CN1037453C - Particulate detergent compositions - Google Patents

Abstract

Particulate compositions are provided incorporating from about 10 % to about 95 % by weight of a crystalline layered silicate material of the formula Na MSixO2x+1 <yH>2<O>, where M is sodium or hydrogen, x is a number from about 1.9 to 4 and y is a number from 0 to about 20 and from about 5 % to about 90 % by weight of a solid water soluble ionisable material selected from organic acids, organic and inorganic acid salts and mixture thereof, said solid water soluble ionisable material naming a mean particle size not greater than about 100 micrometers, said particulate compositions being substantially free of unbound moisture. The particulates can optionally contain up to about 50 % by weight of a surfactant and/or up to about 50 % by weight of other detergent ingredients. Fully formulated detergent compositions incorporating the particulate compositions are also disclosed.

Description

Granular detergent composition and preparation method thereof

The present invention relates to a kind of particulate composition that is mixed with the layered crystal water glass, be suitable for particularly not getting rid of as fabric washing product as a kind of solid detergent or detergent component.

The detergent composition that is mixed with the layered crystal water glass is understood by people in disclosed document, for example, and DE-A-3742043 and EP-A-0337219.The water glass that these documents are told our layered crystal form has shown the rigid sequestering power of superior mineral with respect to the amorphous silicate of correspondence, is favourable as the detergent builders material.

Having disclosed the dish washing agent be made up of crystal water glass and proton donor bonded mixture among the EP-A-0416366 is that 5% o'clock pH value of aqueous solution is less than 10 at detergent content.The type of proton donor has many kinds, comprises mineral acid, organic acid and their water-soluble salt.Yet the purpose of EP-A-0416366 is to reduce the pH value of washings, makes its hormesis minimum to skin and eyes.

The keying action of special washing auxiliary detergent that this application has finds to comprise lamina sodium silicate is very effective to the quantity that reduces inorganic hardness ions in the fabric washing process.This makes the people can prepare obtainable product with super cleaning function, or allows to use less detergent builder to prepare the product with identical cleaning function with the buffering material." concentrate " development of granular detergent product from the nearest high-density and the what is called of small volume, the latter's discovery has special meaning.

For physical appearance and the feature performance benefit of protecting crystalline layered silicate, should not be exposed to it before it is dissolved in washings can the dissolved medium.Will prevent from like this they are added to spraying drying with in the water slurry that forms detergent particles, need add them in the residue of granular solids detergent composition of thorough drying to usually.Yet this solid is highly brittle, and is difficult to mass disposal.

Another characteristics of layered crystal silicate are to dissolve slowlyer in aqueous medium than corresponding amorphous silicate.When the fabric washing machine washing was washed the circulation beginning automatically, this had caused the layered silicate particulate to stick on the fabric, produces the regional area of high pH value (＞12).Some fabric can be damaged in high pH value zone like this, for example wool and some dye for fabrics, particularly when detergent composition be by the adding of the diverting device in the rotary drum that is placed on the washing machine that fabric is housed washing machine in the time.

Though being surprised to find that, the applicant can not overcome above characteristics fully by the particle that forms crystalline layered silicate and water-soluble ionogenic solid material, to less than 10 o'clock, the problem of damage fabric above-mentioned and dye for fabrics also can alleviate in the pH value that does not reduce by 1% particle solution.In fact, according to the present invention, the distilled water solution of 1% (weight) of preferred grain fraction in the time of 20 ℃ the pH value near 11.8, promptly only a bit, and less than the pH value of the solution of under the same conditions 1% layered crystal silicate material than half pH unit's height.

These particles that contain layered crystal silicate and water-soluble ionizable solid material are moisture absorption under field conditions (factors).This has just caused containing the problem that these particulate components are easily lumpd in a humid environment.

Store under such condition, the performance of washing assistant can reduce.Yet the application finds that mixing binding agent in these particles can play mitigate effects to these two problems.Except that causing reducing caking and keep the washing auxiliary detergent performance, introduce this binding agent and also can cause reducing particulate fragility and strengthen operation by improving pneumatic transport efficient.

According to one aspect of the present invention, a kind of particulate composition is provided, be in 1% the distilled water solution during in weight ratio at 20 ℃, the pH value is at least 10, can be used as the laundry with solid detergent component or composition.Described particulate composition contains a kind of mixture closely:

A) the layered crystal silicate material of 10% to 95% (weight), its general formula is NaMSi _xO _2x+1YH2O, M is sodium or hydrogen here, and x is one from 1.9 to 4 a number, and y is one 0 to 20 a number;

B) the water-soluble ionizable solid material of 5% to 90% (weight), they are selected from organic acid, organic and inorganic acid salt and their mixture, and the particulate mean sizes of described water-soluble ionizable solid material is no more than 300 microns;

C) binding agent of 0% to 20% (weight);

D) negatively charged ion of 0% to 50% (weight), nonionic, both sexes or zwitterionics; With

E) above being different from of 0% to 50% (weight) a) to d) the washing composition auxiliary.

Especially, particulate composition is not contain non-binding (freedom) water substantially, just contains weight percent and is no more than 10% unbound water, and being no more than 5% can be better, preferably is no more than 3%.

Containing weight ratio by the preferred particulate composition of the present invention is that 75% to 80% particulate mean sizes is no more than 300 microns Na ₂Si ₂O ₅With weight percent be that 20% to 25% particle mean size is no more than 300 microns citric acid or sodium bicarbonate.

According to a further aspect in the invention, also disclose a kind of selection process of making the laundry with granular detergent composition, said composition contains:

A) general formula of 10% to 95% (weight) is NaMSi _xO _2x+1YH ₂The layered crystal silicate of O, M is sodium or hydrogen here, and x is one 1.9 to 4 a number, and y is one 0 to 20 a number;

B) the water-soluble ionogenic solid material that is selected from organic acid, organic or inorganic hydrochlorate and its mixture of 5% to 90% (weight), the particle mean size of described water-soluble ionizable solid material is no more than 300 microns;

C) by the tackiness agent of 0% to 20% (weight);

Processing step is:

I) component a), b), c) mix and form basic closely mixture uniformly together;

Ii) roll under the wide pressure, in roller press, mixture be pressed into chip material 10 to 30KN/cm,

Iii) chip material is ground into particle, makes its overall dimension be no more than 1200 microns.

The present invention includes by weight percent is the especially granular laundry of the solid detergent composition that the above-described grain fraction of the detergent builder of organic surface active agent, 25%-60% of 5%-30% and 10%-45% is formed.

Laundry of the present invention comprises two basal components with granular detergent composition, i.e. layered crystal silicate and water-soluble ionogenic solid material.According to purpose of the present invention, it should be water miscible, dissolves 10g at least in every 100g distilled water in the time of 20 ℃, forms solution.

The layered crystal silicate material has following general formula:

MaMSi _xO _2x+1YH ₂O M here is sodium or hydrogen, and x is 1.9 to 4 number, and y is 0 to 20 number.Layered crystal silicate has been described in EP-A-0164514, and its preparation method has been described in DE-A-3417649 and DE-A-3742043.According to purpose of the present invention, above the value of x in the general formula be 2,3 or 4, preferably 2, M is sodium preferably, y is 0, the preference of general formula has Na ₂Si ₂O ₅α-, β-, γ-and δ-form.These materials can obtain from Hoechst AG FRG, are respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6, preferably δ-Na ₂Si ₂O ₅, NaSKS-6.

These materials are made free-flowing solid, and granular size is from the 150-1000 micron, and tap density is 800g/l at least, preferably near 900g/l.Yet the crystal that makes is very crisp, is easy to be broken into the particulate that size is no more than 100 microns.

Particle shape of the present invention laundry is with in the washing composition, and layered crystal silicate accounts for the 10%-95% of particle weight, is preferably 50%-90%, and best is from 60% to 80%.

Water-soluble ionizable solid material is selected from organic acid, organic and inorganic acid salt and its mixture, fundamental requirement be these materials should contain at least one PKa value provide less than 9 acid functional groups in and the ability of the hydroxide ion that discharges of layered crystal silicate.

Be surprisingly found out that, be purpose of the present invention, ionizable material needn't be in solution the pH value less than 7, or exist with the hydrionic quantity that can provide the hydroxide ion that produces with the crystalline silicate dissolving to equate.In fact, in a material is stored,, can not eliminate damage although the neutralization reaction of soluble material can reduce the fabric damage degree.

The particle mean size of ionizable material also should be preferably less than 100 microns less than 300 microns, and this makes ionizable material and crystalline silicate be easy to be evenly distributed, and believes when particle is dissolved in the washings also can promote reducing of regional pH value.

Appropriate organic comprises xitix, citric acid, pentanedioic acid, glyconic acid, oxyacetic acid (glycolicacid), oxysuccinic acid, toxilic acid, propanedioic acid, oxalic acid, succsinic acid, tartrate, 1-hydroxyethyl-1,1-di 2 ethylhexyl phosphonic acid (EHDP), amino polymethylene phosphonic acids, as NTMP, EDTMP and DETPMP, and the mixture of aforementioned any acid.Suitable acid-salt comprises sodium bicarbonate, sodium bioxalate, the mixture of sodium pyrosulfate, sodium acid pyrophosphate, acid sodium orthophosphate, sodium hydrotartrate and aforementioned any salt.

For the purposes of the present invention, water-soluble ionogenic acid solid material and layered crystal water glass form that the mixture this point is very important closely.Silicate is wrapped up by ionizable material or both only are blendings, and this is not enough to provide benefit of the present invention.By two components of thorough mixing, both are disperseed fully, this is necessary, finishes the preferable methods of this process and will describe in the back.The granular mixture of resulting layered silicate and water-soluble ionizable solid material, its pH value are at least 10 (1% distilled water solution is canonical measure during with 20 ℃), and the pH value is 11 at least usually, and normal value is at least 11.5.

Particulate composition of the present invention also contains one or more binding agents of 0%-20% (weight).These binding agents help silicon bonded hydrochlorate and ionizable water-soluble material, the particle that has desired physical property with production.Binding agent preferably can form mixture closely with silicate and ionogenic water-soluble material.Preferably 30 ℃-70 ℃ of the molten points of binding agent.The percentage composition that preferred binder accounts for composition is 1%-10%, the optimum 2-5% that accounts for.

Comprise that according to the preferred binding agent of the present invention every mol of alcohol contains the C of 5-100 moles of ethylene oxide ₁₀-C ₂₀Fat alcohol ethoxyl compound, further preferred binding agent is the C that every mol of alcohol contains the 20-100 moles of ethylene oxide ₁₅-C ₂₀The primary aliphatic alcohols ethoxy compound.

According to the present invention, other preferred binder materials comprise some polymer materials, and for example molecular-weight average is 12, and 000-700,000 polyvinylpyrrolidone and molecular-weight average are 600-10,000 polyvinyl alcohol.The multipolymer of maleic anhydride and ethene, methylvinylether or methylacrylic acid, wherein to account for the polymkeric substance of 20 percent (mole) at least be the example that can be used as another polymeric material of binding agent to maleic anhydride.These polymer materialss can be as binding agent or with as water, propylene glycol and every mole of C that contains the oxyethane of 5-100 mole above-mentioned ₁₀-C ₂₀The fat alcohol ethoxyl compound solvent be used in combination as binding agent.The further example that is used as binding agent by the present invention comprises C ₁₀-C ₂₀List or Glycerol dimer ether and C ₁₀-C ₂₀Lipid acid.The solution that comprises some inorganic salt of water glass also can be used for this purpose.

According to the present invention, as fine plain derivative and the homopolymerization of many carboxylic acids or its salt or another example that multipolymer is binding agent of methylcellulose gum, carboxymethyl cellulose and carboxyethyl cellulose.

If not incompatible and do not disturb the synergistic function of layered silicate, particle to be also included within other component commonly used in the detergent composition in essence.Therefore particle can comprise many surfactant granules to the negatively charged ion that accounts for particle weight 50%, positively charged ion, both sexes or zwitterionics or their any mixture and some preferred concrete blending.The example of these tensio-active agents will be described in the back comprehensively.Yet, the any surfactant material that is blended in the particle all can not be introduced a certain amount of non-binding (dissociating) moisture that can be partly dissolved layered silicate, for this purpose, tensio-active agent should be a solid, preferably contain and be not higher than free (non-binding) moisture of 5%, better contain the free water content less than 2%, best is the free water content that contains less than 1%.

Also can contain other component that is no more than particle weight 50%, as long as it meets above-mentioned similarity condition to tensio-active agent.These optional components should be solid at normal temperatures, and should contain the free water content that is no more than with 5% (weight), preferably are no more than 1%.

If the solubleness of layered crystal silicate in the on-aqueous liquid component is little, can mix the on-aqueous liquid component that accounts for particle weight as many as 20% so.This also is applicable to the solid ingredient of using as particulate agglomerant/coating agent usually under molten state.

Particulate composition of the present invention can be multiple physical aspect, as extrudate, pellet, agglomerate, thin slice or extruding particle.All these forms show several specific characters of component of the present invention, are at least 10 as pH in 1% the distilled water solution 20 ℃ the time, form the mixture closely of layered silicate and ionizable thing, and they are substantially devoid of unbound water.

Discovery can be mixed preferred ingredient of the present invention and do not needed to add other and add component and prepare closely knit particle.By technology of the present invention preferred ingredient of the present invention is mixed, under drying conditions, be squeezed into thin slice, pulverize then and obtain the particulate product that particle size is no more than 1200 microns.

The first step is to mix, with layered crystal silicate, preferably δ-Na ₂Si ₂O ₅(NaSKS-6) and the citric acid of anhydrous powder shape or sodium bicarbonate be in the powder blenders that was added to as cube mixing tank or Nautamixer in 80: 20 to 75: 25 by weight.Layered silicate is the form with fine powder, and the particle size as 90% is less than 100 microns, and citric acid or sodium bicarbonate also are fine powders, and average particle size is near 50 microns.These intimate powder mixtures are sent into squeezing roll (the 2200/50P type are by Bepex GmbH, Postfach1142 then, Daimlerstrasse8, Leingarten, Heilbron, FOR makes), it is wide that roll extrusion is that 10-30 KN/cm rolls, and preferably rolls wide near 25 KN/cm.

At shredder (LHM20/16 type condux swinging derrick, by condux-werk GmbH, D6450 Wolfgang bei Hanau, the FDR manufacturing) before pulverizing in, the extruding particulate size that processing sheet product obtains in crusher is between the 150-1140 micron, and the weighted average size of particulate is near 600 microns.The particulate that undergage is 150 microns turns back to pressing steps, and size is sent in second shredder above 1140 microns particle and pulverized, and obtains having the particulate of desired size range.The grain fraction that makes according to above-described technology will illustrate in the back, and this technology has not only protected fabric and dyestuff injury-free, and can obtain having the particle of gratifying physical strength.The particle that obtains by above-described technology does not contain unbound water substantially, does not have water to add in technological process because initial material is moisture yet.

Yet it is favourable mixing other Synergist S-421 95s again except that layered crystal silicate and ionizable water-soluble cpds, particularly aspect the particle formation and to strengthen the stable aspect contain the particulate detergent component be favourable.In order to quicken the particle that silicon bonded hydrochlorate and ionizable water-soluble material production have acceptable physical property, the caking of some type need add one or more binding agents especially.Can account for the 0%-20% of composition weight by binding agent of the present invention.The preferred examples of binding agent and preferred incorporation were described in front.

The preparation of extrudate and pellet relates in the container of a sealing to mix each component and to make mixture pass that aperture produces particle under pressure and auxiliary component is added in layered silicate and the ionizable material and goes, make it to have character as wax, for in extruding or become in the ball equipment and handle easily, this is normally necessary.The add-on of this component accounts for the 0.5%-10% of total particle weight usually, and 1.0%-5.0% is better in adding.

As C ₁₄-C ₁₈Fat alcohol ethoxyl compound the oxyethyl group nonionogenic tenside and all be the representative of the auxiliary component that is fit to of this purpose as the organic polymer materials of polyoxyethylene glycol and maleic anhydride and acrylic acid multipolymer.

Press another aspect of the present invention, detergent composition makes by mixing the layered silicate particle component as a kind of composition.Be used for the detergent composition of laundering of textile fabrics be mixed with usually organic surface active agent, detergent builder, oxygen float from system and as anti-redeposition agent and dirt dispersant, suds suppressor, heavy metal ion chelating agent, enzyme, white dyes, the subsidiary of photoactivated SYNTHETIC OPTICAL WHITNER, spices and pigment.Some product also comprises fabric softener, static inhibitor.The pH value of 1% the distilled water solution of these detergent composition in the time of 20 ℃ is at least 9.5, preferably 10.0-10.5.

The scope that is used in the tensio-active agent in the detergent composition is very wide.The kind of typical negatively charged ion, nonionic, both sexes or zwitterionics is at the Laughlin of publication on December 30th, 1975 and the U.S.P.3 of Heuring, 929, list in 6678, the U.S.P.4 of the Murphy that one group of cats product was published on March 31st, 1981, listed in 259,217.

Here the mixed anion tensio-active agent is suitable, particularly the blend of vitriol, sulfonate and/or carboxylate surface active agent.The mixture of sulfonate commonly used and sulfate surfactant, the weight ratio of sulfonate and vitriol is 5: 1 to 1: 2, preferably 3: 1 to 2: 3, further preferably 3: 1 to 1: 1.Preferred sulfonate includes the particularly alkylbenzene sulfonate of the alkyl of 11-13 carbon atom of 9-15, and α-sulfonated fatty acid methyl ester, and lipid acid wherein is from C ₁₂-C ₁₈, C particularly ₁₆-C ₁₈Fat source in derive out.Positively charged ion in each example is a basic metal, preferably sodium.The living agent alive of preferred vitriol surface is the alkyl-sulphate that 12-22, a particularly 16-18 carbon atom is arranged on the alkyl in the sulfonate sulfate mixture.Another useful tensio-active agent system is two kinds of alkyl-sulphate mixtures of material, and the mean chain length of two kinds of alkyl-sulphates is different separately.By C ₁₄-C ₁₅Alkyl-sulphate and C ₁₆-C ₁₈The mixture of alkyl-sulphate is formed a kind of such system, wherein C ₁₄-C ₁₅And C ₁₆-C ₁₈Weight ratio be 3: 1 to 1: 1.Alkyl-sulphate also can have 10-20 with alkyl, and preferably 10-16 carbon atom and average degree of ethoxylation are 1-6 alkyl ethoxy sulfate mixes.Positively charged ion in each example is a basic metal, preferably sodium.

Being suitable for another anion surfactant of this purpose of the present invention is the sarkosine an alkali metal salt, and its general formula is

R-CON(R ¹)CH ₂COOM

Here R is C ₉-C ₁₇The alkyl or the alkenyl of straight or branched, R ¹Be C ₁-C ₄Alkyl, M is an alkalimetal ion.Preferred examples is lauroyl, Cocoyl (C ₁₂-C ₁₄), the sodium salt of tetradecyl and oil (oleyl) methyl sarkosine.

The condenses that the useful in the present invention nonionogenic tenside of one class is made up of oxyethane, the hydrophobic group is arranged on it, the amphipathic property average ratio (HLB) of the tensio-active agent that obtains is in the scope of 8-17, and preferable range is 9.5-13.5, further preferably 10-12.5.Hydrophobic (oleophylic) group can be regulated in the polyoxyethylated length that can be aliphatics or aromatic and other any special hydrophobic group condensation in nature, and the water-soluble cpds of certain hydrophilic-lipophilic balance is arranged with production.

Particularly preferred such nonionogenic tenside is the C that every mol of alcohol contains the 3-8 moles of ethylene oxide ₉-C ₁₅The primary aliphatic alcohols ethoxy compound, particularly every mol of alcohol contains the C of 6-8 moles of ethylene oxide ₁₄-C ₁₅Primary aliphatic alcohols and every mol of alcohol C of containing the 3-5 moles of ethylene oxide ₁₂-C ₁₄Primary alconol.

Another kind of nonionogenic tenside is the alkyl polyglucoside compound, and its general formula is

RO (CnH _2nO) _tZ _xThis is that z is the deriveding group of glucose, and R is the hydrophobic alkyl of the saturated 12-18 of a containing carbon atom, and t is 0-10, and n is 2 or 3, and x is 1.1-4, and this compound comprises less than 10% unreacted Fatty Alcohol(C12-C14 and C12-C18) with less than the alkyl polyglucoside of 50% short chain.Such compound and they being applied among the EP-B-0070074,0070077,0075996,0094118 in detergent composition is open.

Another preferred nonionic is the surfactant compounds of polyhydroxy fatty acid amide, and its general formula is:

Here R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, preferably C ₁-C ₄Alkyl, C further preferably ₁Or C ₂Alkyl, that best is C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, C preferably ₇-C ₁₉Straight chained alkyl or alkenyl, C further preferably ₉-C ₁₇Straight chained alkyl or alkenyl, C preferably ₁₁-C ₁₇Straight chained alkyl or alkenyl, or their mixture; Z has at least three hydroxyls directly to be associated in straight chain polyhydroxy alkyl on the chain, or its oxidation alkyl derivative, (the preferably ethoxyquin or third oxidation).Derive from reducing sugar in the preferably amination reduction reaction of z and obtain.Further preferred z is a glucose.Suitable reducing sugar comprises that glucose, fructose, maltose, lactose, semi-lactosi, glycosides reveal sugar and wood sugar.Except that above-named one sugar, high glucose corn steep liquor, high fructose corn syrup and high malt sugar corn steep liquor can utilize as starting material.

These corn steep liquors can be used to produce the mixture of the sugar component of z.This should be understood to never gets rid of other suitable starting material.Z is preferably from by-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ₁) (CHOH)-CH ₂Select in the group that OH constitutes, n is the integer of a 3-5 here, R ¹Be H or cyclic or aliphatic monose and its oxidation alkyl derivative.Glucose most preferably, n is 4 here, particularly-CH ₂(CHOH) ₄-CH ₂OH.

In general formula (I), R ¹For example can be the N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ²-CO-N (for example can be that Ke blocks acid amides, stearylamide, oleylamide, laurylamide, cardamom acid amides, decyl amide, palmitic amide, tallow acid amides etc.

Z can be 1-deoxyglucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl or the like.Preferred compound is N-methyl N-1-deoxy-glucose base C ₁₄-C ₁₈Fatty acid amide.

Another kind of tensio-active agent is the semi-polarity tensio-active agent as amine oxide.Suitable amine oxide is selected from single C ₈-C ₂₀, C particularly ₁₀-C ₁₄N-alkyl or alkenyl amine oxide and 1,3-diamines allyl dioxide, the position of Sheng Xia N is replaced by methyl, hydroxyethyl, hydroxypropyl here.

Here also available cats product in the cleaning composition.Suitable quaternary ammonium surfactant is selected from single C ₈-C ₁₆, C particularly ₁₀-C ₁₄N-alkyl or alkenyl ammonium surfactant, wherein the position of Sheng Xia N is replaced by methyl, hydroxyethyl or hydroxypropyl.

Detergent composition comprises the tensio-active agent that accounts for composition weight 5%-30%, normally contains 7%-20%, preferably 10%-15%.

It is preferred mixing the shape tensio-active agent, particularly negatively charged ion-nonionic and negatively charged ion-nonionic-cation mixt.Particularly preferred mixture has been described in GB-A-2040987 and EP-A-0087914.Although tensio-active agent can mix in the composition as mixture, had better control the time of each tensio-active agent adding and optimize the physicals of component and avoid technological problems.

The preferred mode and the order that add tensio-active agent are described in the back.

Be mixed with the washing auxiliary detergent system that the most preferred composition of the cleaning composition of layered silicate particle is made up of one or more nonphosphate washing auxiliary detergents among the present invention.These auxiliary agents comprise, but be not limited to, alkali-metal silico-aluminate, the monomer multi-carboxylate, the homopolymerization of poly carboxylic acid or its salt or multipolymer, (this poly carboxylic acid comprises at least two carboxyls, and each carboxyl is apart to be no more than two carbon atoms), organic phosphonate and amino alkylidenyl many (alkylene phosphonic acids salt), the mixture of carbonate, silicate and any aforementioned each compound.Washing auxiliary detergent accounts for the 25%-60% of system weight, and preferred range is 30%-60%.

The aluminosilicate ion exchange material of certain limit can be used, and the preferred zeolite structured unitary general formula of sodium silicoaluminate is:

Na ₂[(ALO ₂) _z(SiO ₂) _y] XH ₂O z and y here is 6 at least, and the mol ratio of z and y is 1.0-0.5, and x is 5 at least, preferably 7.5-276, further preferably 10-264.Alumino-silicate materials is a hydrated form, crystalline preferably, and the content of combination water is 10%-28%, preferably 18%-22%.

Another feature of above-mentioned aluminosilicate ion exchange material be its mean particle dia at the 0.1-10 micron, preferable range is the 0.2-4 micron.The what is called here " mean particle dia " is meant the mean diameter of ion-exchange material, is measured by traditional analytical technology, for example utilizes scanning electronic microscope or laser particle survey meter to measure.The another feature of silico-aluminate is that its calcium ion exchange capacity is equivalent to 200mgCaCO at least ₃The water hardness/g silico-aluminate (calculating with moisture-free basis) is usually in the scope of 300mg eq./g-352mg eq./g.A feature again of silico-aluminate is its calcium ion-exchanged rate, is to be equivalent to 130mg CaCO at least ₃/ l/min. (g/l) [2 grains (grains) Ca ²⁺/ gallon/min/ (g/gallon)] silico-aluminate (moisture-free basis), based on calcium ion hardness, normally be equivalent to 130mg CaCO ₃/ l/min./and (g/l) [2 grains (grains)/gallon/min./(g/gallon)] to being equivalent to 390mg CaCO ₃Between/the l/min/ (g/l) [6 grains (grains)/gallon/min/ (g/gallon)].

The calcium ion-exchanged rate that is used as the best silico-aluminate of washing auxiliary detergent is to be equivalent to 260mg CaCO at least ₃/ l/min./and (g/l) [4 grains (grains)/gallon/min./(g/l)].

The available aluminosilicate ion exchange material can have been bought on market in the present invention practice, also can be that nature exists, but preferably synthetic obtains.The method of producing aluminosilicate ion exchange material is at US3, the existing discussion in 985,669.The preferred here synthetic aluminosilicate salt ion exchange material that uses is zeolite A, zeolite B by name, zeolite P, X zeolite, the zeolite of zeolite HS and their mixture.Specifically best aluminosilicate ion exchange material is zeolite A, and its general formula is:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] XH ₂O X here is 20-30, preferably 27.Removing general formula is:

Na ₆[(AlO ₂) ₆(SiO ₂) ₆] 7.5H ₂Outside the zeolite HS of O, general formula is:

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂The X zeolite of O also is suitable.

The carboxylate salt washing auxiliary detergent of suitable soluble and monomeric or oligomer can chosen in the scope widely, particularly the first carboxyl acidity constant logarithm (pK ₁) those compounds less than 9, preferably 2-8.5, further preferably 4-7.5.

The logarithm of acidity constant defines by following balance:

Here A is the carboxylate anion of complete ionized washing auxiliary detergent salt, and the equilibrium constant is:

K ₁=[HA]/[H ⁺] [A ^-] and pK ₁=tog ₁₀K ₁

By purpose of the present invention, acidity constant is that 25 ℃ and ionic strength are that zero situation is undefined.Can find literature value (referring to Stability Constant of Metal-Ioncomplexes, special pullicafion No.25, The chemical society, London), people are with suspicion to this, because it passes through potentiometric determination with glass electrode.

Preferred carboxylate salt also can similar pK ₁Ground defines according to their calcium ion stability constant, and definition is:

PKca ²⁺=log ₁₀Kca ²⁺Here Kca ²⁺=[Ca ²⁺A]/[Ca ²⁺] [A]

Particularly, multi-carboxylate's PKca ²⁺Between about 2-about 7, preferably between about 3-about 6.The literature value of stability constant also can find.Stability constant is to be that zero situation is undefined 25 ℃ and ionic strength, press the usefulness glass electrode method mensuration that Anders Ringbom describes at Complexation inAnalytical chemistry (1963).

Although the monomer multi-carboxylate is because its price and performance reason are normally preferred, carboxylate salt or multi-carboxylate's washing auxiliary detergent can be bodily forms monomer shape or oligomeric.

The washing auxiliary detergent of monomeric or oligomer can be by choosing in acyclic, aliphatic, heterocyclic and the aromatic carboxylate salt, and its general formula is

Or

Here R ₁Represent H, replaced arbitrarily by hydroxyl, carboxyl, sulfo group or phosphono or

Receive the C on the polyethyleneoxy part that contains an as many as 2O vinyloxy group ₁-C ₃₀Alkyl or alkenyl; R ₂Represent H, C _1-4Alkyl, alkenyl, hydroxyalkyl, alkaryl, sulfo group or phosphono; X represents singly-bound; O; S; SO; SO ₂Or NR ₁Y represents H, carboxyl, hydroxyl, carboxyl methoxyl group; Or by hydroxyl, any C that replaces of carboxyl _1-30Alkyl, alkenyl; Z represents H or carboxyl; M is the integer of 1-10; N is the integer of 3-6; P, q are the integer of 0-6, and p+q is 1-6; When repeating in given molecular formula, X, Y and Z can have identical or different expression, include a carboxyl in the molecule of at least one Y or Z.

The suitable carboxylate salt that contains a carboxyl comprises water-soluble salt and its belgian patent 831,368 of lactic acid, oxyacetic acid, 82l, disclosed ether derivative in 369,821,370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) diacetic acid, toxilic acid, two glycosides alkyd, tartrate, tartronic acid and fumaric acid; also has German prospectus 2; 446; 686 and 2; 446,687 and US 3,935; the sulfinyl carboxylate salt that 257 ether carboxylate salts of describing and belgian patent 840,623 are described.The multi-carboxylate who contains three carboxyls comprises, particularly water miscible Citrate trianion, aconitate (aconitrates) and citraconate, also just like GB 1,379, the carboxymethyl of describing in 241 contains oxydisuccinic acid salt, GB 1, the newborn oxydisuccinic acid salt of describing in 389,732 (lactoxysuccinates), the succinate derivative that the aminosuccinic acid salt of describing in Holland's application 7205873 is such and as GB1,387, the 2-Evil-1,1 that describes in 447, the oxidation multi-carboxylate of 3-tricarballylic acid salt.

There is the multi-carboxylate of four carboxyls to comprise GB1, the oxygen connection succinate of describing in 261,829,1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and comprise GB-1,398,421 and GB-1,398,422 and US 3,936,448 in the derivative and the GB1 of disclosed sulfosuccinate, the pyrolysated sulfonation Citrate trianion of describing in 439,000.

Alicyclic and heterocyclic multi-carboxylate comprises pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-the tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane-hexacarboxylic acid salt and as the carboxymethyl derivant of the polyhydroxy-alcohol of mountain plough alcohol, mannitol, Xylitol.Aromatic multi-carboxy acid's salt comprises English Patent 1,425, the mellitic acid of describing in 343,1,2,4,5-benzene tetracarboxylic acid and phthalic acid derivatives.

In above-mentioned multi-carboxylate, preferably every mole of hydroxycarboxylate of containing three carboxyls of as many as particularly preferably is Citrate trianion.

By the present invention, the parent acid of the mixture of monomeric or oligomer multi-carboxylate sequestrant and these salt also can be considered as the component of the detergent builder system of detergent composition as citric acid or Citrate trianion/citric acid mixture.

Other water-soluble organic salt that is suitable for is homopolymerization or copolymerization poly carboxylic acid or their salt, and many carboxylic acids comprise two carboxyls at least, and both separately and be separated by and be no more than two carbon atoms.The latter's polymkeric substance is at GB-A-1, discloses in 596,756.It is the multipolymer of the polyacrylate of 2000-5000 and they and maleic anhydride that the example of these salt has molecular weight, and the molecular weight of this multipolymer is 20,000-70,000, particularly about 40,000.

The consumption of these materials accounts for the 0.5%-10% of composition weight usually, and preferred range is 0.75%-8%, and further preferred range is 1%-6%.

Organic phosphonate and amino alkylidenyl many (alkylene phosphonic acids salt) comprise alkali-metal ethane 1-hydroxyl diphosphonate, WSI 3310 salt, vinyl two amido tetramethylene phosphonic acid salt and divinyl three amido pentamethylene phosphonates.Although P contained compound is not best in the composition, need these minimum materials of quantity.

Although water-soluble silicate has many purposes in traditional prescription, be unnecessary according to its existence in composition of the present invention.Yet because layered crystal silicate has formed the part of the washing auxiliary detergent of scrubbed component, must add as a kind of dry mixture composition, thereby soluble silicate is useful works in the spray-dired particle as the detergent composition integral part still.If it is not necessary when particularly mixing aluminosilicate in the spray-dried granules, otherwise particle only includes organic materials.The SiO of suitable silicate ₂: Na ₂The ratio of O is 1.6-3.4, and the ratio of 2.0-2.8 is preferred.

By the present invention, in order to mix layered crystal silicate a part of this purpose as detergent builder in detergent composition, non-phosphoric acid auxiliary agent should account for the 25%-60% of composition weight, preferably accounts for 30%-60%.In preferred scrubbed component thing, should account for the 20-60% of auxiliary agent total amount as the sodium silicoaluminate of zeolite A, monomer or oligomer carboxylate salt account for 5%-30%, and layered crystal silicate accounts for 10%-65%.In these compositions, detergent builder also mix the mixture of auxiliary inorganic and organic additive, but as 35% of yellow soda ash, maleic anhydride/acrylic copolymer, the total amount of auxiliary of its amount as many as.

The detergent composition that is mixed with layered crystal silicate granules composition of the present invention also includes the inorganic perhydrate SYNTHETIC OPTICAL WHITNER of sodium-salt form usually.The incorporation of perhydrate accounts for the 3%-22% of composition usually, further preferably 5%-20%, most preferably 8%-18%.

Perhydrate can be any inorganic salt, as perborate, percarbonate, superphosphate and persilicate, is the particularly perborate or the percarbonate of sodium of basic metal traditionally.Sodium peroxoborate can be that nominal molecular formula is NaBO ₂H ₂O ₂Monohydrate or be NaBO ₂H ₂O ₂3H ₂The tetrahydrate of O.

SPC-D is preferred perhydrate, is that 2Na is arranged ₂CO ₃3H ₂O ₂The addition compound of molecular formula, available its solid crystal thing on market.Most of commercially available material all contains heavy metal chelant in a small amount, as EDTA, and 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (HE DP) or phosphoro-amidate, it is added in process of production.Just mix in the detergent composition although percarbonate can not add protection, preferably utilize the material that is coated with the stain form to finish this process.It is varied to be coated with the stain form, but most economical be that the aqueous solution of the silicate solid of the 2%-10% (normally 3%-5%) with the SPC-D amount is coated with stain, this silicate uses SiO ₂: Na ₂The O ratio is 1.6: 1-3.4: 1, and best 2.8: 1 water glass.Magnesium Silicate q-agent also can be used for being coated with stain, and the stain material that is coated with that other is suitable also has basic metal and alkali-metal vitriol and carbonate.

When heavy metal appears in the yellow soda ash that is used for producing percarbonate, can in hybrid reaction, control by sheltering of sequestrant.Percarbonate yet needs protection heavy metal is occurred in other blending ingredients of product as impurity.By the present invention, for fear of the detrimental action of undesirable stability to percarbonate, in the detergent composition that utilizes percarbonate as perhydrate salt, the amount of iron, copper, magnesium ion can not surpass 25ppm, preferably is less than 20ppm.The cleaning composition that contains the alkali metal percarbonate SYNTHETIC OPTICAL WHITNER with the stability that has strengthened had been done description in applicant's relevant UK Patent Application 9021761.3.

The SYNTHETIC OPTICAL WHITNER system that mixes cleaning composition among the present invention preferably contains solid peroxygen acid blanching parent (bleach-activating agent).

These parents may contain one or more N-or O-acyl group, bleach precursor can one widely scope choose.Suitable kind has the acylated derivatives of acid anhydrides, ester, inferior acid amides and imidazoles and oxime.The example of the useful materials of these kinds is open in GB-A-1586789.Preferred kind is as GB-A-836988, disclosed ester and as disclosed inferior acid amides in GB-A-855735 and 1246338 in 864798,1147871 and 2143231.

Particularly preferred parent compound is N, N, N ¹, N ¹The compound of four acidylates, its general formula is

Here x can be 0 or the integer of 1-6.

Its example has tetra-acetylated methylene diamine (TAMD), x=1 here; Tetra-acetylated ethylene diamine (TAED), i.e. x=2; Tetra-acetylated hexamethylenediamine (TAHD), i.e. x=6.These compounds and analogue compounds thereof have been described in GB-A-907356.Optimum peroxyacid bleach precursor compound is TAED.

Being coated with stain solid peroxygen bleach precursor with a kind of acid makes it disclose in applicant's relevant Britain application 9102507.2 (on February 6th, 1991 is open) the minimum cleaning composition of fabric color damage.

Suitable anti-redeposition and dirt dispersant comprise as the derivatived cellulose of methylcellulose gum, carboxymethyl cellulose, Natvosol and the homopolymerization or the multipolymer of poly carboxylic acid or its salt.This base polymer comprises the multipolymer of maleic anhydride and ethene, methylvinylether or methylacrylic acid, and wherein maleic anhydride accounts for the molar percentage of multipolymer 20% at least.The consumption of these materials accounts for the 0.5%-10% of composition weight usually, further preferably accounts for 0.75%-8%, most preferably accounts for 1%-6%.

Other useful polymer materials is a polyoxyethylene glycol, and particularly molecular weight is at 1000-10000, and preferred molecular weight is 2000-8000, and is preferably about 4000, and consumption is 0.20%-5% (weight), preferably 0.25%-2.5%.The polycarboxylate of these polymkeric substance and aforesaid homopolymerization or copolymerization is kept, the precipitation of fabric soft flocks, is valuable in the improvement of the performance of washing clay and proteinaceous oxidable dirt under the situation that has impurity metal ion to transform bleachability.

Preferred white dyes is anionic.For example: disodium 4,4 '-two-(2-diethanolamine-4-anilino-S-triazine-6-amido) stilbene-2:2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, disodium 4,4 '-(2-morpholino-4-anilino-2-triazine-6-amido) stilbene-2:2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, disodium 4,4 '-two-(2,4-hexichol amido-S-triazine-6-amido) stilbene-2:2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, single sodium 4 ', 4 " two-(2; 4-hexichol amido-S-triazine-6-amido) stilbene-2-sulfonate, disodium 4,4 '-two-(2-aniline-4-(N-methyl-N-2-hydroxyethyl amido)-2-triazine-6-amido) stilbene-2; 2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate; disodium 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl amido)-S-triazine-6-amido) stilbene-2.2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate and sodium 2 (stilbene radicals-4 " (naphthols base 1 ', 2 ': 4,5)-1,2,3 ,-triazole-2 " sulfonate.

To remove agent be terephthalic acid and 1,2 to the available dirt traditionally in the present composition, copolymerization or terpolymer that the difference of-ethylidene glycol and/or propylene glycol is arranged.The example of these polymkeric substance discloses in US 4116885, US 4711730 and EP-0272033.General formula by the preferred polymkeric substance among the EP-A-0272033 is: (CH ₃(PEG) ₄₃) _0.75(POE) _0.25[T-PO) _2.8(T-PEO) _0.4] T (PO-H) _0.25((PEO) ₄₃CH ₃) _0.75Here PEG is-(OC ₂S ₄) O-, PO is (OC ₃S ₆O) and T be (PCDC ₆E ₄CO).

As some polymer materials of polyvinylpyrrolidone (molecular weight is between 5000-20000, and preferred range is 10000-15000), the additive that also can be formed with usefulness stops in the washing process the mutual colour contamination of unstable dyestuff between fabric.

Another selectable detergent component is a suds suppressor, for example the mixture of polysiloxane and silica one polysiloxane.Polysiloxane is used the alkylation polysiloxane usually, and that silica is got usually is very thin, for example various types of silica aerogels and xerogel and hydrophobic silex.These materials can be used as particle and mix, and that the suds suppressor in the particle is advantageously mixed with the form of can disengaging is water miscible or water-dispersion, be actually in the non-surface active waterproof agent carrier.Also can make and press down the infusion dissolving or be dispersed in the liquid vehicle, be applied by being sprayed onto on one or more other components.

Useful polysiloxane Foam Control above-mentioned can be the mixture of above mentioned alkylating polysiloxane and solid silica.This mixture makes by polysiloxane is attached on the solid silica.The representative of preferred polysiloxane Foam Control is (particularly trimethyl silicone hydride) silica of hydrophobic silanization, and the particulate size is the 10-20 millimicron, and specific surface area surpasses 50m ²/ g, this silica and molecular weight are at the dimethyl polysiloxane uniform mixing of about 500-about 200,000, and the weight ratio of the silica of polysiloxane and silanization is about 1: 1-1: 2.

Preferred polysiloxane foam control discloses in people's such as Bartollota US 3,933,672.The polysiloxane suds suppressor that another useful especially suds suppressor is a self-emulsifying, the German patent application DT-OS2 that publishes on April 28th, 1977, the existing description in 646,126.An example of this compound is DC0544, and it is the multipolymer of polysiloxane/ethylene glycol, can buy from Dow Corning.

The consumption of above-described suds suppressor is the 0.001%-0.5% of composition weight normally, and preferable range is 0.01-0.1%.

Preferred mixing method comprises the suds suppressor of liquid form is sprayed onto on one or more main components of composition, perhaps becomes particle separated from one another pressing down the infusion agent, and then and other solid ingredient mixing of composition.Also comprise other foam control material as particulate foaming regulator blending separated from one another, as C ₂₀-C ₂₄Lipid acid, the wax of crystallite, high-molecular weight oxyethane, epoxy propane copolymer, otherwise bad influence can be arranged the dispersiveness of matrix.Open among the people's such as Bartolotta that these foams adjusting particulate technologies of preparing are mentioned in front the US 3,933,672.

Another selectable useful components is one or more enzymes among the present invention.

Preferred enzyme material has commercially available amylase, neutrality and alkaline proteolytic enzyme, lipase, esterase and cellulase, and they are often mixed in detergent composition.Suitable enzyme is at US 3,519, described in 570 and 3,533,139.

According to also mixing fabric softener in the detergent composition of the present invention.These softening agents are inorganic or organic type.The example of inorganic softening agent has GB-A-1, disclosed terre verte in 400,898, and the organic fabric softener has disclosed water-soluble tertiary amine among GB-A-1514276 and the EP-B-0011340.

Single C ₁₂-C ₁₄The mixture of quaternary amine open in EP-B-0026527 and 528.Another useful organic fabric softening agent is as disclosed long-chain acid amides among the EP-B-0242919.The organic constituent of another fabric softener comprises as disclosed high-molecular weight polyethylene oxide in EP-A-0299575 and 0313146.

The add-on of terre verte accounts for the 5%-15% as the dry mixed composition weight of batching remaining sum, preferably 8%-12% usually.Incorporation as the organic fabric softening agent of water miscible tertiary amine or long-chain acid amides material is 0.5%-5%, 1%-3% preferably, and the add-on of high-molecular weight polyethylene oxide material and water-soluble cationic material accounts for 0.1%-2%, preferably 0.15%-1.5%.Understand more more conveniently on other component of composition although add with the form of exsiccant composite grain sometimes or with the form of fused solution it is sprayed onto, these materials can be added to and deliver to spray-drying tower in the water slurry, and the part of composition is carried out spraying drying.

Detergent composition of the present invention is prepared by the whole bag of tricks that comprises dry mixed, spraying drying, agglomeration, granulation usually, and preferable methods comprises the combination of these methods.One preferred makes this method for compositions and comprises the agglomeration in spraying drying, the super mixer and the combination of dry mixed.

The layered crystal silicate granules is very useful in the concentrated granular washing composition, and with respect to the washing composition that traditional laundry is used, cleaning composition of the present invention has higher density.The tap density of high-density composition is at least 650g/l, is at least 700g/l usually, preferably surpasses 800g/l.

Tap density is the measurement device with simple funnel and cup.Funnel is cast with rigid material, and a valve is arranged in its underpart, is used for the thing in the funnel bled being placed in its following and cup co-axial with it.The upper end of funnel is 130mm, and the lower end is 40mm.During installation, make its lower end from basal plane 140mm.The total height of cup is 90mm, and internal height 87mm, internal diameter are 84mm, and the demarcation volume is 500ml.

In order to measure tap density, fill funnel with powder earlier, open valve again and overflow by bleed cup so that have of powder.Cup is taken out down from funnel, scraped from the cup upper edge, scrape off unnecessary powder with the straight flange instrument of knife and so on.The cup of powder is filled in weighing, obtains the weight of powder, doubles to try to achieve its tap density, and unit is g/l.Measurement can repeat.

Concentrated cleaning compositions is blended into usually has a multi-component blending ingredients at least, also promptly is not only to do mixed single component to make composition.The detergent composition that dried mixed each component is formed is powder normally, and dissolving is slow, easily lumps in storage process, and mobility of particle is poor.

Press the preferred detergent composition of the present invention at least by two kinds of multi-component granulometric composition.The first ingredients constitute composition gross weight at least 15%, normally 25%-50% preferably is no more than 35%, the second ingredients constitute 1%-50%, and preferred range is 10%-40%.

First component is one or more particles inorganic and/or organic salt that are mixed with the anion surfactant that accounts for powder weight 0.75%-40% and account for powder weight 99.25%-60%.Particle can have any suitable form such as granular, laminar, coccoid, spherical, ball shape or needle-like, and is preferably granular.These particles itself can form by disc type or the agglomeration of drum-type nodulizing, or form in the line mixer agglomeration, but normally the spraying drying of most of moisture content produces by in hot blast the water slurry spraying of component being removed.These particles advance in high speed cutter mixing tank and/or the extrusion machine enrichment to improve density at reagglomeration then.For the purpose of simplifying the description, first component is described as spray-dried powders afterwards.

The suitable anion surfactant that is used for first component is the slow straight-chain alkyl sulfate of dissolving, and the average carbon atom number of alkyl is 16-22 and straight-chain alkyl carboxylic acid's salt, and the average carbon atom number of alkyl is 16-24.The alkyl of the tensio-active agent of two kind shapes preferably resembles Tallow, beef and marine animal wet goods natural resource deutero-.

The weight percent that forms the consumption of the anion surfactant in the spray-dried powders of first component is 0.75%-40%, is generally 2.5%-25%, 3%-20% preferably, and most preferred is 5%-15%.Can comprise and resemble linear alkylbenzene sulfonate and C ₁₄-C ₁₅The water soluble surfactant active of alkyl-sulphate also can be sprayed on tensio-active agent on the spray-dried powders.

Another major ingredient of spray-dried powders is one or more organic or inorganic salt, and they provide the particulate crystalline structure.These inorganic and/or organic salts can be water miscible or non-water-soluble, and the latter is made up of water-insoluble detergent builder or most of non-water-soluble additive, and they have formed the part of detergent builder here.Suitable water-soluble inorganic salt comprises alkali-metal carbonate and supercarbonate.If silico-aluminate does not constitute the part of spray-dried component, then the amorphous alkali metal silicate also can be used to provide the structure of spraying granule.

Yet in concentrated cleaning compositions, sodium sulfate does not add as independent component, and it is to be impregnated in as the by product as sulphur (sulphur) acid salt surfactant, and what it should be tried one's best lacks.

When aluminosilicate zeolite formed detergent builder component or a part of detergent builder, it preferably directly was not added in other component by dry mixed, but is added in the multi-component component.

First component can comprise the blending ingredients of as many as 15% (weight), as brightener, anti-redeposition agent, photosensitive bleaching agent (as tetrasulfonic acid zinc phthalocyanine) and heavy metal chelant.Here first component is a spray-dried powders, and generally, the weight percentage that is dried to moisture is 7%-11%, preferably accounts for the 8%-10% of the weight of spray-dried powders.Other technology, as agglomeration, the water content of the powder of production is lower, can be in the scope of 1-10%.

Usually, the particle size of first component is preferably greater than 5% (weight percent) that be no more than of 1.4mm, less than 10% (weight percent) that be no more than of 0.15mm.Preferably at least 60%, the powder of optimum at least 80% (weight percent) is between 0.7mm-0.25mm.The tap density of the spray-dried powders that comes out from spray-drying tower is between 540-600g/l.These powder are further handled in ensuing operation, for example reduce particle size in high-speed cutting machine/mixing machine, push again.Operation except that spraying drying also can be used for directly forming highdensity particle.

Second component of preferred composition according to the present invention, is another multi component particle that contains the water soluble surfactant active.

This can be anionic, non-ionic on type, cationic or semi-polar or their mixtures arbitrarily.Suitable tensio-active agent is listed in front, but preferred surfactants is C ₁₄-C ₁₅Alkyl-sulphate, the C of straight chain ₁₁-C ₁₅Alkylbenzene sulfonate and C ₁₄-C ₁₈Fatty methyl ester sulfonate.

Second component can have any suitable physical form, and promptly it can be laminar, coccoid, ball shape, needle-like, strip or granular, and granular can be spraying drying or non-spray-dired agglomerate.Though second component itself can be the water soluble surfactant active in theory, in fact handle in order to be convenient to, which comprises at least a kind of organic or inorganic salt.This just makes particle have certain degree of crystallinity, and obtains the acceptable flowability energy, and these salt can be one or more organic or inorganic salt that occur in first component.

The particle size of second component must be such, when blending, must avoid emanating mutually with the particle of first component.Therefore, be to greatest extent greater than 1.4mm can not surpass 5% (weight), can not surpass 10% less than 0.15mm.

The tap density of second component is relevant with its preparation form.Yet best form is the mechanically mixing agglomeration, it is by exsiccant or there is the component of agglomerant to be added to the disc type cyclone agglomerator, Z-shaped oar mixing tank or preferably line mixer (as by Schugi (Holland) BV, 29chroomstraat 8211 AS, Lelystad, Netherlands and GebruderLodige MaschinenbanGmbH, D-4790 paderborn 1, Elsenerstrasse7-9, Postfach 2050 F.R.G. make) preparation.The tap density of second component that obtains by these methods is between 650g/l-1190g/l, particularly between 750g/l-850g/l.

Preferred compositions includes the alkaline carbonate that accounts for composition weight 3%-15%, preferably 5%-12% in second component.Like this, carbonate accounts for the 20-40% of second composition weight.

Particularly preferred component also is water-fast hydrated aluminosilicate ion-exchange material in second component, and it is previously described artificial synthetic zeolite, accounts for the 10%-35% of second composition weight.The amount of the water-insoluble alumino-silicate materials that mixes in this way accounts for composition weight 1%-10%, preferably 2%-8%.

In a kind of preparation process of second component, tensio-active agent forms in line mixer.The tensio-active agent of liquid acid form is added in the continuous high speed mixing machine (for example Lodige KM mixing tank) with anhydrous sodium carbonate and hydrated sodium aluminosilicate granular mixture, and neutralization forms surfactant salt, keeps the particle characteristics of mixture simultaneously.The agglomeration mixture that obtains has like this formed second component, and then is added in other components of product.In a kind of improvement project of this technology, tensio-active agent is a neutral in advance, is added to as the viscosity slurry on the mixture of other component.In this scheme, mixing machine only is used for each component of agglomeration to form second component.

In the preferable process of making the detergent composition that contains layered crystal silicate of the present invention, constitute the spray dried prod of the part of first grain fraction, with the remaining ingredient remix before, turn to nonionogenic tenside in a small amount and spray.Second grain fraction is with aforesaid preferable methods manufacturing.First and second components and the layered crystal silicate compositions arranged, perhydrate SYNTHETIC OPTICAL WHITNER and any peroxyacid bleach precursor particle, other are as carboxy acid salt chelator's dried ingredients, dirt removes polymkeric substance and enzyme is sent on the travelling belt together, send into again in the horizontal rotary drum, spices and polysiloxane suds suppressor are sprayed onto product here and get on.In most preferred composition, adopt further rotary drum mixing step add on a small quantity (near weight 2%) get very thin crystalline material, to increase its density and to improve the particulate liquidity holding.

The content of the heavy metal ion of necessary control product and relative humidity balance etc. have been found in preferably mixing the concentrated cleaning product of alkali metal percarbonate.The such common energy of composition enhanced stability that contains SPC-D, this is open in the UK Patent Application 9021767.3 (Attorney ' s Docket No.CM343) of application on October 6 nineteen ninety.

Also help transfer system by composition of the present invention, therefore transfer system has formed product in the drum of automatic washing machine when cycles of washing begins high dense district, temporary transient room, has avoided the problem of the loss of product in machine pipe network and pond groove.

Washing composition is sent in the drum can be by realizing at an easy rate in detergent composition is packed into a bag or the container, when cycles of washing begins, washing composition can according to stir, the degree of depth of water discharges soon in the rising of temperature or the drum.In addition, washing machine self also is suitable for detergent composition directly is added in the drum, as the diverting device by entrance door.

The product of detergent composition is wrapped in a sack and the container, the thing to keep the inside that container is normally complete under drying regime does not leak, but when being exposed under the wash environment, can discharge the thing in the container, generally be to be immersed in the container.

Common this container is flexible, as sack or box.Sack can have the fibrous texture of fluid-tight protecting materials, is used for keeping the washing composition in the bag, in EP0018678 disclosed.Or the edge made from water-insoluble synthesizing polymeric material sealing or surrounding edge arranged can the disruptive box in water, this is at EP0011500, has also described in 0011501,0011502 and 0011968.The crisp surrounding edge of a kind of water easily be at the box edge or sealed edge bonding with water-soluble adhesive glue, box is formed by fluid-tight polymeric film, as polyethylene, polypropylene screen.In the sack or container of other form, center soft layer dipping and/or be coated with stain one composition is arranged adds one or more layers skin again, is used for producing as the thin-layer tablet shape product of the aesthetic results of fabric also using.Each layer can be sealed, and makes to keep in use being attached to together, perhaps is separated from each other with water to contact, and makes to be coated with stain or the easier release of impreg.

Another thin layer form is that an embossing deformation layer is arranged, and a series of box-shaped vessels are provided, and puts into a certain amount of detergent composition in box-shaped vessel, also has the second layer to cover on the first layer, and the two-layer part that is in contact with one another seals between box-shaped vessel.Component can particle, paste or fusion form are put into, in adding entry before, thin layer should prevent that the component in the box-shaped vessel from leaking.When contacting with water, two-layer can being separated from each other also can be to keep attaching, and unique requirement is that this structure will guarantee that the washing composition in the box-shaped vessel can be discharged in the solution rapidly.The quantity of the on-chip box-shaped vessel of per unit area is a problem of selecting, normally between every square metre of 500-25000.

According to the present invention, comprise sponge, paper and braiding and non-woven fiber as the suitable material of pliable and tough thin layer.

Yet, the best way of finishing this process by the present invention be by a device that reuses that saturating solid wall not arranged through liquid detergent composition be introduced in the drum in the liquid of fiber.

This device is open in EP0343069 and EP0343070.The latter discloses the device that a kind of pliable and tough crust of the bag shape of stretching from the supporting ring that is with holes is formed, and aperture is adapted such that one bag of enough cycles of washing of product uses.Part washing medium flows through aperture and enters sack, dissolved product, and solution flows out from aperture and enters washing medium.Supporting ring provides a screen fraud device to prevent that product that wet, undissolved from leaking.The typical pattern of this device is to be made of the overhanging thin-walled of stretching from described wheel shape center hub of radiation shape, or is made of the similar structures that the volution thin-walled is arranged.

The present invention illustrates that with following non-restrictive example wherein all percentage ratios are except that specified otherwise, all based on weight.

In detergent composition, the meaning of the breviary symbol of component is as follows:

C ₁₂LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate;

TAS: Tallow, beef sodium alkyl sulfate;

C ₁₄/ 15AS:C ₁₄-C ₁₅Sodium alkyl sulfate;

TAEn: the Tallow, beef alcohol ethoxylates has the n moles of ethylene oxide in every mol of alcohol; 45EY: with average mol be Y ethylene oxide condensation be mainly C _14-15Straight

The chain primary alconol; CnAE _E6.5: with the C of 6.5 moles of ethylene oxide condensations ₁₂-C ₁₃Primary alconol; PEG: polyoxyethylene glycol (molecular weight is indicating thereafter usually); TAED: tetra acetyl ethylene diamine; Silicate: amorphous sodium silicate (SiO ₂: N ₂O is usually thereafter); NaSKS-6: layered crystal silicate δ-Na ₂Si ₂O ₅Carbonate: anhydrous sodium carbonate; Supercarbonate: anhydrous sodium bicarbonate; CMC: Xylo-Mucine; Zeolite-A: hydrated sodium aluminosilicate (Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O), most of

Particle size is between the 1-10 micron; Polyacrylic ester: molecular weight is 4000 acrylate homopolymer; Citrate trianion: citrate dihydrate trisodium; Photosensitization SYNTHETIC OPTICAL WHITNER: four sulfonation zinc phthalocyanine phthalocyanines; MA/AA:1: 4 toxilic acids/acrylic copolymer, molecular-weight average about 80000; MVEMA: maleic anhydride/vinyl methyl ether multipolymer, molecular-weight average are 240,000,

These materials are used NaOH prehydrolysis before adding; Perborate: four water sodium perborate (NaBO ₂3H ₂OH ₂O ₂); One water perborate: anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, experience molecular formula are NaBO ₂H ₂O ₂Percarbonate: SPC-D, 2Na ₂CO ₃3H ₂O ₂Enzyme: mixing protease and amylase that NOVO Industries AS sells; Whitening agent: disodium 4,4 '-two (2-morpholinoes-4-anilino-S-triazine-6

-Ji amine) stilbene-2:2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate;

DETPMP: divinyl triamine five (methylene phosphonic acid), Monsanto sells, commodity

Dequest 20660 by name;

Mix suds suppressor: 25% molten point is 50 ℃ a paraffin, 17% hydrophobic silex, 58% stone

Wax oil.Embodiment 1:a) the 1.1Kg particle size is less than layered crystal silicate δ-Na of 300 microns ₂Si ₂O ₅(SKS-6 is provided by Hoechst.AG) and 0.3Kg particle size be less than 300 microns Citric Acid, usp, Anhydrous Powder, is premix 2 minutes in the Eirich RVO2 mixing tank of 500rpm at rotating speed, forms the intimate mixture of two kinds of powder.Resulting mixture is packed in the loading hopper of Bepex roller press (L200/50P type).One agitator is arranged in the funnel, and rotating speed is 50rpm, and mixture is sent into funnel continuously, is a constant to keep Intake Quantity, guarantees the charging stable and consistent of roller press.Start roller press then, the roll gap of powdered mixture feed cam roller, it is wide that the pressure side between roller is that 25KN/cm rolls.The gained thin slice grinds by LHM20/16 type condux shredder once, screening again, the 0.7Kg mean sizes is 600 microns a particle, have 95% greater than 200 microns, 95% less than 1200 microns.B) as above-mentioned in a) 1.1Kg layered crystal silicate and the 0.3Kg Citric Acid, usp, Anhydrous Powder press a) in the method pre-mixing.Sending into before the roller press loading hopper, TAE50 is sprayed onto on the mixture with the 0.O5Kg fused, and the gained thin slice grinds by the condux shredder, obtains mean sizes and be 600 microns particle, and wherein 95% greater than 200 microns, and 95% less than 1200 microns.If replace the TAE5O nonionogenic tenside also to obtain similar result with 45E7.Embodiment 2 preparation following each composition (representing) with weight part

A B C D C ₁₂LAS 6.27 6.27 6.27 6.27 TAS 4.15 4.15 4.15 4.15 4,5E7 3.85 3.85 3.85 3.85 TAE11 1.14 1.14 1.14 1.14 Wessalith CSs 19.65 19.65 19.65 19.65 citrates 8.0 6.0 0 6.0 MA/AA 5.08 5.08 5.08 5.08 carbonate 15.4 8.7 14.7 11.7-water perboric acids 12.5 12.5 12.5 12.5 TAED 5.0 5.0 5.0 5.0 DETPMP 0.59 0.59 0.59 0.59 CMC 0.83 0.83 0.83 0.83 foam inhibitor 0.47 0.47 0.47 0.47 brightening agent 0.25 0.25 0.25 0.25 light sensitivity bleaching agent 20ppm 20ppm 20ppm 20ppm enzyme 1.4 1.4 1.4 1.4 silicate (ratio is 2.0) 3.5 000 NaSKS6^*0 11.0 11.0 11.0 supercarbonates ^*000 3.9 citric acids ^*00 4.45 0

* represent to prepare by the mode in the similar embodiment 1 as the component of layered crystal silicate granules.

These batchings are used for carrying out as follows the experiment to the fabric color damage:

In the time of 40 ℃, place operating process 5 (non-firm color) that these batchings are carried out the full scale experiment with Hotpoint automatic washing machine (9534/9530 type).The load of every washing machine is 4 cotton bed sheets (3.3Kg), add the special batching of 100g by the fabric of Flexi particles dispersed device in washing machine, fabric also comprises the Fabrics by Borval, Albert street, Huddersfield, 100% the responsive look wool fabric of SYNTHETIC OPTICAL WHITNER of the red-violet colour that West Yorkshire, England provide (design number for No.W3970), the fabric cloth specimen is 43cm * 43cm.12 liters of Ca: Mg of adding are that 3: 1 hardness is that 150ppm (uses CaCO in each washing machine ₃Expression) water.

For the environment of a reinforcement is provided, fabric is placed on the particulate top, and then reverses around its basal plane, makes that fabric remains on around the particulate before washing machine starts.24 replicate(determination)s are all carried out in each processing, with following hierarchy system classification is estimated in the color damage of fabric cloth specimen by panel of experts then.

Three coloured cloth specimen explanation color damages in various degree.Set up one 4 grades standard, 1 grade of expression " in fact not damage ", 4 grades of expressions " major injury " decide intermediate point with three standards, that is: between the various descriptions of color damage

1 basic not damage

2 slight damages

3 damages

4 major injuries

Appraise through discussion with two panel of experts, their result's mean value is as overall grade.When more overall grade, 0.2 difference can be thought tangible difference.

Come relatively to make the degree of injury of batching A, B, C and D in this way, measurement result is as follows:

The overall grade of preparing burden

A 1.2

B 1.8

C 1.4

D 1.2

Whether batching B includes on the layered crystal silicate is had any different with A, and it does not contain amorphous silicate, for keeping the symmetry of basicity, has reduced the consumption of Citrate trianion and carbonate detergent builder.Batching B has verified that the damage of fabric color is caused owing to having mixed the layered crystal silicate that does not add protection.

Can see that batching C of the present invention and D are obviously littler than the fabric pigment damage that B produces, and approach the A for preparing burden.Embodiment 3:

The prescription of the granulated detergent that the laundry is used is similar to the composition C among the embodiment 2 usually, also assesses its damage to fabric color with the washing machine experimental technique among the embodiment 2 simultaneously.

Product is to select for use on TAE50 or the 45E8 with component C difference to be arranged at the blending amount of citric acid and mixing method with as tackiness agent or insulating covering agent only.

The pH value of layered silicate particle composition solution and to contain this particulate washing composition as follows to the overall grade of the damage of fabric color: product serial number particulate composition color damage particulate composition

(component ratio) overall grade pH (1%)

1 with reference to (No.NaSKS-6 ^*) 1.2 NA

2 NaSKS-6+ dry mixed lemons

Lemon acid 78,/22 1.9 11.5

3 NaSKS-6+ citric acids 78,/22 1.1 11.8

4 NaSKS-6, citric acid, TAE50 ^*

(76/21/3) (part neutralization) 1.3 12.1

5 NaSKS-6, citric acid, TAE50 ^*

(76/21/3) 1.1 11.8

6 NaSKS-6, citric acid, 45E8 ^*

(76/21/3) 1.1 11.8

7 NaSKS-6 cover (10% lemon

Acid+4%TAE50) 2.0 11.8

* be the component A among the embodiment 2

* makes by the method among the embodiment 1 roll extrusion together

Comparative product 2 and reference product 1 just as can be seen since blending NaSKS-6 silicate and layered crystal silicate is closely mixed with citric acid, the color damage is aggravated.Comparative product 3 and product 2 find that if layered crystal silicate closely mixes with citric acid, then the color damage alleviates, and the color damage that relative product 3 with citric acid (product 4) produces in the part is slight having degenerated under these conditions.The existence of product 5 and 6 explanation agglomerate auxiliary agents can not influence the advantage that layered crystal silicate and citric acid are combined closely and produced.Final product 7 has illustrated under experiment condition can not reduce the fabric color damage with citric acid parcel NaSKS-6.

Claims (40)

1. a conduct is done washing with the particulate composition of solid detergent or detergent component, and the pH value of its distilled water solution of 1% is at least 10 in the time of 20 ℃, it is characterized in that it is the intimate mixture that is selected from following component:

A) general formula of 10%-95% (weight) is NaMSi _xO _2x+1YH ₂The layered crystal silicate of O, M is sodium or hydrogen here, and x is the number of 1.9-4, and y is the number of 0-20;

B) 5%-90%'s (weight) contains the water-soluble ionizable solid material of at least 1 pKa value less than 9 acid functional groups, be selected from organic acid, organic and inorganic acid salt and its mixture, the particulate mean sizes of described water-soluble ionizable solid material is no more than 300 microns;

C) at least a tackiness agent of 0%-20% (weight);

D) tensio-active agent of 0%-50% (weight) is selected from negatively charged ion, nonionic, both sexes and zwitterionics and its mixture;

E) 0%-50%'s (weight) is different from above-mentioned detergent component a)-d).

2. according to the particulate composition of claim 1, comprise the layered crystal silicate of 50%-90% and the water-soluble ionogenic solid material of 10%-50%.

3. according to the particulate composition of claim 1, it is characterized in that ionizable material comprises the organic acid that is selected from following acid: xitix, citric acid, pentanedioic acid, succsinic acid, toxilic acid, oxysuccinic acid, propanedioic acid, oxalic acid, oxyacetic acid, glyconic acid and their any mixture.

4. according to the particulate composition of claim 1, it is characterized in that ionizable material comprises and is selected from following inorganic acid salt: sodium bicarbonate, sodium acid pyrophosphate, acid sodium orthophosphate, sodium pyrosulfate and their any mixture.

5. according to the particulate composition of claim 1, it is extrudate, pellet, agglomerate, thin slice or extruding particle form.

6. according to the particulate composition of claim 5, be mixed with the auxiliary organic constituent of 0.5%-10% (weight).

7. according to the particulate composition of claim 6, it is characterized in that auxiliary organic constituent is nonionogenic tenside, polyethylene glycols or the polymkeric substance detergent builder of ethoxylation or their any mixture.

8. according to the particulate composition of claim 7, contain the solid C of 1%-5% (weight) ₁₄-C ₁₈Alcohol ethoxylate.

9. according to the particulate composition of claim 1, described detergent component is selected from the SYNTHETIC OPTICAL WHITNER that comprises inorganic perhydrate, bleaching activity body and photosensitivity SYNTHETIC OPTICAL WHITNER, include sequestrant and other polymer materialss, white dyes, suds suppressor, enzyme, fabric softener, vitriol, carbonate and their any mixture that organic phosphonates, anti-redeposition agent, dirt dispersant and dirt remove agent.

10. want 1 particulate composition according to right, it is characterized in that, the amount of tackiness agent is 1%-10%, and described at least a tackiness agent is the C that every mol of alcohol contains the 5-100 moles of ethylene oxide ₁₀-C ₂₀Alcohol ethoxylate.

11. the particulate composition according to claim 10 is characterized in that, at least a tackiness agent is the C that every mol of alcohol contains the 20-100 moles of ethylene oxide ₁₅-C ₂₀Primary alcohol ethoxylate.

12. according to the particulate composition of claim 1, wherein said layered crystal silicate has general formula δ-Na ₂Si ₂O ₅(NaSKS-6).

13. according to the particulate composition of claim 12, the general formula that includes 50%-90% is δ-Na ₂Si ₂O ₅(NaSKS-6) the ionizable material of the solid, water soluble of layered crystal silicate material and 10%-50%.

14. particulate composition according to claim 12, it is characterized in that ionizable material comprises and is selected from following organic acid: xitix, citric acid, pentanedioic acid, succsinic acid, toxilic acid, oxysuccinic acid, propanedioic acid, oxalic acid, oxyacetic acid, glyconic acid and their any mixture.

15. the particulate composition according to claim 12 is characterized in that, ionizable material comprises and is selected from following inorganic acid salt: sodium bicarbonate, sodium acid pyrophosphate, acid sodium orthophosphate, sodium pyrosulfate or their any mixture.

16. the particulate composition according to claim 12 is characterized in that, at least a tackiness agent is the C that every mol of alcohol contains the 5-100 moles of ethylene oxide ₁₀-C ₂₀Alcohol ethoxylate.

17. the particulate composition according to claim 12 is characterized in that, at least a tackiness agent is the C that every mol of alcohol contains the 20-100 moles of ethylene oxide ₁₅-C ₂₀Primary alcohol ethoxylate.

18. according to the particulate composition of claim 12, the particle mean size that comprises 75%-80% (weight) is no more than δ-Na of 300 microns ₂Si ₂O ₅(NaSKS-6) and the particle mean size of 20%-25% (weight) be no more than 300 microns sodium bicarbonate or citric acid.

19. according to the particulate composition of claim 12, it is extrudate, pellet, agglomerate, thin slice or extruding particle form.

20. according to the particulate composition of claim 19, blending has the auxiliary organic constituent of 0.5%-10% (weight).

21. the particulate composition according to claim 20 is characterized in that, auxiliary organic constituent is selected from nonionogenic tenside, polyoxyethylene glycol or the polymkeric substance detergent builder of ethoxylation or their any mixture.

22., be mixed with the solid C of 1%-5% (weight) according to the particulate composition of claim 20 ₁₄-C ₁₈Alcohol ethoxylate.

23. a method of making particulate composition, described particulate composition are the intimate mixtures that is selected from following component:

A) general formula of 10%-95% (weight) is NaMSi _xO _2x+1YH ₂The layered crystal silicate material of O, M is sodium or hydrogen here, and x is the number of a 1.9-4, and y is the number of a 0-20;

B) 5%-90%'s (weight) contains the water-soluble ionizable solid material of at least 1 pKa value less than 9 acid functional groups, be selected from organic acid, organic and inorganic acid salt and its mixture, the particle mean size of described water-soluble ionizable material is no more than 300 microns;

C) at least a tackiness agent of 1%-20% (weight) is characterized in that may further comprise the steps:

I) mix a), b) and c) component, form closely, basic mixture uniformly;

Ii) roll under the wide pressure, in roller press, mixture is pressed into sheeting at 10-50kN/cm;

Iii) pulverize described thin slice, obtain the particle that overall dimension is no more than 1200 microns.

24. the method according to claim 23 is characterized in that, pressure be roll about 25kN/cm wide.

25. the method according to claim 23 is characterized in that, described particulate average largest dimension is about 600 microns.

26. the method according to claim 23 is characterized in that, in step (i) one or more detergent components that account for composition total weight maximum 50% is joined component a), b) and if any c) in.

27. the method according to claim 23 is characterized in that, in the step (i) in component a), c b) and if any) mix the common organic solid material that the back adds 0.5%-10% (weight).

28. the method according to claim 23 is characterized in that, common organic solid material is to be sprayed onto component a) with the fused form, b) and if any c) mixture on.

29. a method of making particulate composition, described particulate composition are the mixtures closely of following component:

A) general formula δ-Na of 10%-95% (weight) ₂Si ₂O ₅(NaSKS-6) layered crystal silicate material;

B) 5%-90%'s (weight) contains the water-soluble ionogenic solid material of at least 1 pKa value less than 9 acid functional groups, be selected from organic acid, organic and inorganic acid salt and its mixture, the particle mean size of described water-soluble ionizable solid material is no more than 300 microns;

C) one or more tackiness agents of 1%-20% (weight); It is characterized in that comprising the steps:

(i) blending ingredients a), b) and c), form one closely, basic mixture uniformly;

(ii) roll under the wide pressure and in roller press, mixture be pressed into sheeting at 10-50kN/cm,

(iii) pulverize described sheeting, obtain the particle that maximum particle size is no more than 1200 microns.

30. the method according to claim 29 is characterized in that, pressure be roll about 25kN/cm wide.

31. the method according to claim 29 is characterized in that, described particulate average largest dimension is about 600 microns.

32. the method according to claim 29 is characterized in that, in step I) in, one or more scrubbed component that as many as accounted for particulate composition weight 50% join component a), b) and if any c) in.

33. the method according to claim 29 is characterized in that, in step I) in, in component a), c b) and if any) mix the common organic solid material that the back adds 0.5%-10% (weight).

34. the method according to claim 29 is characterized in that, common organic solid material is to be sprayed onto component a) with the fused form, b) and if any c) mixture on.

35. a solid detergent composition contains the organic surface active agent of 5%-30% (weight), the described particulate composition of claim 1 of the detergent builder of 25%-60% (weight) and 10%-45% (weight).

36. the granular detergent composition according to claim 35 is characterized in that, detergent builder are selected from crystalline and amorphous sodium silicoaluminate zeolite, Trisodium Citrate, yellow soda ash and its any mixture.

37. according to the granular concentrated cleaning compositions of claim 36, density is 650g/l at least.

38. the solid detergent according to claim 35 is washed composition, wherein said layered crystal silicate has general formula δ-Na ₂Si ₂O ₅(NaSKS-6).

39. the granular detergent compositions of root claim 38 is characterized in that, detergent builder are selected from crystalline and amorphous sodium silicoaluminate zeolite, Trisodium Citrate, yellow soda ash and its any mixture.

40. according to the concentrated granular detergent composition of claim 39, its density is 650g/l at least.