid salt of sodium and potassium, Sodium polymetaphosphate, wherein the polymerization degree is in about 6-21 scope, and the salt of phytic acid.Phosphatic builder material preferably includes tetrasodium pyrophosphate or even more preferably anhydrous tripoly phosphate sodium STPP.

Suitable water soluble detergency promoter compound comprises the water-soluble monomer multi-carboxylate, or their sour form, homopolymerization or copolymerization poly carboxylic acid or their salt, wherein poly carboxylic acid comprises at least two carboxyls that are separated from each other by no more than two carbon atoms, borate, and the mixture of any aforesaid compound.Carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligomer types, though the monomer multi-carboxylate generally is preferred for cost and performance.The suitable carboxylic salt that contains a carboxyl comprises lactic acid, the water soluble salt of oxyacetic acid and their ether derivant.The multi-carboxylate of containing two carboxyls comprises succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, the water-soluble salt of tartronic acid and fumaric acid, and ether carboxylate and sulfinyl carboxylate salt.Containing the multi-carboxylate of three carboxyls or their acid comprises, especially water-soluble citrate, aconitate and citraconate and succinate derivative, as be described in English Patent No.1,379, carboxymethyl oxygen base succinate in 241 is described in English Patent No.1,389, newborn oxygen base succinate in 732, with the aminosuccinic acid salt and the oxygen Quito carboxylate salt material that are described in the Netherlands patent applications 7205873, as be described in English Patent No.1,387,2-oxa--1,1 in 447,3-tricarballylic acid salt.The most preferred poly carboxylic acid that contains three carboxyls is a citric acid, and preferably with 0.1-15 weight %, more preferably the amount of 0.5-8 weight % exists.

The multi-carboxylate of containing four carboxyls comprises oxygen base disuccinate (be disclosed in English Patent No.1,261,829 in), 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.Containing the substituent multi-carboxylate of sulfo group comprises and is disclosed in English Patent 1,398,421 and 1,398, in 422 and in U.S. Patent No. 3,936, the sulfo-succinic acid salt derivative in 448, with be described in English Patent No.1, the sulfonation pyrolysis Citrate trianion in 439,000.Preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate up to three carboxyls, especially Citrate trianion.

The mixture of the parent acid of monomer or oligomeric multi-carboxylate's sequestrant or they and they salt, for example citric acid or Citrate trianion/citric acid mixture also are considered to useful builder component.The borate washing assistant, and can under washing composition storage or wash conditions, the boratory washing assistant that contains borate formation material of generation here be useful water soluble detergency promoter.

The example of organic polymer comprises water-soluble organic homopolymerization or copolymerization poly carboxylic acid or their salt, and wherein poly carboxylic acid comprises and is no more than at least two carboxyls that two carbon atoms are separated from each other.The polymkeric substance of back one type is disclosed in GB-A-1,596,756.The example of this type of salt is to have the multipolymer that MWt is the polyacrylate of 1000-5000 and they and maleic anhydride, and this analog copolymer has 2000 to 100,000, especially 40,000 to 80,000 molecular weight.The polyamino compound here also is useful, comprises from aspartate-derived those, and as at EP-A-305282, those that describe among EP-A-305283 and the EP-A-351629.

Partly soluble or insoluble washing-aid compound

Composition of the present invention can contain the solvable or insoluble washing-aid compound of part that exists in detergent base component and/or optional supplementary component.When existing, typically, they are with 0.5-60 weight %, preferred 5-50 weight %, and most preferably the total amount of 8-40 weight % is present in this detergent composition.The example of water-insoluble washing assistant comprises sodium aluminium silicate largely.As previously discussed, in one embodiment of the invention preferably, only there is a spot of aluminosilicate washing assistant.

Suitable aluminosilicate zeolites has formula Na _z[(AlO ₂) z (SiO ₂) y] xH ₂The structure cell that O represents, wherein z and y are at least 6; The mol ratio of z and y be 1.0 to 0.5 and x be at least 5, preferred 7.5-276, more preferably 10-264.Aluminosilicate material is hydrated form and preferably crystalline, contains 10-28%, more preferably the water of the combining form of 18-22%.

The aluminosilicate zeolites class can be a crude substance, but preferably synthetic source.Synthetic crystal type aluminosilicate ion exchange material can be with ProductName zeolite A, zeolite B, and zeolite P, X zeolite, zeolite HS and their form of mixtures are purchased.Zeolite A has following formula:

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

Preferred aluminosilicate zeolites in addition is a zeolite MAP builder.Zeolite MAP can be with 1-80%, and more preferably the amount of 15-40wt% exists.Zeolite MAP is described among the EP384070A (Unilever).It is defined as silicon/aluminum ratio and is not more than 1.33, preferably in the 0.9-1.33 scope and the more preferably alkali metal aluminosilicate of the zeolite P type in the 0.9-1.2 scope.It is desirable to silicon/aluminum ratio value especially and be not more than 1.15 and more especially be not more than 1.07 zeolite MAP.Aspect preferred, the zeolite MAP detergent builders has with median particle d ₅₀The granularity of value representation is the 1.0-10.0 micron, more preferably 2.0-7.0 micron, most preferably 2.5-5.0 micron.d ₅₀The particle of value representation 50wt% has the diameter less than this numerical value.Granularity especially can be by common analytical technology as the microscopy that uses scanning electronic microscope or utilize laser particle size meter described here to measure.Determine d ₅₀Other method of value is disclosed in EP384070A.

Dyestuff, spices, enzyme, white dyes

Here, the preferred component of composition is dyestuff and painted particle or stigma grain, and they can be bleaching susceptibility.Dyestuff used herein can be the aqueous solution or the non-aqueous solution of dyestuff or dyestuff.Preferably, dyestuff is the aqueous solution that comprises dyestuff, and content is for obtaining suitable painted any level of detergent particles or stigma grain, preferably make the amount of dye solution reach dyed particles up to 2wt%, or more preferably up to 0.5wt%, as mentioned above.This dyestuff also can with the non-aqueous carrier material, as comprise the non-aqueous liquid material mixing of nonionic surface active agent.Randomly, dyestuff also comprises other composition, and as organic binder material, it also can be a non-aqueous liquid.Dyestuff can be any suitable dyestuff.The specific examples of suitable dye comprises E104-food dye Huang (quinoline yellow), E110-food dye Huang 3 (sunset yellow FCF), E131-food dye indigo plant 5 (patent blue V), ultramarine blue (trade mark), E133-food dye indigo plant 2 (brilliant blue FCF), E140-natural green 3 (chlorophyll and CHLOROPHYLLINE), green 7 (the chlorating copper phthalocyanines) of E141 and Pigment.Preferred dyestuff can be Monastral Blue BV slurry (trade(brand)name) and/or Pigmasol green (trade(brand)name).

The in addition preferred composition of the present composition is spices or flavor compositions.Any flavor compositions can here use.Spices also can be encapsulated.Preferred spices contains at least a component with lower molecular weight volatile constituent, for example has the molecular weight of 150-450 or preferred 350.Preferably, perfume composition comprises oxygen containing functional group.Preferred functional group is an aldehyde, ketone, alcohol or ether functional group or their mixture.

Be used for here particle or in addition very preferably the composition of composition be one or more additional enzymes.Preferred additional enzymes material comprises the lipase that is purchased that is incorporated into usually in the detergent composition, at, amylase, neutrality and Sumizyme MP, cellulase, restriction endonuclease (endolases), esterase, polygalacturonase, Sumylact L and peroxidase.Suitable enzyme is in US patent 3,519,570 and 3,533, discussion arranged in 139.

Preferably be purchased proteolytic enzyme and comprise those that sell with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), those that sell with trade(brand)name Maxatase, Maxacal and Maxapem by Gist Brocades, those that sell by Genencor International, and sell with trade(brand)name Opticlean and Optimase by Solvay Enzymes those.Proteolytic enzyme can be incorporated in the composition of the present invention, adds with the amount of the 0.0001-4wt% organized enzyme that is equivalent to said composition.Preferably amylase comprises, for example at GB-1, and the α-Dian Fenmei of describing in detail among 269,839 (Novo).Preferably be purchased amylase and comprise, those that sell with trade(brand)name Rapidase by Gist-Brocades for example, and by Novo Industries A/S with trade(brand)name Termamyl, those that Duramyl and BAN sell.Amylase very preferably can be to be described among the PCT/US9703635 and in WO95/26397 and WO96/23873 those.Amylase can be incorporated into the amount of 0.0001-2wt% organized enzyme in the composition of the present invention.The steatolysis endonuclease capable is with 0.0001-2wt%, preferred 0.001-1wt%, and most preferably the amount of the active lipolytic enzyme of 0.001-0.5wt% exists.Lipase can be fungi or bacterial origin, for example from the mould genus of humic, the lipase of Thermomycessp. or Rhodopseudomonas (comprising pseudomonas pseudoalcaligenes (Pseudomonaspseudoalcaligenes) or Pseudomonas fluorescens (Pseudomas fluorescens)) produces bacterial strain and obtains.From the chemistry of these bacterial strains or the lipase of gene modification mutant acquisition here also is useful.Preferred lipase is from the pseudomonas pseudoalcaligenes deutero-, and it is described among the European patent EP-B-0218272 of mandate.Here other preferred lipase is to obtain by expressing this gene from Humicola lanuginosa clone gene and as host's aspergillus oryzae, as described in European patent application EP-A-0258068, it is from Novo Industri A/S, Bagsvaerd, Denmark is purchased with trade(brand)name Lipolase.This lipase also is described in the United States Patent (USP) 4,810,414 of authorizing people such as Huge-Jensen on March 7th, 1989.

The composition here also preferably contains the hydrophilic white dyes of 0.005-5wt% some type as previously discussed of having an appointment.Example is the Tinopal-UNPA-GX of Ciba-Geigy Corporation ^TMAnd Tinopal-CBS-X ^TMOther comprises the Tinopal5BM-GX of Ciba Geigy Corporation ^TM, Tinopal-DMS-X ^TMWith Tinopal AMS-GX ^TM

The photobleaching agent

The photobleaching agent is the composition described here or the preferred component of component.Here preferred photobleaching agent comprises the compound with porphines or porphyrin structure.Porphines and porphyrin use as synonym in the literature, but porphines is represented without any the simplest substituent porphyrin as usual; Its mesoporphyrin is the group of porphines.Alleged in this application porphines will comprise porphyrin.The porphines structure optimization comprises metallic element or positively charged ion, preferred Ca, Mg, P, Ti, Cr, Zr, ln, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn.Preferably, photobleaching compound or component are selected from following these substituting group and are replaced: alkyl, and as methyl, ethyl, propyl group, the tertiary butyl and aromatic ring system, as pyridyl, pyridyl N-oxide compound, phenyl, naphthyl and anthryl structure division.Photobleaching compound or component can have solubilizing group as substituting group.Another selection or in addition, the photobleaching agent can comprise the polymeric constituent that can make photobleaching compound solubilising, PVP for example, PVNP, PVI or their multipolymer or their mixture.Photobleaching compound very preferably is the compound with phthalocyanine structure, and they preferably have above-mentioned metallic element or positively charged ion.

Phthalocyanine can be substituted, for example substituted phthalocyanine structure on one or more positions of 1-4,6,8-11,13,15-18,20,22-25,27 atom positions.

The organic polymer composition

Here, organic polymer is a preferred supplementary component and preferably as the component of any granular component such as detergent base component (they are as binding agent) and exist.For organic polymer, it refers to be used as usually any basically polymerizable organic compound of dispersion agent and antiredeposition and soil-suspending agent in detergent composition, any comprising in the high molecular organic polymer that is expressed as the clay flocculating agent here comprises according to quaternized ethoxylation of the present invention (gathering) amine clay soil and removing/anti redeposition agent.Organic polymer is typically being equivalent to the 0.01-30 weight % of composition or component, preferred 0.1-15 weight %, and most preferably the amount of 0.5-10 weight % is incorporated in the detergent composition of the present invention.Contain and be selected from toxilic acid, vinylformic acid, the terpolymer of the monomeric unit of poly aspartic acid and vinyl alcohol, those that especially have 5,000 to 10,000 molecular-weight average also are suitable.Other organic polymer that is fit to be incorporated in the detergent composition described here comprises derivatived cellulose, as methylcellulose gum, and carboxymethyl cellulose, Vltra tears and Natvosol.

Other useful organic polymer is a polyoxyethylene glycol, especially has molecular weight 1000-10000, more special 2000-8000 and most preferably about 4000 those.Here polymeric component very preferably is cotton and non-cotton soil release polymers, and this is according to people's such as people's such as Scheibel United States Patent (USP) 4,968,451 and Gosselink United States Patent (USP) 5,415,807 with especially according to US patent application No.60/051517.Here the another kind of organic compound of Shi Yonging is preferred clay suspending agent/anti redeposition agent, can be ethoxylation positively charged ion monoamine and two amines, has following formula:

Wherein X is selected from H, C ₁-C ₄Non-ionic group in alkyl or hydroxy alkyl ester or ether or their mixture, a is 0-20, preferred 0-4 (for example, ethylidene, sec.-propyl, hexa-methylene), b is 1 or 0; For positively charged ion monoamine (b=0), n is at least 16, and representative value is 20-35; For cationic diamine (b=1), n is about at least 12, and representative value is about 12 to about 42.Other dispersion agent/anti redeposition agent used herein is described in EP-B-011965 and US4, in 659,802 and US4,664,848.

When existing, the polymer-type dye transfer inhibitor is generally with 0.01-10%, the amount of preferred 0.05-0.5% exists and is preferably selected from polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinylpyrrolidonepolymers polymers or their binding substances, wherein these polymkeric substance can be cross-linked polymers.

The polymer-type stain remover is called " SRA " below, can randomly be used for component of the present invention or composition.If use, SRA is generally with 0.01-10.0 weight %, 0.1-5 weight % typically, and the amount of preferred 0.2-3.0 weight % is used.Preferred SRA typically the possess hydrophilic property segment so that the surface of hydrophobic fibre such as polyester and nylon produces wetting ability, with have hydrophobic chain segment to be deposited on the hydrophobic fibre and after washing and rinse cycle end, to remain adhered on the fiber, thus serve as the anchoring agent of hydrophilic segment.This can make and be easier to cleaning in the washing process of spot in the back that occurs after handling with SRA.Preferred SRA comprises the oligopolymer terephthalate, typically prepares by the method that comprises at least one transesterification/oligomerization, usually uses metal catalyst such as titanium (IV) alkoxide.Can prepare this type of ester via the additional monomer that, two, three, four or more a plurality of position are introduced in the ester structure by using, not form intensive crosslinked one-piece construction certainly.

Suitable SRA for example is described in U.S. 4,968,451 in November 6 nineteen ninety of J.J.Scheibel and E.P.Gosselink.Other SRA comprises the end capped terephthalic acid 1 of nonionic of the U.S. 4,711,730 of 8 days December in 1987 bulletin that is issued to people such as Gosselink, 2-propylene glycol/polyethylene glycol polyester.Other example of SRA comprises: part-and all-end capped oligomer ester of negatively charged ion of the U.S. 4,721,580 that is issued to the 26 days January in 1988 of Gosselink; Be issued to the nonionic end-blocking block polyester oligopolymer of the U.S. 4702857 of 27 days October in 1987 bulletin of Gosselink; And Maldonado, the US4 that announce people's such as Gosselink 31 days October in 1989,877,896 negatively charged ion (especially sulfo group aroyl) end-blocking terephthalate class.SRAs also comprises: the simple copolymer block of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyoxyethylene or polyoxytrimethylene terephthalate, and referring to US3,959,230 (Hays, on May 25th, 1976) and US3,893,929 (Basadur, on July 8th, 1975); Derivatived cellulose is as the hydroxy ethers cellulose polymer compound that is purchased from Dow as METHOCEL; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose, referring to US4,000,093 (on December 28th, 1976, people such as Nicol); And methyl cellulose ether, it has about 1.6 to about 2.3 average substitution degree for each dehydrated glucose unit (methyl) and about 80 soltion viscosities to about 120 centipoises (measuring down at 20 ℃ as 2% aqueous solution).This type of material can be used as METOLOSE SM100 and METOLOSE SM200 is purchased, and they are the trade(brand)names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK manufacturing.

Other classification of SRA is included in people's such as Violland US4, and 201,824 and people's such as Lagasse US4,240,918; People's such as Tung US4, those that describe in 525,524 and people's such as Violland US4,201,824.

Press down foam system

The detergent composition here especially when coming formulating of recipe for the composition that is used for machine-washing, can comprise and press down foam system, and the latter to be being equivalent to the 0.01-15 weight % of composition or component, preferred 0.02-10 weight %, and most preferably the amount of 0.05-3 weight % exists.The suitable foam system that presses down used herein can comprise any basically known defoaming compounds, comprising for example polysiloxane defoaming compounds and 2-alkyl alcanol defoaming compounds or soap.Defoaming compounds is meant that here the solution that for example is used to suppress by detergent composition produces, and especially is stirred foaming or any compound that foams or the mixture of these compounds that produces down at this solution.

Particularly preferred defoaming compounds used herein is the siloxanes defoaming compounds that is defined as comprising any defoaming compounds of silicone components here.This type of siloxanes defoaming compounds also typically comprises the silica component.Here use with term " siloxanes " commonly used in industry and comprise the many relative higher molecular weight polymer that contains siloxane unit and various types of alkyl.Preferred siloxanes defoaming compounds is a siloxanes, has the unitary polydimethylsiloxane of trimethyl silyl end-blocking especially.Other suitable defoaming compounds comprises monocarboxylic acid lipid acid and its soluble salt, as described in US patent 2,954,347 (September 27 nineteen sixty, Wayne St.John).Other suitable defoaming compounds comprises, high-molecular-weight aliphatic ester (for example fatty acid triglyceride) for example, the fatty acid ester of monohydroxy-alcohol, aliphatics C ₁₈-C ₄₀Ketone (for example stearone) N-alkylation aminotriazine; as three-to six-alkyl melamine or two-to four-alkyl diamine chlorotriazine; they as cyanuryl chloride and 2 or the product of the uncle of containing 1-24 carbon atom of 3mol or secondary amine, propylene oxide form two stearic amides and single stearyl-two basic metal (for example sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.

The preferred foam system that presses down comprises that content is equivalent to the 50-99wt% of siloxanes defoaming compounds, and the defoaming compounds of preferred 75-95wt% preferably includes the polydimethylsiloxane of fusion; Content is equivalent to the 1-50wt% of siloxanes/silica defoaming compounds, the silica of preferred 5-25wt%, wherein silica/siloxanes defoaming compounds is to be equivalent to the 5-50wt% of compound dispersing agent, the amount of preferred 10-40wt% is introduced, comprise that most preferably content is the siloxane glycol rake multipolymer of 0.5-10%, its ratio with the polyalkylene oxide base content of 72-78% and oxyethane and propylene oxide is 1: 0.9 to 1: 1.1, as the DCO544 that is purchased from DOW Corning, and comprise the inert support fluid compound, comprise that most preferably content is 5-80wt%, preferred 10-70wt% has a 5-50, the C of the ethoxylation degree of preferred 8-15 ₁₆-C ₁₈Ethoxylated alcohol.

Granulous very preferably presses down foam system and is described among the EP-A-0210731.EP-A-0210721 discloses other preferred granulous and has pressed down foam system.

Other foam that presses down very preferably is the mixture that comprises dimethione or siloxanes (as polydimethylsiloxane), aluminosilicate and multi-carboxy acid copolymer (as laic acid and acrylic acid multipolymer).

Other optional member that is fit to be included in the composition of the present invention comprises colorant and filling salt, and wherein sodium sulfate is preferred filling salt.

Composition very preferably contains the organic acid of the 2-10 weight % that has an appointment, optimization citric acid.In addition, preferably combine, also have the neutralizing agent of a small amount of (for example being lower than about 20wt%) with carbonate facics, buffer reagent, phase modifier, hydrotropic agent, enzyme stabilizers, polyprotonic acid, foaming regulator, opalizer, antioxidant, sterilant and dyestuff are as the US patent of announcing in 25 days Augusts in 1981 that are issued to people such as Barrat 4, described in 285,841 (it is for reference to be incorporated herein this paper) those.

Detergent composition can comprise the chlorine type SYNTHETIC OPTICAL WHITNER as annexing ingredient.Yet because detergent composition of the present invention is a solid, most liquid chlorine type SYNTHETIC OPTICAL WHITNER is not suitable for these detergent composition, and only granular or Powdered chlorine type SYNTHETIC OPTICAL WHITNER is suitable for.In addition, chlorine type SYNTHETIC OPTICAL WHITNER can be joined in the detergent composition by the user when washing process begins or in washing process.Chlorine type SYNTHETIC OPTICAL WHITNER can make and form hypochlorous acid (salt) material in aqueous solution.The hypochlorite ion is by chemical formula OCl ^-Expression.Those SYNTHETIC OPTICAL WHITNER that obtain hypochlorous acid (salt) material in aqueous solution comprise basic metal and alkaline-earth metal hypochlorite, hypochlorite affixture, chloramines, chlorimide, chloro-acid amide class and chlorine imide.Concrete example comprises clorox, potassium hypochlorite, generation Losantin, generation magnesium hypochlorite, chlorating Trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, Surchlor GR 60, Surchlor GR 60 dihydrate, trichlorocyanuric acid, 1,3 dichloro 5,5 dimethyl hydantoin, the N-Clofenamide, chloramine-T, dichloramine-T, chloramine B and dichloramine B.The preferred SYNTHETIC OPTICAL WHITNER that is used for the present composition is a clorox, potassium hypochlorite, or their mixture.Preferred chlorine type SYNTHETIC OPTICAL WHITNER is Triclosan (trade(brand)name).

Most of above-mentioned hypochlorite generation type SYNTHETIC OPTICAL WHITNER can be with solid or conc forms purchase and soluble in water in preparation of compositions process of the present invention.In the above-mentioned substance some can be purchased with aqueous solution form.

The machine washing method

The machine washing method typically is included in the washing machine with dissolving therein or having disperseed contain the dress material that water lotion processing have dirt of the machine washing of the present invention of significant quantity with detergent composition at this.The detergent composition of significant quantity is meant at 5-65 and rises dissolving in the washing lotion of volume or disperseed the product of 10g-300g that this is typical products dosage and a washing lotion volume commonly used in the machine washing method of routine.Preferred washing machine can be so-called low filled-type machine.

Aspect preferred use, stiff dough cleans compositions formulated or hand washing so that it is suitable for.Other preferred aspect, detergent composition is pre-treatment or soaks composition, being used for pre-treatment or immersion has dirt and contaminated fabric.

Embodiment

The following examples provide just to illustrational purpose, do not think the scope that limits claims by any way.

The abbreviation of Shi Yonging in an embodiment

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

LAS: straight chain C _11-13Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

CxyAS: C ₁X-C ₁The y sodium alkyl sulfate

Branching (Branched) AS: be described in the branched-alkyl sulfuric acid among the WO99/19454

Sodium

C ₄₆SAS: C ₁₄-C ₁₆Secondary (2,3) sodium alkyl sulfate

CxyEzS: condensation the C of z mol oxyethane ₁X-C ₁The y alkyl sulfide

Acid sodium

CxyEz: condensation the C of average z mol oxyethane ₁X-C ₁Y master

Want straight chain primary alcohol

QAS???????????????：R ².N+(CH3)2(C2H4OH)，R ²＝C ₁₂-C ₁₄

QAS1??????????????：R ².N+(CH3)2(C2H4OH)，R ²＝C ₈-C ₁₁

APA: C ₈-C ₁₀The amidopropyl dimethylamine

Soap: from 80/20 mixture of butter and coco-nut oil fatty acid

Deutero-straight-chain alkyl 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 ₁₄Cat head is held back lipid acid entirely

STPP: anhydrous sodium tripolyphosphate

TSPP: tetrasodium pyrophosphate

Zeolite A: the general formula of primary particle size in the 0.1-10 micrometer range is

Na ₁₂(AlO ₂SiO ₂) 1227H ₂The hydrated aluminum silicate of O

(expressing with weight) based on anhydrous form

NaSKS-6: formula d-Na ₂Si ₂O ₅The crystalline layered silicate citric acid of expression: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: anhydrous sodium carbonate: granularity 200 μ m are to 900 μ m supercarbonates: anhydrous sodium bicarbonate, size-grade distribution 400 μ m and

Silicate between the 1200 μ m: unbodied water glass (SiO ₂: Na ₂O=2.0: 1) vitriol: anhydrous sodium sulphate sal epsom: anhydrous magnesium sulfate Citrate trianion: 86.4% active citrate trisodium dihydrate, granularity

Be distributed as 425-850 μ mMA/AA: 1: 4 toxilic acid/acrylic acid multipolymer, mean molecule

Measure about 70,000MA/AA (1): 4: 6 toxilic acid/acrylic acid multipolymers, mean molecule

Measure about 10,000AA: the polyacrylic acid sodium polymer CMC of molecular-weight average 4,500: the plain ether of sodium carboxyme-thylcellulose fibre: the polymerization degree 650, available from Shin Etsu Chemicals

Methyl cellulose ether proteolytic enzyme: proteolytic ferment, have the organized enzyme of 3.3wt%, by

NOVO Industries A/S is with trade(brand)name

Savinase sells proteolytic enzyme I: proteolytic ferment, have the organized enzyme of 4wt%, as

Described in the WO95/10591, by Genencor Int.

Inc sells.Alcalase: proteolytic ferment, have the organized enzyme of 5.3wt%, by

NOVO Industries A/S sells cellulase: cellulolytic enzyme has the activity of 0.23wt%

Enzyme, by NOVO Industries A/S with trade(brand)name

Carezyme sells amylase: amylolytic enzyme, have the organized enzyme of 1.6wt%, by

NOVO Industries A/S is with trade(brand)name

Termamyl 120T sells lipase: lipolytic enzyme, have the organized enzyme of 2.0wt%, by

NOVO Industries A/S is with trade(brand)name

Lipolase sells lipase (1): lipolytic enzyme, have the organized enzyme of 2.0wt%, by

NOVO Industries A/S is with trade(brand)name

Lipolase Ultra sells Endolase: endoglucanase, have the organized enzyme of 1.5wt%,

Sell PB4 by NOVO Industries A/S: have nominal general formula NaBO ₂3H ₂OH ₂O ₂Peroxyboric acid

Sodium tetrahydrate PB1: have nominal general formula NaBO ₂H ₂O ₂Anhydrous peroxyboric acid

Sodium SYNTHETIC OPTICAL WHITNER percarbonate: have nominal general formula 2Na ₂CO ₃3H ₂O ₂SPC-D NOBS: the nonanoly acyloxy benzene sulfonate NAC-OBS of sodium-salt form: (6-nonanoyl amido caproyl) oxygen base benzene sulfonate TAED: tetra acetyl ethylene diamine DTPA: diethylene triaminepentaacetic acid(DTPA) DTPMP: diethylenetriamine five (methylene phosphonic acid salt), by

Monsanto sells EDDS: quadrol-N, N '-disuccinic acid, (S, S) isomer with trade(brand)name Dequest 2060

Sodium salt.Photoactivation SYNTHETIC OPTICAL WHITNER: be encapsulated in SYNTHETIC OPTICAL WHITNER (1) the dextrin soluble polymer

Sulfonation zinc phthalocyanine phthalocyanine photoactivation SYNTHETIC OPTICAL WHITNER: be encapsulated in SYNTHETIC OPTICAL WHITNER (2) the dextrin soluble polymer

Sulphonation aluminum phthalocyanine brightener 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium salt brightener 2: 4,4 '-two (4-anilino-6-morpholino-1,3,5-

Triazine-2-yl) Stilbene-2:2 '-disulfonic acid disodium amino)

Salt HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid PEGx: polyoxyethylene glycol, molecular weight is x (typical case 4,000) PEO: polyethylene oxide, molecular-weight average 50,000TEPAE: ethylidene five amine ethoxylate PVI: polyvinyl imidazol, molecular-weight average 20,000PVP: polyvinylpyrrolidonepolymers polymers, molecular-weight average

60,000PVNO: polyvinylpyridine N-oxide polymer, average mark

Son amount 50,000PVPVI: the copolymerization of Polyvinylpyrolidone (PVP) and vinyl imidazole

Thing (molecular-weight average 20,000) QEA: two ((C ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-

(CH ₃) two ((C ₂H ₅O)-(C ₂H ₄O)) _n, n=wherein

20-30SRP1: the end capped polyester SRP2 of negatively charged ion: diethoxyization is gathered (terephthalic acid 1,2-propylene glycol

Ester) lack block polymer PEI: molecular-weight average 1800 and average degree of ethoxylation are 7

The poly-ethylidene Asia of an individual ethyleneoxy group residue/nitrogen

Oxyalkylene amine antifoams: siloxanes-oxyalkylene copolymers is arranged as dispersion agent

The dimethione Foam Control, Foam Control

With the ratio of dispersion agent be 10: 1 to 100: 1 opalizers: water base single vinylbenzene latex mixture, by BASF

Aktiengesellschaft trade(brand)name Lytron

621 sell wax: paraffin HMEO: hexamethylene-diamine four (oxyethane) 24

Embodiment 1: the preparation of effervescent granules

Reach a collection of citric acid and the yellow soda ash of 2kg that prepared the composition with 64wt% citric acid/36wt% yellow soda ash in 5 minutes by mix following composition under the speed setting value of 9 (the highest) shelves in Hosokawa Mikron ' Nautamix ' DBY-5R rotary screw mixing machine: the 1280g granularity is 200-400 μ m, be purchased (particulate grade: Citric Acid, usp, Anhydrous Powder 16/40) from Citrique Belge, with use Hosokawa Mikron Air-Classifying Mill (ACM15) to be milled to the anhydrous sodium carbonate (light soda ash is purchased from Brunner Mond) of 5 μ m median particle in advance.Mixture is compacting in Bepex compression set (roller diameter 200mm, width 50mm) then: the powder of premix is toppled in the hopper of compressing roller top.Hopper has the vertical screw that powder is delivered to roller.By regulating feed screw speed, these two rollers are packed together applied force (being known as force of compression) are adjusted to 80kN.The material of compacting is collected with fracture and not damaged beading form, is grinding in Hosokawa Bepex F200 FlakeBreaker under 1 grade the speed setting value then.This equipment is made up of the roll cover (RollingCage) that 1000 μ m screen clothes are housed.

The material of being produced by Flake breaker is placed on the vibration screening device that the sieve size is 355 μ m (Retsch, model AST200) then.The material that rests on the screen cloth is that conceivable median particle is the finished particle material (the effervescent granules A in following table) of 620 μ m, and fine powder is told to carry out recirculation.

Use provides each component of consumption in table 1 following mixture repeats this process (respectively estimate one's own ability and provide with the wt% based on effervescent granules), produces other effervescent granules material B-E.

Table 1

Effervescent granules	???B	???C	???D	???E
Effervescent granules	???B	???C	???D	???E	Citric acid	???40	???10	???55	???-
Oxysuccinic acid	???20	???30	???-	???35	Citric acid	???40	???10	???55	???-
Oxysuccinic acid	???20	???30	???-	???35	Tartrate	???-	???-	???-	???15
Yellow soda ash	???25	???70	???-	???40	Tartrate	???-	???-	???-	???15
Yellow soda ash	???25	???70	???-	???40	Sodium bicarbonate	???15	???-	???45	???10

These effervescent granules material are introduced in the detergent composition then, described in embodiment 2-6.

Embodiment 2

By form aqueous slurries, the spraying drying pellet that forms in spray-drying tower that particulate material produces then with the composition that provides among the embodiment 3 below and then with 5wt%TAED as the additional detergent composition, the 1wt% suds suppressor, 7.5wt% yellow soda ash and 2.5wt% sodium sulfate mix in the Eirich mixing tank.The aqueous solution of PEG-4000 (35wt% solid) is sprayed to mixture, allows its granulation 5 minutes.The product that is obtained is through sieving the particle that is collected between 300 and 1200 microns.10wt% SPC-D, 0.5wt% spices and 1wt% enzyme (mixture that comprises the granula of starch-containing enzyme, cellulase, proteolytic enzyme and lipase) are done then and are added and mixing.The mixture of being produced has 59% eRH.Then the effervescent granules material of any of 10wt% formulation H-E or these mixture is joined in this mixture in the Nautamix cone mixer, clamp-on subsequently in the washing composition carton box.

Embodiment 3

On the Countercurrent Spray Dryer of 300 ℃ inlet air temperatures, produce spray-dired pellet.Agglomerated thing and other adulterant (referring to table 2) mix in the intermittent type cylindrical blender with the spraying drying pellet.Detergent base has 38% eRH.Add effervescent granules A then, then the product branch is installed in the washing composition carton box.Other example of detergent composition of the present invention can prepare by any mixture that uses effervescent granules material B-E or particulate material A-E.

Table 2 Spraying drying pellet 50%The raw material of spray-drying pellet composition accounts for wt%LAS 10.4 tallow alkyl sulfate 1.6EDDS 0.4 brightener 15 0.1 magnesium sulfate 0.7Sokalan CP5 2.5HEDP 0.3 sodium carbonate 8.4 sodium sulphate 23.5 Wessalith CSs 40.0 other (water, spices etc.) of total amount12.07

100.0 Anion surfactant agglomerated thing 10%The raw material of agglomerated thing composition accounts for the wt%C of total amount ₄₅Alkyl ethoxylate sulfate (EO0.6) 29.1 zeolite A 45.0 yellow soda ash, 15.1 polyoxyethylene glycol (MW4000) 1.3 other (water, spices etc.) 9.5

100.0 Percarbonate 10% TAED 5% Effervescent granules 10% Accessory constituent 15%

Embodiment 4

Repeat embodiment 3, just the spraying drying pellet carries out drying under 350 ℃ higher tower inlet temperature, removes some combination water.In this case, detergent base eRH is 24%.

Embodiment 5

The detergent base of production example 3 again in the Nautamix cone mixer, and add 5% overdried zeolite to it.(overdried zeolite is zeolite A, has crystal water over half to remove by the additional drying operation).The detergent base that is obtained has 12% eRH.Then 10% effervescent granules B is joined in this base-material, the product branch is installed in the washing composition carton box.Other embodiment can any mixture any or particulate material A-E prepares among the effervescent granules material B-E by using.

Embodiment 6

The spray-dried granules material of the prescription that will describe in following table 3A and 3B, agglomerated thing and washing assistant agglomerated thing at first join Lodige KM with 660kg ^TMIn 600 mixing tanks, the cylinder rotating speed is that 100RPM and cutter speed are 3600RPM.The mixture that is obtained is joined in the fluidized bed dryer.Randomly, in first stage of the three phases in fluidized bed dryer the aqueous solution (30wt% solid) of PEG-4000 is sprayed on the mixture.The product that is obtained is through sieving the particle that is collected between about 600 to about 1100 μ.Fine powder material is recycled to Lodige KM, and the macrobead material is ground and be recycled to fluidized bed dryer.Add the dried interpolation detergent component in the following table then and carry out spray agent (spray-on).Detergent base eRH typical case is about 14%.

Table 3A

Following composition is according to of the present invention.

	A	B	C	D	E	F	G	H	I
	A	B	C	D	E	F	G	H	I	Spray-dired pellet
LAS	10.0	10.0	15.0	5.0	8.0	10.0	-	-	-	Spray-dired pellet
LAS	10.0	10.0	15.0	5.0	8.0	10.0	-	-	-	TAS	-	1.0	-				-	-	-
MBAS		-		5.0	8.0					TAS	-	1.0	-				-	-	-
MBAS		-		5.0	8.0					C ₄₅AS	-	-	1.0		1.0	2.0	-	-	-
C ₄₅AE ₃S	-	-		1.0			-	-	-	C ₄₅AS	-	-	1.0		1.0	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			-	-	-	QAS			1.0	1.0			-	-	-
DTPA, HEDP and/or EDDS	0.3	0.3	0.5	0.3			-	-	-	MgSO4	0.5	0.5	0.1	-			-	-	-
Trisodium Citrate	-	-	-	3.0	5.0		-	-	-	MgSO4	0.5	0.5	0.1	-			-	-	-
Trisodium Citrate	-	-	-	3.0	5.0		-	-	-	Yellow soda ash	10.0	7.0	15.0		10.0	10.0	-	-	-
Sodium sulfate	5.0	5.0	-	-	5.0	3.0	-	-	-	Yellow soda ash	10.0	7.0	15.0		10.0	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	-	-	-	-	-	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	-	-	-	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	-	-	-	-	PEG4000	-	2.0	-	1.0	-	1.0	-	-	-
QEA	1.0	-	-	-	1.0	-	-	-	-	Brightener	0.05	0.05	0.05	-	0.05	-	-	-	-
Silicone oil	0.01	0.01	0.01	-	-	0.01	-	-	-	Brightener	0.05	0.05	0.05	-	0.05	-	-	-	-
Silicone oil	0.01	0.01	0.01	-	-	0.01	-	-	-
Agglomerated thing
Agglomerated thing										LAS			-	-	-	-	2.0	2.0	-
MBAS			-	-	-	-	-	?-	1.0	LAS			-	-	-	-	2.0	2.0	-
MBAS			-	-	-	-	-	?-	1.0	C ₄₅AS			-	-	-	-	2.0	?-	-
AE ₃			-	-	-	-	-	1.0	0.5	C ₄₅AS			-	-	-	-	2.0	?-	-
AE ₃			-	-	-	-	-	1.0	0.5	Carbonate			-	-	-	1.0	1.0	1.0	-

Table 3A (continuing)

Trisodium Citrate			-	-	-	-	-	-	5.0
Trisodium Citrate			-	-	-	-	-	-	5.0	CFAA					-	-	-	-	-
Citric acid			-	-	-	4.0	-	1.0	1.0	CFAA					-	-	-	-	-
Citric acid			-	-	-	4.0	-	1.0	1.0	QEA			-	-	-	2.0	2.0	1.0	-
SRP			-	-	-	1.0	1.0	0.2	-	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			-	-	-	-	-	-	-	Zeolite A			-	-	-	15.0	26.0	15.0	16.0
Water glass			-	-	-	-	-	-	-	PEG	-	-	-	-	-	-	4.0	-	-
										PEG	-	-	-	-	-	-	4.0	-	-
										The washing assistant agglomerated thing
SKS-6	6.0	-	-	-	6.0	3.0	-	7.0	10.0	The washing assistant agglomerated thing
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 and add granular component										LAS	4.0	5.0	-	-	5.0	3.0	-	10.0	12.0
Do and add granular component										Effervescent granules A	8.0	10.0			12.0			2.0	4.0
Effervescent granules B			10.0							Effervescent granules A	8.0	10.0			12.0			2.0	4.0
Effervescent granules B			10.0							Effervescent granules C				4.0
Effervescent granules D						8.0				Effervescent granules C				4.0
Effervescent granules D						8.0				Effervescent granules E							2.0
QEA	-	?-	?-	0.2	0.5	-	-	-	-	Effervescent granules E							2.0
QEA	-	?-	?-	0.2	0.5	-	-	-	-	NACAOBS	3.0	-	-	1.5	-	-	-	2.5	-
NOBS	-	3.0	3.0	-	-	-	-	-	5.0	NACAOBS	3.0	-	-	1.5	-	-	-	2.5	-
NOBS	-	3.0	3.0	-	-	-	-	-	5.0	TAED	2.5	-	-	1.5	2.5	6.5	-	1.5	-
MBAS	-	-	-	8.0	-	-	8.0	-	4.0	TAED	2.5	-	-	1.5	2.5	6.5	-	1.5	-
MBAS	-	-	-	8.0	-	-	8.0	-	4.0	LAS (thin slice)	10.0	10.0	-	-	-	-	-	8.0	-
										LAS (thin slice)	10.0	10.0	-	-	-	-	-	8.0	-
										Spray agent
Brightener	0.2	0.2	0.3	0.1	0.2	0.1	-	0.6	-	Spray agent
Brightener	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	-	Dyestuff	-	-	-	0.3	0.05	0.1	-	-	-
AE7	-	-	-	-	-	0.5	-	0.7	-	Spices	-	-	-	0.8	-	0.5	-	0.5	-

Table 3A (continuing)


										Dried addition material
Citrate trianion	-	-	20.0	4.0	-	5.0	15.0	-	5.0	Dried addition material
Citrate trianion	-	-	20.0	4.0	-	5.0	15.0	-	5.0	Percarbonate	15.0	3.0	6.0	10.0	-	-	-	18.0	5.0
Perborate	-	-	-	-	6.0	18.0	-	-	-	Percarbonate	15.0	3.0	6.0	10.0	-	-	-	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	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 (sealing)	0.6	0.5	0.5	-	0.3	0.5	0.2	0.1	0.6	Carbonate	0.0	10.0	-	-	-	5.0	8.0	10.0	5.0
Spices (sealing)	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	-	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	-	-	-	6.0	6.0	-	-	-	5.0
Painted carbonate (blueness, green)	0.5	0.5	1.0	2.0	-	0.5	0.5	0.5	1.0	Citric acid	-	-	-	6.0	6.0	-	-	-	5.0
Painted carbonate (blueness, green)	0.5	0.5	1.0	2.0	-	0.5	0.5	0.5	1.0	SKS-6	-	-	-	4.0	-	-	-	6.0	-
Filler adds to 100%										SKS-6	-	-	-	4.0	-	-	-	6.0	-

Table 3B

Following composition is according to of the present invention.

	A	B	C	D	E	F	G	H	I
	A	B	C	D	E	F	G	H	I	The spraying drying pellet
LAS	10.0	10.0	16.0	5.0	5.0	10.0	-	-	-	The spraying drying pellet
LAS	10.0	10.0	16.0	5.0	5.0	10.0	-	-	-	TAS	-	1.0	-				-	-	-
MBAS	-	-	-	5.0	5.0		-	-	-	TAS	-	1.0	-				-	-	-
MBAS	-	-	-	5.0	5.0		-	-	-	C ₄₅AS	-	-	1.0		2.0	2.0	-	-	-
C ₄₅AE ₃S	-	-	-	1.0			-	-	-	C ₄₅AS	-	-	1.0		2.0	2.0	-	-	-
C ₄₅AE ₃S	-	-	-	1.0			-	-	-	QAS	-	-	1.0	1.0			-	-	-

Table 3B (continuing)

DTPA, HEDP and/or EDDS	0.3	?0.3	0.3	0.3			-	-	-
DTPA, HEDP and/or EDDS	0.3	?0.3	0.3	0.3			-	-	-	MgSO4	0.5	0.4	0.1	-			-	-	-
Trisodium Citrate	1.0	12.0	17.0	3.0	5.0		-	-	-	MgSO4	0.5	0.4	0.1	-			-	-	-
Trisodium Citrate	1.0	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	-	-	-	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	-	-	-	-	-	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	-	-	-	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	-	-	-	-	PEG4000	-	2.0	-	1.0		1.0	-	-	-
QEA	1.0	-	-	-	1.0	-	-	-	-	Brightener	0.05	0.05	0.05	-	0.05	-	-	-	-
Silicone oil	0.01	0.01	0.01	-	-	0.01		-		Brightener	0.05	0.05	0.05	-	0.05	-	-	-	-
Silicone oil	0.01	0.01	0.01	-	-	0.01		-
Agglomerated thing
Agglomerated thing										LAS	-	-	-	-	-	-	2.0	?2.0	-
MBAS	-	-	-	-	-	-	-	-	1.0	LAS	-	-	-	-	-	-	2.0	?2.0	-
MBAS	-	-	-	-	-	-	-	-	1.0	C ₄₅AS	-	-	-	-	-	-	2.0	-	-
AE ₃	-	-	-	-	-	-	-	1.0	?0.5	C ₄₅AS	-	-	-	-	-	-	2.0	-	-
AE ₃	-	-	-	-	-	-	-	1.0	?0.5	Carbonate	-	-	-	-	4.0	1.0	1.0	1.0	-
Trisodium Citrate	-	-	-	-	-	-	-	-	5.0	Carbonate	-	-	-	-	4.0	1.0	1.0	1.0	-
Trisodium Citrate	-	-	-	-	-	-	-	-	5.0	CFAA	-	-	-		-	-	-	-	-
Citric acid	-	-	-	-	-	4.0	-	1.0	1.0	CFAA	-	-	-		-	-	-	-	-
Citric acid	-	-	-	-	-	4.0	-	1.0	1.0	QEA	-	-	-	-	-	?2.0	2.0	1.0	-
SRP	-	-	-	-	-	1.0	1.0	0.2	-	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	-	-	-	-	-	-	-	-	-	Zeolite A	-	-	-	-	-	15.0	26.0	15.0	16.0
Water glass	-	-	-	-	-	-	-	-	-	PEG	-	-	-	-	-	-	4.0	-	-
										PEG	-	-	-	-	-	-	4.0	-	-

Table 3B (continuing)

The washing assistant agglomerated thing
The washing assistant agglomerated thing										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	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 and add granular component
Do and add granular component										Effervescent granules A	8.0		4.0	4.0	-		2.0	2.0	4.0
Effervescent granules B		10.0								Effervescent granules A	8.0		4.0	4.0	-		2.0	2.0	4.0
Effervescent granules B		10.0								Effervescent granules D						8.0
QEA	-	-	-	0.2	0.5	-	-	-	-	Effervescent granules D						8.0
QEA	-	-	-	0.2	0.5	-	-	-	-	NACAOBS	3.0	-	-	1.5	-	-	-	2.5	-
NOBS	-	3.0	3.0	-	-	-	-	-	5.0	NACAOBS	3.0	-	-	1.5	-	-	-	2.5	-
NOBS	-	3.0	3.0	-	-	-	-	-	5.0	TAED	2.5	-	-	1.5	2.5	6.5	-	1.5	-
MBAS	-	-	-	8.0	-	-	8.0	-	4.0	TAED	2.5	-	-	1.5	2.5	6.5	-	1.5	-
MBAS	-	-	-	8.0	-	-	8.0	-	4.0	LAS (thin slice)	-	-	-	-	-	-	-	8.0	-
										LAS (thin slice)	-	-	-	-	-	-	-	8.0	-
										Spray agent
Brightener	0.2	0.2	0.3	0.1	0.2	0.1	-	0.6	-	Spray agent
Brightener	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	-	Dyestuff	-	-	-	0.3	0.05	0.1	-	-	-
AE7	-	-	-	-	-	0.5	-	0.7	-	Spices	-	-	-	0.8	-	0.5	-	0.5	-
										Spices	-	-	-	0.8	-	0.5	-	0.5	-
										Dried addition material
Citrate trianion	4.0	-	3.0	4.0	-	5.0	15.0	-	5.0	Dried addition material
Citrate trianion	4.0	-	3.0	4.0	-	5.0	15.0	-	5.0	Percarbonate	15.0	3.0	6.0	10.0	-	-	-	18.0	5.0
Perborate	-	-	-	-	6.0	18.0	-	-	-	Percarbonate	15.0	3.0	6.0	10.0	-	-	-	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	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	-	-	-	-	-	5.0	8.0	10.0	5.0

Table 3B (continuing)

Spices (sealing)	0.6	0.5	0.5	-	0.3	0.5	0.2	0.1	0.6
Spices (sealing)	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	-	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	-	-	-	6.0	6.0	-	-	-	5.0
Painted carbonate (blue, green)	0.5	0.5	-	2.0	-	0.5	0.5	0.5	1.0	Citric acid	-	-	-	6.0	6.0	-	-	-	5.0
Painted carbonate (blue, green)	0.5	0.5	-	2.0	-	0.5	0.5	0.5	1.0	SKS-6	-	-	-	4.0	-	-	-	6.0	-
Filler adds to 100%										SKS-6	-	-	-	4.0	-	-	-	6.0	-

Claims

1. one kind comprises and the reactive behavior particulate material of two kinds of granular reactants that react is understood in reaction when promoting fluid contact, and wherein the ratio of first reactant and the granule number of second reactant (i.e. the ratio of first reactant and the numbers of particles of second reactant) is at least 50: 1.

2. according to the reactive behavior particle of claim 1, wherein second reactant is at least 2: 1 with the ratio of the median particle of first reactant.

3. according to the reactive behavior particle of claim 1 or claim 2, wherein reaction promotes fluid to comprise the water of gas phase or liquid phase.

4. according to the reactive behavior particle in any aforementioned claim, wherein particle is that separately at least a of effervescent granules and first and second kinds of reactants is respectively alkali source and acid source.

5. according to the reactive behavior particle of any aforementioned claim, wherein the ratio of first reactant and the granule number of second reactant (i.e. the ratio of first kind of reactant and the numbers of particles of second kind of reactant) is at least 500: 1.

6. according to the reactive behavior particle of any aforementioned claim, wherein second reactant is at least 8: 1 with the ratio of the median particle of first reactant.

7. according to the reactive behavior particle of any aforementioned claim, wherein the fabric width of the granularity of each reactant is to be not more than 2.

8. according to the reactive behavior particle of any aforementioned claim, wherein the median particle of second reactant is preferably greater than 100 μ m.

9. according to the reactive behavior particle of any aforementioned claim, wherein the median particle of first reactant preferably is lower than 50 μ m.

10. according to the reactive behavior particle in any aforementioned claim, it is that effervescent granules and first kind of reactant comprise that alkali source and second kind of reactant comprise acid source.

11. according to the reactive behavior particle of any aforementioned claim, wherein first reactant exists with the amount that is equivalent to particulate 15-70wt%.

12. according to the reactive behavior particle of any aforementioned claim, wherein second reactant exists with the amount that is equivalent to particulate 35-75wt%.

13. according to the reactive behavior particle of any aforementioned claim, a kind of citric acid that comprises in the middle of first and second reactants wherein, and the in first and second reactants the two comprise the carbonate alkali source that is selected from yellow soda ash and sodium bicarbonate or their mixture.

14. according to the reactive behavior particle of any aforementioned claim, it contains the total moisture content of the 0.5wt% that is lower than effervescent granules.

15. a detergent composition, it contains the reactive behavior particle and the detergent base as effervescent granules of with good grounds any aforementioned claim.

16. according to the detergent composition of claim 15, wherein detergent base has and is not more than 30% eRH.

17. a method for compositions for preparing according to claim 15 or claim 16, wherein detergent base comprises the detergent base component, and this component at first by spray drying method for preparation, is mixed with the reactive behavior particle then.

18. one kind prepares according to any one reactive behavior particulate method among the claim 1-17, wherein first and second reactants are made particle by the coalescent method of pressure after mixing.

19. according to the method for claim 18, wherein the pressure agglomeration step is to carry out being lower than under 35% the relative humidity.

20. according to the method for claim 19, wherein the mixing of first and second reactants is also carried out being lower than under 35% the relative humidity.

21. a method of washing stain surfaces, the method for especially machine-washing, it comprises that the detergent composition dissolving that will comprise effervescent granules forms the aqueous solution and also the stain surfaces of this solution with the needs washing contacted.