CN100348489C

CN100348489C - Surface-treated particle of water-soluble inorganic compound, process for producing the same, and particulate detergent composition

Info

Publication number: CN100348489C
Application number: CNB2004800108449A
Authority: CN
Inventors: 增井宏之; 中村直辉; 永野达生; 堀江弘道; 松永聪; 永安克也; 永田聪; 甲纯人; 三宅深雪; 比田井绘里
Original assignee: Lion Corp
Current assignee: Lion Corp
Priority date: 2003-04-24
Filing date: 2004-04-23
Publication date: 2007-11-14
Anticipated expiration: 2024-04-23
Also published as: CN1777561A

Abstract

Surface-treated water-soluble inorganic compound particles obtained by treating the surface of core particles of a water-soluble inorganic compound with an organic or inorganic, water-soluble polymer and further treating the surface of the resultant particles with a sparingly water-soluble compound. The surface-treated water-soluble inorganic compound particles do not agglomerate even when wetted under the conditions of a low water temperature and a low stirring force. The particles have excellent solubility during laundering. They have excellent flowability and can be prevented from adhering to a granulator during production.

Description

Surface-treated particle of water-soluble inorganic compound and manufacture method thereof and granular detergent composition

Technical field

The present invention relates to surface-treated particle of water-soluble inorganic compound.Particularly relate to the surface-treated particle of water-soluble inorganic compound that the powder mixes alkaline agent passes through in the granular detergent composition.

Background technology

Before this, be to solve variety of problems such as operability, slaking, storage stability and solvability, proposed by water-soluble high-molecular compound to the method (spy opens flat 3-53000 communique) of grain granulation, to the method (spy opens the 2001-293354 communique) of particle surface bag quilt with relevant solid particulate.

In the granular detergent composition field, usually observe the detergent particles that contains tensio-active agent in washing in the winter time the gelation cohesion and incomplete dissolved phenomenon.Particularly in recent years, the bath raio (bath ratio) of following the maximization owing to washing machine to cause descends and because the minimizing of the rinsing water yield that energy-saving design causes, and is used in usually earlier powder detergent to be soaked the method for placing use etc. before the washing.Owing to do like this, when washing the winter of using water at low temperature, the incomplete dissolved situation of washing composition take place easily.For addressing this problem, proposed on the detergent particles surface with the method for water-soluble polymer bag quilt (spy opens flat 7-242899 communique).

On the other hand, proposed to mix various particulate technology in order to give the various functions of granulated detergent.In such occasion, mixed particle interacts, and can cause other problem of the decreased solubility of granulated detergent.Particularly, when advancing in detergent particles with powder mixes water-soluble inorganic compound, water-soluble inorganic compound contact with water water and the time, can fierce cohesion generate aggregate with detergent particles, this has just caused incomplete dissolved problem.

For addressing this problem, propose be washed the agent particulate with ionic surfactant pack simultaneously, with water soluble organic substance solution and/or pressed powder bag by the technology of an alkali metal salt one side (spy opens the 2002-266000 communique).

Yet, in above-mentioned motion, the washing composition under the condition of clothing class coexistence and the solvability of washing composition condensation product are not estimated, when lacking whipping force and use water at low temperature to carry out Actual laundering, as suppress the washing composition condensation product to reach incomplete dissolved technology be inadequate.With regard to its dissolving that fully consider to suppress water-soluble inorganic compound this viewpoint of generating heat also is inadequate.

Further, as the technology that solves the problem that is produced when mixing between the powder, for example, proposed with after having granulation things such as the powder that can be insoluble to water or bleach-activating agent with the water-soluble high-molecular compound bag of the functional group of polyvalent metal ion reaction, technology (the flat 11-514402 communique of special table, the spy opens clear 63-130522 communique) with multivalent metallic ion crosslinking.But these technology also are improving storage stability and morphological stability when cooperating with many waterborne compositions is a purpose, are not the technology of inhibition formation of condensation product when dissolving.

In addition, for being the particle of water-soluble inorganic compound of purpose, all coating techniques have been proposed with powder mixes in granulated detergent.

The technology (spy opens clear 63-20398 communique, special table 2001-505240 communique) of the dispersiveness when improving particulate dissolution rate and washing for example, has been proposed by water-soluble high-molecular compound the water-soluble inorganic compound granulation.Have again, for water-soluble inorganic compound, proposed slightly water-soluble mineral compound such as multiple alkalimetal silicate are mixed, or make the technology of its compoundization and support the technology (spy open flat 8-60200 communique, spy are opened flat 4-275400 communique, the spy opens the 2000-34496 communique) of the dense silicate solutions of spraying on the body at water-soluble inorganic compound.

Can yet these coating techniques be also so that contribution is arranged is the main starting point to improving particulate storage stability and clearing power, suppress the formation of washing composition condensation product when washing with water at low temperature, prevent that incomplete dissolving from but not knowing.

On the other hand, for deliquescent problem, also proposed with the technology of slightly water-soluble (organic) compound with mineral compound bag quilt about water-soluble inorganic compound.For example, the technology as the control dissolution rate has proposed the method (spy opens the 2001-510501 communique) with higher alcohols bag quilt.

Have again, as under the condition that adds abundant whipping force, incomplete dissolved technology when improvement is washed with water at low temperature, proposed by soap bag quilt method (spy opens flat 1-229098 communique, the spy opens flat 10-237498 communique), when the acid precursor bag by anion surfactant is by the water-soluble alkali inorganic particle in surperficial neutral method (spy opens the 2001-81498 communique, the spy opens flat 10-158699 communique) etc., but its effect is uncertain.

Further, as other coating technique in the granulated detergent field, proposed by being washed the technology of agent composition with aluminosilicate and water-soluble polymer bag, obtained to have mobile improved effect and suppress that fine powder forms the detergent composition of effect and by with (spy show the 2000-505834 communique, the spy opens flat 6-172800 communique) such as the good granulated detergents of the storage stability of silica dioxide granule and water-soluble polymer bag quilt.

Have again, also proposed by various combinations such as water-soluble binder such as anion surfactant commonly used in the granulated detergent, nonionogenic tenside, water-soluble inorganic compound, polyoxyethylene glycol, the preparation particle, make the activity stabilized method of enzyme and SYNTHETIC OPTICAL WHITNER etc., suppress the method etc. (spy open flat 6-192697 communique, spy are opened flat 4-345700 communique, the spy opens flat 3-265699 communique) of the hydrolysis of tensio-active agent self.

Yet the formation of washing composition condensation product prevented that its incomplete dissolved effect from being sufficient when hardly these methods of putting down in writing in these each documents suppressed to wash with water at low temperature for what is called.

As mentioned above, wish to have the generation of the washing composition condensation product that causes in the time of can preventing from effectively under water at low temperature and the inadequate state of whipping force, to wash, and be in the suds and show good deliquescent particle of water-soluble inorganic compound, and cooperate this particle and the flowability after the prolonged preservation, the granular detergent composition that non-solidified nature is good.

Summary of the invention

The purpose of this invention is to provide surface-treated particle of water-soluble inorganic compound; even it is the wetting condensation product that also do not form under the state of low water temperature and weak whipping force; and be in the suds and shown outstanding solvability, good fluidity, adhering to tablets press in the time of can preventing to make.Further, cooperating this particulate granular detergent composition is the flowability after the prolonged preservation, the granular detergent composition that non-solidified nature is good.

The inventor finds by with the organic or inorganic water-soluble high-molecular compound water-soluble inorganic compound nuclear particle being carried out surface treatment, and the water insoluble chemical compound is handled surface treated again and the surface-treated particle of water-soluble inorganic compound that forms can reach above-mentioned purpose.

That is, provide following invention.

[1]. a kind of surface-treated particle of water-soluble inorganic compound, it is characterized by the organic or inorganic water-soluble high-molecular compound that is used as the 1st surface treatment agent the water-soluble inorganic compound nuclear particle is carried out surface treatment, further, its processed surface slightly water-soluble compound of being used as the 2nd surface treatment agent is handled.

[2] .[1] surface-treated particle of water-soluble inorganic compound put down in writing, it has the water-soluble inorganic compound nuclear particle and contains the 1st surface treatment of water-soluble high-molecular compound and formed the 2nd surface treatment that contains the slightly water-soluble compound on part or all surface on the 1st surface treatment formed on part or all surface on this nuclear particle surface.

[3] .[2] surface-treated particle of water-soluble inorganic compound put down in writing, it is characterized by in water that above-mentioned the 1st surface treatment has shown heat generation in dissolving or the dispersion process, above-mentioned the 2nd surface treatment has shown heat absorptivity in dissolving or the dispersion process in water, and the full surface treatment that the 1st surface treatment and the 2nd surface treatment form in dissolving or the dispersion process in water has shown heat absorptivity.

[4] .[1]～any surface-treated particle of water-soluble inorganic compound of being put down in writing in [3], it is characterized by the water-soluble inorganic compound nuclear particle is yellow soda ash or salt of wormwood.

[5] .[1]～any surface-treated particle of water-soluble inorganic compound of being put down in writing in [4], it is characterized by water-soluble high-molecular compound and be a kind of from vinyl macromolecular compound, polyose, its derivative and polyester macromolecular compound, selecting, two or more.

[6] .[1]～any surface-treated particle of water-soluble inorganic compound of being put down in writing in [4], it is characterized by water-soluble high-molecular compound is the compound with carboxyl.

[7] .[1]～any surface-treated particle of water-soluble inorganic compound of being put down in writing in [4], it is characterized by water-soluble high-molecular compound is water glass.

[8] .[1]～any surface-treated particle of water-soluble inorganic compound of being put down in writing in [7], it is characterized by the slightly water-soluble macromolecular compound is anionic surfactant acid precursor and/or its salt.

[9] .[8] in the surface-treated particle of water-soluble inorganic compound put down in writing, it is characterized by anionic surfactant acid precursor is lipid acid.

[10] .[1]～any surface-treated particle of water-soluble inorganic compound of being put down in writing in [9], it is characterized by, it is the alkaline agent that granular detergent composition cooperates usefulness.

[11]. the manufacture method of surface-treated particle of water-soluble inorganic compound is characterized by and comprises following the 1st operation and the 2nd operation.

The 1st operation: in the water-soluble inorganic compound nuclear particle, add the water-soluble high-molecular compound aqueous solution, the water-soluble inorganic compound nuclear particle is carried out the surface-treated operation with water-soluble high-molecular compound.

The 2nd operation: in the 1st operation treated water dissolubility mineral compound nuclear particle, add the slightly water-soluble compound, above-mentioned particle is carried out the surface-treated operation.

[12] .[11] manufacture method put down in writing, it is characterized by the slightly water-soluble compound is anionic surfactant acid precursor.

[13] .[12] manufacture method put down in writing, the temperature of the surface-treated particle of water-soluble inorganic compound when it is characterized by the 2nd operation one and finishing be the fusing point of anionic surfactant acid precursor or more than.

[14]. a kind of granular detergent composition, it is characterized by any surface-treated particle of water-soluble inorganic compound of being put down in writing of containing in (a) [1]～[10] and, (b) contain the particle of tensio-active agent, it contains tensio-active agent and mineral compound.

[15] .[14] granular detergent composition put down in writing, it is characterized by at (b) and contain in the particle of tensio-active agent, contain water-soluble high-molecular compound.

[16] .[14] or [15] granular detergent composition of being put down in writing, the use level that it is characterized by the slightly water-soluble compound in (a) surface-treated particle of water-soluble inorganic compound is less than 10 quality %, and the use level that (b) contains the tensio-active agent in the particle of tensio-active agent is 10～50 quality %.

[17]. a kind of washing methods, it is characterized by with an any washing bath that contains surface-treated particle of water-soluble inorganic compound and the washes of being put down in writing that contains in [1]～[10], with bath raio 7～15L/kg, wash temperature is washed for 5～12 ℃.

The simple declaration of accompanying drawing

The 1st figure is the caloric receptivity of the dissolving of display surface treating part when disperseing and the graph of a relation of the maximum temperature rising degree that obtained by the mensuration of wetting thermal value.

Embodiment

Surface-treated particle of water-soluble inorganic compound of the present invention is with the organic or inorganic water-soluble high-molecular compound water-soluble inorganic compound nuclear particle to be carried out surface treatment, and further the water insoluble chemical compound is handled the particle that forms again to this surface treated.

Water-soluble inorganic compound

Water-soluble inorganic compound of the present invention is for having a 1g/100g or bigger in the time of 5 ℃, preferred 2g/100g or bigger, more preferably the water-soluble mineral compound of 3g/100g or bigger water solubility.If such water-soluble mineral compound, there is no particular limitation, can be independent a kind or two or more suitably be used in combination.

As preferred water-soluble inorganic compound, can enumerate general conduct and clean the compound that component is used.As such compound, can enumerate carbonate, supercarbonate and sesquicarbonate class, vitriol and sulfites, phosphoric acid salt and polyphosphoric acid salt, silicate, nitrate and nitrites, muriate etc.Wherein, preferred carbonate, Sulfates, polyphosphoric acid salt, preferred especially yellow soda ash, salt of wormwood, sodium sulfate, vitriolate of tartar, tripoly phosphate sodium STPP.

As water-soluble inorganic compound, to cleaning the contribution of ability, the pH value that can be more suitable for using 5 ℃ saturated aqueous solution is 8 or higher water-soluble alkali inorganic salt.

Further, also can be fit to water-soluble alkali inorganic salt and other the composite salt of water-soluble alkali inorganic salts in addition, for example, the burkeite of the composite salt of yellow soda ash and sodium sulfate (burkeite) etc. is exactly its representational example.The water-soluble alkali inorganic salt can be independent a kind or two or more suitably be used in combination.

The occasion of water-soluble inorganic compound wetting formation cohesion piece under weak whipped state has very dark relation with the condensing of hydrate crystal of water-soluble alkali inorganic salt.Preferred the present invention is applicable to for the material that becomes hydrate crystal under the temperature of 20 ℃ of less thaies easily.As such a material most preferably is neutral inorganic such as alkaline, inorganic salts such as yellow soda ash, salt of wormwood and sodium sulfate.

The water-soluble inorganic compound nuclear particle can obtain by common method, its median size, preferred 100～1500 μ m, more preferably 200～1000 μ m.During median size less than 100 μ m, exist and carry out the inconvenient situation of surface treatment, surpass 1500 μ m, then have the situation of the solvability reduction of water-soluble inorganic compound by water-soluble high-molecular compound.Such water-soluble inorganic compound nuclear particle can use and sell on the market.Have, median size gets according to the assay method of putting down in writing among the embodiment described later again.

In the water-soluble inorganic compound nuclear particle available on the market, various grades are arranged, of the present invention utilize unqualified.For example, contain the impurity of sneaking in the manufacturing engineering and be also contained in the scope of the present invention for the preserving stabilizer of guaranteeing the quality and the water-soluble alkali inorganic salt of oxidation inhibitor.

The organic water-soluble macromolecular compound

The organic water-soluble macromolecular compound of the 1st used surface treatment agent in the surface treatment as above-mentioned water-soluble inorganic compound, be 40 ℃ for 100g water with 0.1g or more, preferred 0.2g or more, more preferably 2g or more concentration and water homogeneous blended macromolecular compound.If such organic water-soluble macromolecular compound, there is no particular limitation, can be independent a kind or two or more suitably be used in combination.

As the organic water-soluble macromolecular compound, can enumerate natural high moleculer eompound, semi-synthetic macromolecular compound and synthetic macromolecular compound etc.Particularly, can use vinyl macromolecular compound, polyose, polyethers macromolecular compound, polyester macromolecular compound, peptide family macromolecule compound, urethane and derivative thereof etc.Wherein, preferably from vinyl macromolecular compound, polyose, its derivative and polyester macromolecular compound, select a kind or two or more appropriate combination uses.

As the vinyl macromolecular compound, for example, can enumerate ethylene-like polymer metal carboxylate (acrylic polymer compound), ethylene-like polymer sulfonate, polyvinyl pyridine salt, polyvinyl imidazole _ salt (imidazoluim) etc.As polyose, can use various natural or synthetic polyoses.

As the polyester macromolecular compound, for example, can enumerate unitary multipolymer of terephthalic acid and ethylene glycol and/or propylene glycol or trimer etc.As such example, the Texcare4291 that sells on the market (manufacturing of Clariant company), TexcareSRN-300 (manufacturing of Clariant company) etc.

As the object lesson of peptide family macromolecule compound or derivatives thereof, can enumerate gelatin, casein, albumin, collagen, polyglutamate, polyaspartic acid salts, polylysine, poly arginine and derivative thereof etc.

As urethane, for example, can enumerate aqurous ployurethane etc.In addition, other water-soluble high-molecular compounds such as polyoxyethylene glycol also can use.

Especially, from the easy hydration this point of water-soluble inorganic compound, water-soluble inorganic compound is being carried out preferably bringing into play the immersion effect in the initial stage that contacts with water under the surface-treated state with water-soluble organic macromolecule compound.As water-soluble organic macromolecule compound, can enumerate hydrophilic functional groups' such as having anionic property, both sexes, nonionic material with such characteristic.

As water-soluble organic macromolecule compound, for example, can enumerate the macromolecular compound with carboxyl, sulfo group, water-soluble polysaccharides with anionic property base with anion-radicals.

As water-soluble organic macromolecule compound with carboxyl, for example, can enumerate polymkeric substance and salt thereof that monomer polymerizations such as making vinylformic acid, toxilic acid, methylene-succinic acid, equisetic acid, methylacrylic acid, fumaric acid, 2-hydroxyl acrylic, citraconic acid becomes, and the ethylene-like polymer carboxylic acid (salt) of the multipolymer of these monomers and other vinyl monomer and salt thereof etc.

As water-soluble high-molecular compound with sulfo group, for example, can enumerate the polymkeric substance and the salt thereof of the monomer polymerization one-tenth that makes acrylamide propanesulfonic acid (methacrylamidepropanesulfonic acid), Methacrylamide propanesulfonic acid, styrene sulfonic acid etc., and the ethylene-like polymer sulfonic acid (salt) of the multipolymer of these polymkeric substance and other polyvinyls and salt thereof etc. etc.

As water-soluble polysaccharides, for example, can enumerate polysaccharide aldehyde, alginate, polyaspartic acid salts, carrageenan, hyaluronate, chondroitin sulfate, carboxymethyl cellulose etc. with anionic property base.

As the amphoteric water-soluble macromolecular compound, for example, can enumerate vinyl monomer and have the multipolymer of the vinyl monomer of cationic base, Amphiphatic high polymer with carboxybetaine base or sultaine base vinyl with anionic property base, particularly, can enumerate vinylformic acid/copolymer of dimethylaminoethyl methacrylate, vinylformic acid/diethylaminoethyl methacrylate multipolymer etc.

As the nonionic water-soluble high-molecular compound, polyoses such as synthetic macromolecular compounds such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ethyl ether, polyoxyethylene glycol, Natvosol, guar gum, dextran, pullulan for example.

In the middle of this, preferably good in the initial stage immersion effect that contacts with water, the compound of dissolving or heating when disperseing in water.Consider this point, the preferred polyvinyls that uses with carboxyl or sulfo group, the ethylene-like polymer carboxylic-acid that the anionic property base content of per unit mass is high is suitable especially.

Particularly, the salt of the salt of the salt of polyacrylate, vinylformic acid/maleic acid, vinylformic acid/itaconic acid copolymer, alkyl acrylate copolymer and these derivative etc. are the most suitable.

The weight-average molecular weight of organic water-soluble macromolecular compound of the present invention is 500 or higher, and is preferred 1,000～1,000,000, more preferably 1,000～200,000.Have, the molecular-weight average of macrogol is represented the molecular-weight average of cosmetic material benchmark (the 2nd edition note) record among the present invention again.Have, organic water-soluble macromolecular compound weight-average molecular weight is for being the measured value that reference material obtains according to gel permeation chromatography with the macrogol among the present invention again.

As with the organic water-soluble macromolecular compound water-soluble inorganic compound being carried out the surface-treated method, there is no particular limitation.For example, can enumerate in water-soluble inorganic compound the method for adding, mix or being coated with the machine water-soluble high-molecular compound etc.The organic water-soluble macromolecular compound is suitable as the aqueous solution and is used for surface treatment.This aqueous solution of interpolation preferably splashes in the water-soluble inorganic compound that stirs the fluidization state or sprays.

Inorganic water-soluble high-molecular compound

On the other hand, inorganic water-soluble high-molecular compound is at 40 ℃, and with 0.1g or more, preferred 0.2g or more is more preferably with 2g or higher concentration and water homogeneous blended compound for 100g water.If such inorganic water-soluble compound, there is no particular limitation, can independent a kind or two or more appropriate combination uses.As inorganic water-soluble high-molecular compound, the solution hydrolysis condensation reaction that preferably will contain the precursor compound of metal alkoxide obtains, preferred especially silicate.

Silicate just is engaged in the soap since ancient times, as water glass and known, according to its structure, can be according to anionic typoiogical classification (the Friedrich Liebau that classifies, " Structural Chemistry of Silicates " 72 pages, Springer-Verlag, distribution in 1985).

At length, available crosslinked oxygen number (Si-O-Si) with Si bonded oxygen is classified, corresponding to its crosslinked oxygen several 4,3,2,1,0 can be categorized as Q4, Q3, Q2, Q1, Q0 unit (Y.Tsunawaki respectively, N.Iwamoto, T.Hattori and A.Mitsubishi, J.Non-Cryst.Solids, the 144th volume, 369 pages (1981)).

As silicate, from giving full play to this point of treatment effect, preferably comprise Q2 unit and/or Q3 unit, have SiO ₂/ M ₂O mol ratio (M represents basic metal here) is 1.6～4, preferred 2～3.5 alkalimetal silicate, preferred especially water glass.

As with inorganic water-soluble high-molecular compound water-soluble inorganic compound being carried out the surface-treated method, there is no particular limitation.For example can enumerate in water-soluble inorganic compound add, mix or bag by the method for its inorganic water-soluble high-molecular compound etc.Inorganic water-soluble high-molecular compound is suitable as the aqueous solution and is used for surface treatment.This aqueous solution of interpolation preferably splashes in the water-soluble inorganic compound that stirs the fluidization state or sprays.

The slightly water-soluble compound

Used slightly water-soluble compound among the present invention is at 20 ℃, to the not enough 2g/100g of solubleness of water, and preferred not enough 1g/100g, the more preferably compound of not enough 0.1g/100g, preferably the initial stage that contacts with water has the compound of hydrophobic interaction.In addition, have 200 ℃ or lower, preferred 0～160 ℃, more preferably 20～80 ℃, most preferably the organic compound of 40～60 ℃ fusing point is suitable.The slightly water-soluble compound can appropriate combination uses a kind or two or more.

As the slightly water-soluble compound, for example can enumerate higher fatty acid, dicarboxylic acid, higher alcohols, HLB5 or lower, preferred 3 or the glyceryl ester of the oxirane adducts of lower higher alcohols or higher fatty acid, high-grade aliphatic ester, higher fatty acid etc.

As higher alcohols, have carbonatoms 12～22, more preferably the alcohol of the carbon chain length of carbonatoms 14～18 is suitable, particularly, can enumerate dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol etc.

As HLB5 or lower, preferred 3 or the lower higher alcohols or the oxirane adducts of higher fatty acid, 1～3 moles of ethylene oxide adducts of the alcohol of carbonatoms 16～22 or lipid acid is suitable, particularly, can enumerate 1 moles of ethylene oxide adducts of cetyl alcohol, 3 moles of ethylene oxide adductss of Stearyl alcohol, 1 moles of ethylene oxide adducts of palmitinic acid etc.

As high-grade aliphatic ester, the methyl esters of palmitinic acid, tetradecanoic acid, stearic acid, eicosanoic acid, docosoic acid etc. or ethyl ester etc. are suitable.

As the glyceryl ester of higher fatty acid, lauric acid, palmitinic acid, stearic acid etc. single, two or Witepsol W-S 55 be suitable.

Have again, heat absorption is with the heating of control water-soluble inorganic compound when wetting in the early stage, along with washing is set out by becoming water-soluble this point with the neutralization reaction of water-soluble inorganic compound etc. at leisure,, preferably use anionic surfactant acid precursor as the slightly water-soluble compound.

As anionic surfactant acid precursor, anionic surfactant acid precursor is all applicable arbitrarily.Acid precursor as anion surfactant, can enumerate saturated or unsaturated fatty acids (average carbon chain length 8～22), straight or branched alkyl (average carbon chain length 8～18) Phenylsulfonic acid, chain alkyl (average carbon chain length 10～20) sulfonic acid, long-chain olefin (average carbon chain length 10～20) sulfonic acid, long-chain monoalkyl (average carbon chain length 10～20) sulfuric ester, polyoxyethylene (mean polymerisation degree 1～10) chain alkyl (average carbon chain length 10～20) ether sulfuric ester, polyoxyethylene (mean polymerisation degree 3～30) alkyl (average carbon chain length 6～12) phenylate sulfuric ester, alpha-sulfo-fatty acid (average carbon chain length 8～22), the long-chain monoalkyl, dialkyl group or sesquialter alkyl phosphate, the polyoxyethylene monoalkyl, dialkyl group or sesquialter alkyl phosphate etc.

As anionic surfactant acid precursor, preferred saturated or unsaturated fatty acids (average carbon chain length 8～22), more preferably have carbonatoms 8～18 carbon chain length.Particularly, can enumerate saturated fatty acids such as capric acid, lauric acid, tetradecanoic acid, palmitinic acid, unsaturated fatty acidss such as oleic acid etc., in the middle of this, from the viewpoint of storage stability, the saturated fatty acid of preferred carbonatoms 12～18, as consider manufacturing, more preferably lauric acid then.

As to handled the water-soluble inorganic compound on surface with the 1st surface treatment agent, further the method for water insoluble chemical compound treat surface is not particularly limited.For example, can enumerate in surface-treated water-soluble inorganic compound add, the mixing water insoluble chemical compound, or bag is by its method etc.It is liquid that the fusion of slightly water-soluble compound is become, and this liquid is splashed into or sprays and add to advance to be in method in the surface-treated water-soluble inorganic compound that stirs flow state.

Each components matching amount in the surface-treated particle of water-soluble inorganic compound of the present invention is as follows.

The preferred use with respect to the surface-treated particle of water-soluble inorganic compound total amount is 60～99.8 quality %, especially preferably uses the water-soluble inorganic compound of 70～97 quality %.During water-soluble inorganic compound less than 60 quality %, exist, on the other hand,, then exist the amount of treatment agent just to become very little, can not finish the surface-treated situation as surpassing 99.8 quality % as the sufficient inadequately situation of alkaline agent.

The preferred use with respect to the water-soluble inorganic compound nuclear particle is 0.1～10 quality %, especially preferably uses the organic water-soluble macromolecular compound of 0.5～8 quality %.During less than 0.1 quality %, existence can not obtain the situation of surface-treated effect, surpasses 10 quality %, then has can become very little situation of the use level of mineral compound.

Cooperating the occasion of inorganic water-soluble high-molecular compound, the preferred use with respect to the water-soluble inorganic compound nuclear particle is 1～30 quality %, especially preferably uses the inorganic water-soluble high-molecular compound of 10～28 quality %.During less than 1 quality %, existence can not obtain the situation of surface-treated effect, when surpassing 30 quality %, has can become very little situation of the use level of mineral compound.

The preferred use with respect to handle surperficial water-soluble inorganic compound nuclear particle with the 1st surface treatment agent is 0.1～10 quality %, especially preferably uses the slightly water-soluble compound of 2～8 quality %.During less than 0.1 quality %, existence can not obtain the situation of surface-treated effect, when surpassing 10 quality %, has can become very little situation of the use level of mineral compound.

Have again,, in the scope of not damaging effect of the present invention, also can contain tensio-active agent and become to grade arbitrarily with the particulate that (b) described later contains tensio-active agent as other compositions.

Surface-treated particle of water-soluble inorganic compound

Surface-treated particle of water-soluble inorganic compound of the present invention carries out surface treatment with the organic or inorganic water-soluble high-molecular compound to the water-soluble inorganic compound nuclear particle, and further, the water insoluble chemical compound is handled its surface treated.Surface of the present invention is to comprise that the primary particle surface of particle of water-soluble inorganic compound or granulation make about 2～30 1 particle condense into one particle of water-soluble inorganic compound group's (contain 2 particle or flocculated particle) any one of full surface.Have, in the occasion that becomes the particle of water-soluble inorganic compound group, the small concave depth on surface is 0.01～50 μ m again.

On the surface of water-soluble inorganic compound nuclear particle, there are the water-soluble high-molecular compound form layers in water-soluble high-molecular compound and slightly water-soluble compound on the surface of water-soluble inorganic compound nuclear particle, can there be the slightly water-soluble compound in its skin, also can become chaotic randomly state.From the viewpoint of solvability and storage stability, preferably in the existence of the outermost layer slightly water-soluble compound of surface-treated particle of water-soluble inorganic compound more than water-soluble high-molecular compound.Viewpoint from manufacturing is arranged again, preferably in the existence of the near surface water-soluble high-molecular compound of water-soluble inorganic compound nuclear particle more than the slightly water-soluble compound.

The special preferred structure of surface-treated particle of water-soluble inorganic compound is to have part or all surface on water-soluble inorganic compound nuclear particle and its particle surface to go up the structure that contains the 2nd surface treatment of slightly water-soluble compound on the 1st surface treatment that contains water-soluble high-molecular compound of forming and part or all surface on the 1st surface treatment.

Particularly the particle of water-soluble inorganic compound of carboxylate salt etc. can become alkalescence usually when contacting with water and water-soluble polymer solution.Therefore, the slightly water-soluble compound is the occasion of the acid precursor of anion surfactants such as higher fatty acid, is neutralized on particle surface by the 2nd surface treatment.In the many occasions of amount of the acid precursor of the anion surfactant that adds, a part can not cause neutralization reaction, and gets off so that the form of acid precursor is remaining.The neutral condition of the acid precursor of anion surfactant also can wait and examine or check with differential scanning calorimetry (Differential Scanning Calorimetry).Like this, because have in complete neutral occasion of the acid precursor of particle surface anion surfactant and part neutral occasion, though utilize acid precursor and/or its salt formation the 2nd surface treatment of anion surfactant, no matter which occasion all is suitable for utilization as the surface-treated particle of water-soluble inorganic compound among the present invention.

Have again, as other compositions on the 1st surface treatment and the 2nd surface treatment, in the scope of not damaging effect of the present invention, also can suitably contain binding agent, dispersion agent, solubilizing agent, pH regulator agent, slightly water-soluble compound various additives such as tensio-active agent in addition.Containing the occasion of tensio-active agent, in the surface-treated particle of water-soluble inorganic compound, preferred less than 10 quality %, more preferably 5 quality % or lower, most preferably 1 quality % or lower.In addition, the lipid acid that cooperates as the slightly water-soluble compound etc. is not contained in the use level of the tensio-active agent in the surface-treated particle of water-soluble inorganic compound.

Among the present invention, further, the 1st surface treatment has shown heat generation in to the dissolving of water or dispersion process, above-mentioned the 2nd surface treatment has shown heat absorptivity in to the dissolving of water or dispersion process, the full surface treatment that preferred the 1st surface treatment and the 2nd surface treatment form shows heat absorptivity in to the dissolving of water or dispersion process.

Owing to have such characteristic, the condensation product that forms between inhibition water-soluble inorganic compound nuclear particle and the detergent particles, be suppressed at the dissolving heating of the initial stage water-soluble inorganic compound of contact water at low temperature, and in the washing that adds whipping force, although under weak stirring, also can demonstrate fast dissolution characteristics significantly.

Can do following consideration about the condensation product that forms between water-soluble inorganic compound nuclear particle and the detergent particles, in granular detergent composition, do and mix such water-soluble inorganic compound, owing to contact many violent heatings with water.For example, the solution heat of yellow soda ash is-24.57kJ/mol (General Chemical Industrial Products company, SODAAsh Technical ﹠amp; Handling Guide record), the hydration heat of sodium sulfate is-79.58kJ/mol (chemical brief guide record), this is in the dissolution process of water-soluble inorganic compound to water, the heating that is caused by hydration is very big, because the characteristic that the heating that the hydration of formation mineral ion causes is given birth to more than the induced labor of the much bigger institute of the desired heat absorption of the destruction of the lattice of mineral compound.

Water-soluble inorganic compound and detergent particles with such characteristic are supplied with rinse bath together, as long as make it become wetting regime by water at low temperature, will acutely generate heat, and near the temperature the particle rises.This temperature rises, and makes detergent particles nearby be changed to the liquid crystal shape from solid on the one hand and causes gelation, has also promoted the dissolving of mineral compound self on the other hand, has formed oversaturated dissolved state in the part.Mineral compound under this oversaturated dissolved state cools off before stirring with a large amount of water as with water at low temperature, and then condensing becomes crystal of hydrate.Therefore, formed the cohesion piece of the detergent particles that is involved in gelation.

In order to suppress the formation of this cohesion piece, the heating the when water-soluble inorganic compound that suppress to become the gelation of detergent particles and hydration agglomerative reason effectively dissolves in water.That is, be necessary to have the hydration of the water-soluble inorganic compound that generates heat in the dissolution process capable of blocking, or deprive the processing of the such characteristic of heating that hydration produces.On the other hand because heating promotes dissolution process effectively, for guaranteeing in the washing dissolved characteristic rapidly, complete closed and water to contact or all deprive the such processing of hydration heat be unsuitable.

For the time both take into account, the 1st surface treatment has shown heat generation in to the dissolving of water or dispersion process, above-mentioned the 2nd surface treatment has shown heat absorptivity in to the dissolving of water or dispersion process, because the full surface treatment that the 1st surface treatment and the 2nd surface treatment form shows heat absorptivity in to the dissolving of water or dispersion process, controlled the dissolving heating of water-soluble inorganic compound nuclear particle, and, in the washing that adds whipping force, although under weak stirring, also can provide dissolution characteristics rapidly.

The 1st surface treatment has shown heat generation in to the dissolving of water or dispersion process, above-mentioned the 2nd surface treatment has shown heat absorptivity, and concrete heat is different and different according to the balance of kind, treatment capacity, the 1st surface treatment and the 2nd surface treatment of the treatment agent that uses, treatment condition.The heat of the full surface treatment that the 1st surface treatment and the 2nd surface treatment form absorbs heat preferred 30～80J/g particle, more preferably 40～70J/g particle.In addition, the J/g particle refers to the heat (J) (the following description too) of every inorganic compound particle 1g.

Have, the 1st surface treatment shows the immersion effect again, and the 2nd surface treatment shows that hydrophobicity is fit to.In this occasion, preferably be controlled at the wetting speed of the initial stage that surface-treated particle of water-soluble inorganic compound contacts with water.

That is because wetting speed is influence the dissolution time chief reason, even the treating part to the dissolving of water or the heat when disperseing absorb heat, if wetting speed is too fast, the dissolving that becomes the water-soluble inorganic compound of nuclear will be carried out.Its result, the water-soluble inorganic compound of superfluous stripping is exposed to the regelation that causes crystal of hydrate in the water at low temperature, can form the cohesion piece.On the other hand, cause the slow excessively occasion of wetting speed,, have not exclusively dissolved situation of surface-treated particle of water-soluble inorganic compound former state ground owing to hindered dissolving itself in the hydrophobic interaction surplus.

According to above reason, further, more preferably has the treating part of the wetting speed in the certain limit.

Usually, wetting speed changes with the different of test portion amount according to measuring method, in the present invention, in the occasion of measuring according to the Washburn method that describes in detail later, the every 0.5g of surface-treated particle of water-soluble inorganic compound by wetting speed wetting and that capillary phenomenon causes, in the scope between preferred 100～400 minutes, more preferably in the scope between 200～400 minutes.

The physical property values of surface-treated particle of water-soluble inorganic compound of the present invention has no particular limits, and loose density is generally 0.3g/cm ³Or higher, preferred 0.5～1.4g/cm ³, more preferably 0.6～1.2g/cm ³No matter loose density excessive or too small also exist in to mix with other particles use the time stage easy situation that all can become.Preferred 200～2000 μ m of median size, more preferably 300～1500 μ m are arranged again.As median size less than 200 μ m, specific surface area is excessive, and existence may be not easy to obtain to suppress the situation of the effect of hydration, on the other hand, as surpassing 2000 μ m, then exists the solvability of surface-treated particle of water-soluble inorganic compound itself to understand the situation of variation.Further, preferred slope of repose is below 70 °, more preferably below 50 °.There is the situation of particulate operability difference in the slope of repose as crossing 70 °.Have, the mensuration of loose density and median size is carried out according to the method for embodiment record described later again.

Moisture in the surface-treated particle of water-soluble inorganic compound, from viewpoint for the curing (caking) preventing to store, preferred 8 quality % or lower, more preferably 7 quality % or lower, preferred especially 6 quality % or lower.Have, the amount of moisture among the present invention is measured with predetermined heating decrement method among the JISK3362-1998 again.

The manufacture method of surface-treated particle of water-soluble inorganic compound

Below, describe in detail with regard to the manufacture method of surface-treated particle of water-soluble inorganic compound of the present invention.The manufacture method of surface-treated particle of water-soluble inorganic compound of the present invention comprises the 1st following operation and the 2nd operation.

The 1st operation: in the water-soluble inorganic compound nuclear particle, add the water-soluble high-molecular compound aqueous solution, the water-soluble inorganic compound nuclear particle is carried out the surface-treated operation by water-soluble high-molecular compound.

The 1st operation is to add the water-soluble high-molecular compound aqueous solution in the water-soluble inorganic compound nuclear particle, by water-soluble high-molecular compound the water-soluble inorganic compound nuclear particle is carried out the surface-treated operation.

The water-soluble inorganic compound nuclear particle is filled in granulating and coating described later (coating) device, adds the water-soluble high-molecular compound aqueous solution therein, carry out surface treatment.

The water-soluble high-molecular compound aqueous solution, occasion at the organic water-soluble macromolecular compound is generally 0.1～90 quality %, preferred 0.5～80 quality %, more preferably 1～60 quality %, viscosity (using 25 ℃ measured value of Brookfield type viscosity agent) is 0.001～100Pas, the organic water-soluble macromolecular compound aqueous solution of preferred 0.0005～50Pas.In the occasion of inorganic water-soluble high-molecular compound, be generally 1～60 quality %, preferred 5～55 quality %, the more preferably inorganic water-soluble high-molecular compound of 10～50 quality %.The interpolation water inlet solubleness high molecular compound aqueous solution preferably splashes in being in the water-soluble inorganic compound nuclear particle that stirs the fluidization state or sprays.

The 2nd operation is to add the slightly water-soluble compound in the 1st operation treated water dissolubility mineral compound nuclear particle, and above-mentioned particle is carried out the surface-treated operation.

To be filled in granulation bag described later by in the device with the 1st operation treated water dissolubility mineral compound nuclear particle, add the slightly water-soluble compound therein, carry out surface treatment.Preferably in being in usefulness the 1st operation treated water dissolubility mineral compound that stirs flow state, splash into or spray to add and advance as the liquid slightly water-soluble compound of fused.

In the above-mentioned the 1st and the 2nd operation,, can enumerate following method as with the concrete granulation method for coating of water-soluble inorganic compound nuclear particle.(1). in the water-soluble inorganic compound nuclear particle, add (water-soluble high-molecular compound, slightly water-soluble compounds) such as treatment agents, with the method for stirring blade stirring-granulating bag quilt; (2) on one side. the water-soluble inorganic compound nuclear particle is rotated, Yi Bian the treatment agent of spraying etc. carry out the rotation comminution granulation of granulation bag quilt; (3). the water-soluble inorganic compound nuclear particle is flowed, Yi Bian the treatment agent of spraying etc. carry out the fluidized bed granulation of granulation bag quilt etc. on one side.

Above-mentioned the 1st operation, reaching the 2nd operation can carry out with same granulation method for coating and device respectively, also can be with several granulation method for coating and device combination.Below, various methods, manufacturing installation, condition etc. are described.

(1). the stirring-granulating method

The stirring-granulating method can be used the stirring-granulating device of arbitrary form.Wherein, preferably the stir shaft that is equipped with paddle is arranged, form the device of the structure in gap when stirring blade rotates between stirring blade and the wall of container in inside center.Preferred 1～the 30mm in gap, more preferably 3～10mm.The not enough 1mm in gap can be because adhesion layer transships mixing machine easily.Surpass 30mm, then because the decrease in efficiency that compresses, exist size-grade distribution broaden, in addition the granulation time elongated, the situation that throughput reduces.As stirring granulating machine, for example, can enumerate Henschel (Henschel) mixing machine (manufacturing of Mitsui three pond chemical industry machines (strain)), high-speed mixer (dark river industry (strain) is made), vertical granulator devices such as ((strain) Powrex manufacturings) with this spline structure.The tempering tank that especially preferably has transverse mode has stir shaft at the center of cylinder, and this stir shaft has the mixing machine that stirring blade carries out the mixed form of powder.As such mixing machine, for example, Loedige mixing machine ((strain) Mastubo manufacturing), PloughShare mixing machine (Pacific Ocean machine worker (strain) manufacturing).

The granulation condition that is fit in the stirring-granulating method is as follows.

(i) Froude number (Fr number)

About the stirring-granulating method, preferred 1～16 with following formula defined Froude number, more preferably 2～9.As Froude number less than 1,, there is the inadequate situation of surface treatment because fluidization is insufficient.On the other hand, then excessive as surpassing 16 for the particulate shearing force, there is the ruined situation of surface treating part branch.

Fr＝V ²/(R×g)

V: the circumferential speed of the end of stirring blade (m/s)

R: the rotation radius of stirring blade (m)

G: universal gravity constant (m/s ²)

(ii) cutting knife rotation number

In the stirring-granulating method, in the stirring granulating machine that uses,, be equipped with the cutting knife of high speed rotating for promoting compressing and the meal pulverizing of particulate matter.As the speed of rotation of cutting knife, the rotation number of the destroyed degree of surface treatment does not preferably take place.The speed (circumferential speed) of preferred cutting knife end is 30m/s or lower, more preferably 0～20m/s or lower.

(iii) granulation time

In the stirring-granulating method, preferred 0.5～20 minute of the average retention time in the granulation time in the granulation of intermittent type and the granulation of continous way, more preferably 3～10 minutes.Granulation time (residence time) less than 0.5 minute, the time is too short, for the granulation control that obtains suitable median size and loose density becomes difficult, the situation that exists size-grade distribution to broaden.Surpass 20 fens, overlong time, the situation that has throughput to descend.

The (iv) filling ratio of water-soluble inorganic compound nuclear particle

In the stirring-granulating method, as the filling ratio (add-on) of water-soluble inorganic compound nuclear particle to tablets press, below the 70 volume % of the full internal volume of preferred mixing machine, more preferably 15-40 volume %.Filling ratio (add-on) surpasses 70 volume %, has the mixing efficiency in mixing machine to reduce, and is unsuitable for carrying out the situation existence of granulation.

(the v) addition means of treatment agent

In the stirring-granulating method, for being in the particle that the stirs flow state treatment agents such as adding the water-soluble high-molecular compound aqueous solution, slightly water-soluble compound that preferably splash into or spray.In the particle of stationary state, splash into or add after the treatment agent etc., begin to stir, also can be operated by the granulation bag.But, for improving bag, preferably for the particle that the stirs flow state interpolation that splashes into or spray by property.

(2). rotate comminution granulation

The rotation comminution granulation can use the rotation prilling granulator of arbitrary form.Wherein, the form of the cylinder rotation treatment of preferred cylinder shape particularly preferably possesses the form of the baffle plate of arbitrary shape.As the cylinder type tablets press; can enumerate horizontal circle tubular tablets press, Japanese powder industry technological associations compile, and circular cone cylinder type tablets press, the multi-level cone cylinder type tablets press of record in the 1st edition the 1st printing of granulation handbook, have the cylinder type tablets press of stirring blade etc.

The suitable granulation condition of rotating in the comminution granulation is as follows.

(i) treatment time

Treatment time in the intermittent type, the average retention time in the continous way, preferred 5～120 minutes, more preferably 10～90 minutes, preferred especially 10～40 minutes with the following formula definition.As above-mentioned deficiency of time 5 minutes, can not obtain high loose density, as surpassing 120 fens, then throughput descends or particle destroys.

Tm＝(m/Q)×60

Tm: average retention time (min)

M: the particle hold-up (kg) in the rotary-type mixing machine of container

Q: the ability in the continuous operation (kg/hr)

(ii) Froude number (Fr)

Froude number with the following formula definition preferably becomes 0.01～0.8 condition.Froude number 0.05～0.7, more preferably 0.1～0.65.As Froude number less than 0.01, can not get the particle of homogeneous and high bulk density, on the other hand, as surpassing 0.8, in the occasion of cylinder type mixing machine, particle can disperse, and can not cause to cut off normally and mix.

Fr＝V ²/(R×g)

V: the circumferential speed (m/s) of the rotary-type mixing machine most peripheral of container

R: from the radius (m) of the thoughtful rotation center of the rotary-type mixing machine outermost of container

G: universal gravity constant (m/s ²)

(iii) volume filling ratio (X)

With the volume filling ratio of following formula definition, preferably become the condition of 15～50 volume %.The volume filling ratio is 20～45 volume % more preferably, preferred especially 25～40 volume %.As volume filling ratio less than 15 volume %, throughput is bad, on the other hand, as surpassing 50 volume %, then can not produce and good cut off and mix.

Volume filling ratio (X)=(M/ ρ)/V * 100

M: the charging capacity (g) of the water-soluble inorganic compound nuclear particle in the rotary-type mixing machine of container

ρ: the loose density of water-soluble inorganic compound nuclear particle (g/L)

V: the volume of the rotary-type mixing machine of container (L)

The (iv) interpolation way of treatment agent

In rotating comminution granulation, add treatment agents such as the water-soluble polymer aqueous solution, slightly water-soluble compound for the particle spraying of rotational flow.After in the particle that remains static, splashing into or adding treatment agent etc., begin to stir, also can be operated by the granulation bag.But, for improving bag, preferably for the particle that the stirs flow state interpolation that splashes into or spray by property.

(3) fluidized bed granulation

In fluidized bed granulation, can use the fluid bed granulation unit that constitutes by fluidized-bed body, propeller, fan, air-breathing strainer, airheater and water cooler, spraying plant, particle collector etc. of arbitrary form.For example, Japan powder technology association compiles, and the intermittent type fluid bed granulation unit (top spraying type, side spray formula, end spraying type etc.) of record in the 1st edition the 1st printing of granulation handbook, jet flow fluid bed granulation unit, spray fluid bed granulation unit, semi continuous fluid bed granulation unit (formula, sidewall discharge formula etc. are got rid of in breaker plate counter-rotating discharge formula, bottom), continous way fluidized granulator (horizontal type multiple-chamber type, round shape etc.) are all applicable.As the example that utilizes of concrete device, can enumerate the MIXGRAD series [the former making manufacturing in (strain) great river] of the Glatt-POWREX series [(strain) POWREX manufacturing] of intermittent type fluidized granulator, mobile dressing machine series [the former making manufacturing in (strain) great river], continous way fluidized granulator etc.

As the granulation condition in the thermopnore comminution granulation, the thickness of preferred raw material powder layer when static is about 50～500mm.Then, after fluidised bed is blown, is made flow of powder, treatment agents such as the beginning spray water solubleness high molecular compound aqueous solution, slightly water-soluble compound.As spray nozzle, good for making body spray except that common pressurized nozzles, preferably use 2 fluid tips.About preferred 5～500 μ m of droplet mean diameter at this moment.Because along with the granulation of carrying out of spraying also becomes big carrying out particle diameter, while will adjust wind speed and carry out granulation in order to keep the fluidization state.Wind speed is adjusted in the scope of 0.2～4.0m/s, the wind-warm syndrome degree is 5～70 ℃, preferred 7～65 ℃.Preferred regularly the removing with pulse of air on one side made on one side attached to the microparticle on the bag dust filter.

In the occasion made from the manufacture method of above-mentioned surface-treated particle of water-soluble inorganic compound, the temperature of the surface-treated particle of water-soluble inorganic compound after the 2nd operation one finishes is preferably more than the fusing point of anionic surfactant acid precursor.Particularly, when in the 2nd operation, adding the slightly water-soluble compound, preferably to note the temperature of treated water dissolubility mineral compound nuclear particle in the 1st operation.Particularly, preferably make more than the fusing point of this particulate temperature than slightly water-soluble compound.In addition, when adding the slightly water-soluble compound, during the fusing point of not enough this slightly water-soluble compound of the temperature of treated water dissolubility mineral compound nuclear particle, the temperature of the surface treatment water-soluble inorganic compound nuclear particle after preferably the surface treatment that is caused by the slightly water-soluble compound finishes is more than the fusing point of slightly water-soluble compound in the 1st operation.If this temperature is lower than fusing point, the granulation bag is by the dispersed homogeneity variation of the slightly water-soluble compound in the device, and the slightly water-soluble compound causes surface treatment insufficient.

The surface-treated particle of water-soluble inorganic compound that obtains with above-mentioned method also can further carry out surface treatment with the fine powder of organic or inorganic.As surface-treated particle of water-soluble inorganic compound is further carried out the surface-treated fine powder, can enumerate normal temperature solid tensio-active agent, hard soap, aluminosilicate, oil-absorbing carrier, clay mineral etc.

As tensio-active agent, can enumerate anion surfactant, cats product, nonionogenic tenside.As hard soap, can enumerate alkali, non-alkali-metal hard soap, as aluminosilicate, A type, P type, X type etc. are arranged, as oil-absorbing carrier, silica, silicate compound, the moisture uncrystalline silicon hydrochlorate of spherical porous matter etc. are arranged, can enumerate montmorillonite, nontronite, beidellite, pyrophyllite, saponite, hectorite, rich magnesium montmorillonite, talcum etc. as clay mineral.These can independent a kind or two or more uses of appropriate combination.Wherein, preferred non-alkali-metal hard soap, talcum, aluminosilicate.Because non-alkali-metal hard soap and talcum are hydrophobic, so prevent the cohesion of water-soluble inorganic compound, aluminosilicate is as the component of catching Ca and general, be used for the surface-treated occasion separately, playing effect as the treatment agent on the surface of mixed detergent particles.

The particle diameter of these fine powders for the median size of surface-treated particle of water-soluble inorganic compound, preferably has 1/5 or 1 time lower particle diameter, and more preferably 1/10 or lower.In addition, for surface-treated particle of water-soluble inorganic compound, preferred fine powder use level is 0.1～10 quality %, more preferably 1～8 quality %.

With the surface-treated particle of water-soluble inorganic compound that above-mentioned method obtains, classification only utilizes the surface-treated particle of water-soluble inorganic compound of desired granularity as required.As sorting equipment, also applicable general known any sorting equipment, sieve is particularly suitable for utilizing.Wherein, Gyro formula sieve, horizontal screen and vibratory screening apparatus are suitable for.For the sieve of plane inclined a little, Gyro formula sieve be to the sieve of horizontal circumferential motion.Horizontal screen be to the plane inclined sieve reciprocating sieve almost parallel a little with face.Vibratory screening apparatus be with the direction of compass screen surface almost right angle on give and the sieve of vibration rapidly.Preferably the time to the sieve feed is 5 seconds or longer, has again, and for improving the efficient of sieve, the preferred use patted ball (tapping ball).As the concrete example of such sieve, can enumerate Gyro-shifter (the work manufacturing of (strain) moral longevity), Rotex Screener (manufacturing of (strain) Seishin enterprise), Dalton vibratory screening apparatus ((strain) Da1ton manufacturing) etc.The caused vibration of sieve, 60～3000 times/it is suitable to be divided into, and preferably gives and 100～2500 times/minute more preferably 150～2000 times/minute vibration.Less than 60 times/minute, grading effect can worsen as the vibration number of sieve, as surpassing 3000 times/minute, then can increase and send out dirt.

In with the isolating surface-treated particle of water-soluble inorganic compound of classification operation, about fine powder, preferably drop into tablets press together once more with the water-soluble inorganic compound nuclear particle, supply with the granulation bag and be operated.Again relevant for coarse meal, be suitable for being crushed into and the same particle diameter of water-soluble inorganic compound before the granulation bag is operated, and then and the water-soluble inorganic compound nuclear particle drop into tablets press together, supply with the granulation bag and be operated.As at this moment pulverizing the pulverizer that coarse meal is used, preferably has the machine of sizing screen and rotating blade.As such pulverizer, can enumerate Fitz grinding machine (Hosakawamicron (strain) manufacturing), New Speed grinding machine (field, ridge Seiko (strain) manufacturing), Feather grinding machine (Hosakawamicron (strain) manufacturing) etc.Have again, pulverize while also can in pulverizer, flow into the cold wind cooling.With the powder classification of cyclonic separator with cold wind and pulverizing, this moment also can the classification fine powder.Further, by multistage pulverizing, it is narrower that size-grade distribution becomes.As the circumferential speed of the blade end of pulverizer, preferred 15～90m/s, more preferably 20～80m/s, preferred especially 25～70m/s.Less than 15m/s, grindability is insufficient as the end circumferential speed, as surpassing then over grind of 90m/s.

For making surface-treated particle of water-soluble inorganic compound reach high bulk density, little slope of repose, after the surface treatment of above-mentioned the 1st operation and the 2nd operation, preferably comprise the 3rd operation: control the operation that the lip-deep hydrate crystal of water-soluble inorganic compound nuclear particle after the surface treatment of the 2nd operation is grown up.Like this, the surface shape slyness that is kept surface-treated particle of water-soluble inorganic compound.Grow up as hydrate crystal, then the surface of water-soluble inorganic compound nuclear particle can produce a lot of convex-concaves, and loose density descends, and it is big that the slope of repose becomes.According to the occasion difference, also there is hydrate crystal failure surface processing layer, condense mutually with the hydrate crystal of giving prominence near surface-treated particle of water-soluble inorganic compound, become the coagulative situation of firm hydration.

As the method that suppresses hydrate crystal, can enumerate the surface-treated particulate method after [1] cooling the 2nd operation, the surface-treated particulate method after [2] dry the 2nd operation etc.At this wherein, from keeping this point of solvability well, preferred [1] method of cooling.

[1] the surface-treated particulate method of cooling after the 2nd operation if can be cooled to surface-treated particle of water-soluble inorganic compound 30 ℃ or lower, and preferred 25 ℃ or lower, there is no particular limitation.The preferred 5 ℃/hr of speed of cooling or higher, more preferably 10 ℃/hr or higher.There is no particular limitation for method of cooling and device, is divided into by the heat-transfer surface that is cooled as refrigerating unit and carries out refrigerative device and the device that utilizes air-flow.For example, as the refrigerating unit that utilizes the refrigerative heat-transfer surface, can enumerate Torus Disk (Hosokawa micro (strain) manufacturing), Frigomix (a day clear engineering (strain) is made) etc.As the refrigerating unit that utilizes air-flow, can enumerate thermopnore.Utilize example as concrete device, can enumerate the MIXGRAD series (the former making manufacturing in (strain) great river) of Glatt-POWREX ((strain) POWREX manufacturing), mobile dressing machine series (the former making manufacturing in (strain) great river), continous way fluidized granulator etc.In view of peeling off and broken possibility of the surface treatment of surface-treated particle of water-soluble inorganic compound, preferably utilize thermopnore.

[2] the surface-treated particulate method after dry the 2nd operation if can be with the surface-treated particle of water-soluble inorganic compound drying, and then there is no particular limitation.Particularly, can enumerate the drying means of same device used in utilization and the aforesaid method [1] as drying installation, at this moment, the temperature of the heat catalysis of heat-transfer surface and air-flow is 50～300 ℃, preferred 60～250 ℃.

Granular detergent composition

Though the surface-treated particle of water-soluble inorganic compound that obtains according to above-mentioned manufacture method can preferably be mixed into granular detergent composition as alkaline agent and detergent particle swarm directly as the composition use of granulated detergent.Normally from containing the particle of tensio-active agent, this particle contains tensio-active agent and mineral compound to this detergent particle swarm, and selection constitutes in the middle of enzyme granulate, bleach particle and the bleach activator particles etc.Blending ratio (mass ratio), preferred surface treatment of water-soluble inorganic compound particle/detergent particle swarm=3/97～97/3, more preferably 5/95～95/5, further preferred 10/90～90/10.

Granular detergent composition can be by obtaining surface-treated particle of water-soluble inorganic compound and any mixing of detergent particle swarm.As its blending means, applicable dry type is mixed.The mixing machine that uses can use mixing machine arbitrarily as long as can mix fully between the various particles.As mixing machine, can be fit to usage level round shape, double cone shape, V-type, rotation-mixing machines such as revolution type.Also available stirring granulating machine, rotation tablets press are arranged again.Preferred usage level round shape or double cone shape, 0～50 ℃ of temperature, Fr is several, and 0.01～0.2 (calculating from the formula that provides previously) mixed down.At this moment, the interpolation sequence independence of various particles and the composition beyond it is critical.

As granular detergent composition, preferably contain (a) above-mentioned surface-treated particle of water-soluble inorganic compound and, (b) contain the particle of tensio-active agent, it contains tensio-active agent and mineral compound.For preventing at granular detergent composition at the container internal classification, (a1) surface-treated particle of water-soluble inorganic compound and the ratio (a1)/(b1) that (b1) contains the particulate median size of tensio-active agent, preferred 0.5～2, more preferably 0.5～1.5, preferred especially 0.6～1.3.In addition, (a2) through surface-treated particle of water-soluble inorganic compound and (b2) contain the ratio (a2)/(b2) of the particulate loose density of tensio-active agent, preferred 0.5～2, more preferably 0.6～1.5, preferred especially 0.7～1.4.

(a) surface-treated particle of water-soluble inorganic compound is in the heavy use level of granular detergent composition, preferred 1～50 quality %, more preferably 5～40 quality %, preferred especially 10～30 quality %.On the other hand, (b) contain the use level of particle in granular detergent composition of tensio-active agent, preferred 10～97 quality %, more preferably 30～95 quality %, preferred especially 50～90 quality %.

(a) surface-treated particle of water-soluble inorganic compound and the particulate that (b) contains tensio-active agent cooperate the particle (mass ratio) of ratio (a) particle/(b), and be preferred 1/99～50/50, and more preferably 5/95～40/60, preferred especially 10/90～30/70.Mass ratio surpasses 50/50, and then mobile and solvability is variation significantly.

(b) particle that contains tensio-active agent contains tensio-active agent and mineral compound.As tensio-active agent, can enumerate anion surfactant, nonionogenic tenside, cats product and amphoterics.These can independent a kind or two or more appropriate combination uses.

As anion surfactant,, can use various anion surfactants so long as employedly in the former washing composition there is no special qualification.For example, can enumerate following anion surfactant.

(1) has the alkylbenzene sulfonate (LAS) that carbonatoms is the straight or branched of 8～18 alkyl

(2) carbonatoms is 10～20 alkyl-sulphate (AS) or alkenyl sulfate

(3) carbonatoms is 10～20 alpha-alefinically sulfonate (AOS)

(4) carbonatoms is 10～20 alkylsulfonate

(5) added and have alkyl or the alkenyl that carbonatoms is 10～20 straight or branched, average addition mole number is the sulfated alkyl ether (AES) or the alkenyl ether sulfate of 10 moles or lower oxyethane, propylene oxide, butylene oxide ring or its mixture.

(6) added and have alkyl or the alkenyl that carbonatoms is 10～20 straight or branched, average addition mole number is the alkyl ether carboxy acid salt or the alkenyl-carboxylic salt of 10 moles or lower oxyethane, propylene oxide, butylene oxide ring or its mixture.

(7) carbonatoms is 10～20 alkyl polyols ether sulfates such as alkyl glycerol ether sulfonate

(8) carbonatoms is 10～20 higher fatty acid salt

(9) carbonatoms is 8～20 saturated or unsaturated alpha-sulfo-fatty acid (α-SF) salt or its methyl, ethyl or a propyl ester etc.

As anion surfactant, the an alkali metal salt of preferred linear alkyl benzene sulphonic acid (LAS) (for example, sodium or sylvite etc.), AOS, α-SF, an alkali metal salt (for example, sodium or sylvite etc.) of AES, an alkali metal salt (for example, sodium or sylvite etc.) of higher fatty acid.

As nonionogenic tenside, for example, can enumerate following nonionogenic tenside.

(1) carbonatoms 6～22, preferably average 3～30 moles of addition on 8～18 fatty alcohol, polyoxyalkylene alkyl (or alkenyl) ether of the oxirane of preferred 5～20 moles carbonatoms 2～4

Wherein, polyxyethylated (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable for.As fatty alcohol used herein, can enumerate primary alconol, secondary alcohol etc.Have, its alkyl has side chain also passable again.As fatty alcohol, preferred primary alconol.

(2) polyxyethylated (or alkenyl) phenylate

(3) the oxirane addition is in the ester junction of long-chain fat acid alkyl ester, for example, and with the represented fatty acid alkyl ester alcoxylates of following general formula (I) (fatty acid alkylester alkoxylate)

R ¹CO(OA) _nOR ²

(in the formula, R ¹CO represents carbonatoms 6～22, preferred 8～18 fatty acid residue, OA representative ring oxidative ethane, 1, carbonatomss such as 2-propylene oxide are 2～4, the addition unit of preferred 2～3 oxirane, and n represents the average addition mole number of oxirane, be generally 3～30, preferred 5～20 number.R ²For having the alkyl that carbonatoms is 1～3 substituent rudimentary (carbonatoms 1～4).)

(4) polyoxyethylene sorbitan fatty acid ester

(5) polyoxyethylene sorbitan carboxylic ester

(6) polyoxyethylene fatty acid ester

(7) polyoxyethylene solidifies Viscotrol C

(8) glycerol fatty acid ester

In the above-mentioned nonionogenic tenside, fusing point is polyxyethylated (or alkenyl) ether of 9～16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether at 50 ℃ or lower HLB, at the fatty acid methyl ester ethoxylate of addition of ethylene oxide on the fatty acid methyl ester, the fatty acid methyl ester oxyethyl group propoxylated glycerine etc. of addition of ethylene oxide and 1,2 epoxy prapane all is suitable on fatty acid methyl ester.Have, these nonionogenic tensides can independent a kind or two or more appropriate combination uses again.

Have, the HLB of the nonionogenic tenside among the present invention is the value of trying to achieve according to the method for Griffin (with reference to Jitian, advance in rattan, Da Yuan, the mountain and compile altogether, " new edition tensio-active agent handbook ", industrial books Co., Ltd., 1991 years, the 234th page) again.

In addition, the fusing point among the present invention is the value of measuring according to the melting point determination of record among the JIS K0064-1992 " fusing point of chemical preparations and melting range measuring method ".

As cats product, for example, can enumerate following salt.

(1) two chain alkyl two short-chain alkyl type quaternary ammonium salts

(2) single-long-chain alkyl three short-chain alkyl type quaternary ammonium salts

(3) tri-long-chain alkyl list short-chain alkyl type quaternary ammonium salt

(above-mentioned chain alkyl is represented carbonatoms 12～26, and preferred 14～18 alkyl, short-chain alkyl are represented carbonatoms 1～4, preferred 1～2 alkyl, benzyl, carbonatoms 2～4, preferred 2～3 hydroxyalkyl, or polyoxyalkylenes.)

As tensio-active agent, can enumerate amphotericses such as imidazolines and amido betaines class.

(b) contain tensio-active agent in the particle of tensio-active agent, from the viewpoint of cleaning, preferred anionic tensio-active agent and nonionogenic tenside are more preferably and with anion surfactant and nonionogenic tenside.Occasion in anion surfactant and nonionogenic tenside and usefulness, the mass ratio of the use level of anion surfactant and nonionogenic tenside (anion surfactant/nonionogenic tenside) preferred 0.1～10, more preferably 0.2～8, preferred especially 0.3～7.

The use level of tensio-active agent, from (a) and surface-treated particle of water-soluble inorganic compound blended solvability and mobile viewpoint, (b) contain preferred 10～50 quality %, more preferably 15～40 quality % in the particle of tensio-active agent.Cooperate as surpassing 50 quality %, mobile variation is as less than 10 quality %, solvability variation.

(b) contain the particle of tensio-active agent, further contain mineral compound.Therefore, the mobile effect that can be improved.As mineral compound, there is no particular limitation, can use whole mineral compound contained in following inorganic component, reductive agent, the extender, can independent a kind or two or more appropriate combination uses.As mineral compound wherein, preferred yellow soda ash, salt of wormwood, sodium sulfate, aluminosilicate.

(b) use level that contains mineral compound in the particle of tensio-active agent is 10～80 quality %, preferred 20～70 quality %, more preferably 30～60 quality %.Amount as mineral compound is very few, and mobile variation is sent out dirt as causing powder excessively at most.

(b) contain the particle of tensio-active agent, preferably further contain water-soluble high-molecular compound, like this, can further improve flowability and solidified nature after the long-time preservation.As water-soluble high-molecular compound, can enumerate with above-mentioned (a) surface-treated particle of water-soluble inorganic compound in the same compound of water-soluble high-molecular compound enumerated.In addition, used here water-soluble high-molecular compound can be the same with (a) water-soluble high-molecular compound, also can be different.Contain the water-soluble high-molecular compound in the particle of tensio-active agent as (b), preferred acrylic polymer compound and cellulose family macromolecule compound, as the acrylic polymer compound, the multipolymer of preferred acrylate copolymer, vinylformic acid/toxilic acid.As the Mierocrystalline cellulose macromolecular compound, preferably carboxymethyl cellulose (CMC).The weight-average molecular weight of water-soluble high-molecular compound preferred 1,000～100,000.Water-soluble high-molecular compound can independent a kind or two or more appropriate combination uses.

(b) use level that contains the water-soluble high-molecular compound in the particle of tensio-active agent is 0.1～10 quality %, preferred 0.5～9 quality %, more preferably 1～8 quality %.The use level of water-soluble high-molecular compound such as very few can not get the purpose effect, and as too much, then (b) contains the solvability variation of the particle of tensio-active agent itself.

Contain in the particle of tensio-active agent at (b) of the present invention, except that above-mentioned necessary composition, can contain following any composition.Mineral compound is necessary composition, will repeat at length to record and narrate below again.Water-soluble high-molecular compound also will repeat to record and narrate.These any compositions can independent a kind or two or more appropriate combination uses.

(1) cleans component

Contain the clean component that is cooperated in the particle of tensio-active agent as (b), can enumerate inorganic and organic constituent.

(1-1) inorganic component

As inorganic component, for example, can enumerate phosphoric acid salt such as neutral salt such as basic salt, sodium sulfate such as yellow soda ash, salt of wormwood, sodium bicarbonate, S-WAT, concentrated crystal soda, water glass, crystallinity lamina sodium silicate, amorphism lamina sodium silicate, orthophosphoric acid salt, pyrophosphate salt, tri-polyphosphate, metaphosphate, hempa hydrochlorate, phytate, with following general formula (II)

x ¹(M ₂O)·Al ₂O ₃·y ¹(SiO ₂)·w ¹(H ₂O) (II)

(in the formula, M represents alkali metal atoms such as sodium, potassium, x ¹, y ¹And w ¹The mole number of representing each composition, general x ¹Expression 0.7～1.5, y ¹The number of expression 0.8～6, w ¹Represent positive number arbitrarily.) represented crystallinity aluminosilicate, with following general formula (III), (IV)

x ²(M ₂O)·Al ₂O ₃·y ²(SiO ₂)·w ²(H ₂O) (III)

(in the formula, M represents alkali metal atoms such as sodium, potassium, x ², y ²And w ²The mole number of representing each composition, general x ²Expression 0.7～1.2, y ²Expression 1.6～2.8, w ²Expression 0 or positive number arbitrarily.)

x ³(M ₂O)·Al ₂O ₃·y ³(SiO ₂)·z ³(P ₂O ₅)·w ³(H ₂O) (IV)

(in the formula, M represents alkali metal atoms such as sodium, potassium, x ³, y ³, z ³And w ³The mole number of representing each composition, general x ³Expression 0.2～1.1, y ³Expression 0.2～4.0, z ³Expression 0.001～0.8, w ³Expression 0 or positive number arbitrarily.)

Represented amorphous aluminosilicate etc.In inorganic component, preferred yellow soda ash, salt of wormwood, water glass, tripoly phosphate sodium STPP, sodium aluminium silicate.

(1-2) organic constituent

As organic constituent, for example, can enumerate aminocarboxylates such as nitrilotriacetic acid(NTA) salt, edetate, Beta-alanine diacetate, aspartic acid diacetate, methylglycine diacetate, iminobisuccinate; Hydroxyl amino carboxylate salts such as Serine diacetate, oxyimino disuccinate, hydroxyethylethylene diamine tri-acetic acid salt, dihydroxyethylglycin salt; Hydroxycarboxylates such as hydroxyl acetate, tartrate, Citrate trianion, gluconate; Ring such as pyromellitic acid salt, benzo polycarboxylate, pentamethylene tetracarboxylic acid hydrochlorate carboxylate salt; Ether carboxylates such as carboxymethyl Tartronate, carboxyl methoxy succinate, oxyethane succinate, tartrate list or disuccinate; Methylene-succinic acid, fumaric acid, tetramethylene-1, the polymkeric substance or the multipolymer of 2-dicarboxylic acid, succsinic acid, aspartic acid etc.; Polyoses such as polyose oxide compounds such as starch, Mierocrystalline cellulose, amylose starch, pectin and carboxymethyl cellulose.

In these organic constituents, optimization citric acid, aminocarboxylate, hydroxyl amino carboxylate salt, polyacrylate, vinylformic acid/maleic acid, polyacetal carboxylation, particularly oxyimino disuccinate, weight-average molecular weight are 1,000～80, the weight-average molecular weight of putting down in writing in the clear 54-52196 communique of the salt of vinylformic acid/maleic acid of 000, polyacrylate and Te Kai is 800～1,000,000, preferred 5,000～200,000 polyacetal carboxylations such as metaldehyde acid are for being suitable for.

The use level of organic constituent contains preferred 0.5～20 quality %, more preferably 1～10 quality % in the particle of tensio-active agent at (b).

In addition, dirty dispersed purpose from improve clearing power, washings, inorganic component such as organic constituent such as optimization citric acid salt, aminocarboxylate, hydroxyl amino carboxylate salt, polyacrylate, vinylformic acid/maleic acid, polyacetal carboxylation and zeolite is also used.

(2) dissolution accelerator

As containing the dissolution accelerator that cooperates in the particle of tensio-active agent at (b), for example, can enumerate yellow soda ash, inorganic ammonium salt such as ammonium sulfate, ammonium chloride, carbonatomss such as paratoluenesulfonic acid sodium salt, sodium xylene sulfonate, isopropyl benzene sodium sulfonate are water-soluble substanceses such as 1～5 the benzene sulfonate with short-chain alkyl, Sodium Benzoate, benzene sulfonic acid sodium salt, sodium-chlor, citric acid, D-glucose, urea, sucrose.

Wherein, preferred salt of wormwood, sodium-chlor, from improving the balance of deliquescent effect and cost, preferred especially salt of wormwood.

Cooperating the occasion of salt of wormwood, from improving this point of deliquescent effect, its use level contains preferred 1～15 quality % in the particle of tensio-active agent at (b), more preferably 2～12 quality %, preferred especially 5～10 quality %.

Cooperating the occasion of sodium-chlor, from improving this point of deliquescent effect, its use level contains preferred 1～10 quality % in the particle of tensio-active agent at (b), more preferably 2～8 quality %, preferred especially 3～7 quality %.

(3) swelling property water-insoluble substance

As the swelling property water-insoluble substance that (b) contains in the surfactant granules to be cooperated, can enumerate cellulose powder, crystallinity Mierocrystalline cellulose, wilkinite etc.

(4) fluorescent agent: two (triadinyl amino-stilbene) disulfonic acid derivatives (" Tinopal AMS-GX "), two (sulfo group styryl) biphenyl salt (Tinopal CBS-X) etc.

(5) antistatic agent: cats products such as dioxane fundamental mode quaternary ammonium salt etc.

(6) recontaminate prevents agent: derivatived celluloses such as carbonyl methyl cellulose etc.

(7) extender: sodium sulfate, vitriolate of tartar etc.

(8) reductive agent: S-WAT, potassium sulfite etc.

(9) spices

(10) pigment

(11) bleach activating catalyzer

The bleach activating catalyzer, transition metal atoms such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, molybdenum and dentate form coordination compound by nitrogen-atoms and Sauerstoffatom etc., as the transition metal that contains, preferred nickel, manganese etc., preferred especially manganese.

(b) contain preferred 200～1500 μ m of particulate median size of tensio-active agent, more preferably 250～1000 μ m, preferred especially 300～700 μ m.In addition, the preferred 0.4～1.2g/cm of loose density ³, more preferably 0.5～1.0g/cm ³The mensuration of median size and loose density is carried out according to the method for embodiment record.

From solvability and storage stability, (b) contain preferred 4～10 quality % of particulate water content of tensio-active agent, more preferably 5～9 quality %, preferred especially 5～8 quality %.

(b) particle of tensio-active agent can obtain by following prilling process.Can enumerate with raw material powder and binder constituents (tensio-active agent, water, liquid polymer etc.) mediate mix after, and meanwhile the broken comminution granulation of kneading of the extruding pelletization method of extruding pelletization, the broken granulation of solid that obtains after kneading mixed, in raw material powder, add tackiness agent with the stirring-granulating method of stirring blade stirring-granulating, make raw material powder rotate the granulation of spray adhesive composition the rotation comminution granulation, make the flow thermopnore comminution granulation etc. of spraying liquid tackiness agent granulation of raw material powder.In these comminution granulations spendable concrete device and condition like the spy open 2003-105400 communique, spy open 2003-238998 communique, Japanese powder technology association make up record such as a handbook the 1st edition like that.

Granular detergent composition of the present invention, the viewpoint of the curing (conglomeration) when preventing to store, preferred (a) surface treatment water-soluble cpds particle and (b) contain the particulate any one party of tensio-active agent, preferred both sides use the fine powder of organic or inorganic to carry out surface treatment.As these fine powders, if 1 particle diameter is below the 30 μ m, the fine powder of preferred 0.1～10 μ m, then there is no particular limitation, as an example, can enumerate normal temperature solid tensio-active agent, long-chain fat acid alkaline earth metal salt, aluminosilicate, silica, clay mineral etc.Wherein, preferred aluminosilicate.

When to (a) particle and/or (b) particle carried out surface-treated with fine powder, the preferred amounts of fine powder was 0.1～10 quality % in granular detergent composition, more preferably 0.3～5 quality %, preferred especially 0.5～3 quality %.

From solvability and storage stability, the preferred 10 quality % or lower of the water content of granular detergent composition of the present invention, more preferably 4～9 quality %, preferred especially 5～8 quality %.

Among the present invention, (a) surface-treated particle of water-soluble inorganic compound that especially preferably satisfies following condition reaches the particulate combination that (b) contains tensio-active agent.

(a) the particulate water-soluble inorganic compound is yellow soda ash or salt of wormwood, water-soluble high-molecular compound is a kind of selecting from vinyl macromolecular compound, polyose or derivatives thereof and polyester macromolecular compound or two or more, (a) the use level less than 10 quality % of the slightly water-soluble compound in the particle, and the use level that (b) contains the tensio-active agent in the particle of tensio-active agent is 10～50 quality %.

In granular detergent composition of the present invention, contain the particle of tensio-active agent except that (a) surface-treated particle of water-soluble inorganic compound and (b), can contain the particle of other enzyme granulate, bleach particle, bleach activator particles etc.

(1) enzyme granulate

Enzyme in the enzyme granulate can directly use the enzyme granulate of present granulous clothing with employed market sale in the washing composition.Particularly, can enumerate cellulases such as amylase, Celluzyme 0.7T such as Savinase 12T, Kannase 12T, 24T, proteolytic enzyme such as Everlase 8T, Deozyme, lipase such as Lipolase Ultra 50T, Lipex50T, Termamyl 100T (above is the manufacturing of Novozymes company), Maxaca l45G, Maxapem 30G, Properase 1000E (above is the manufacturing of Genencor company).

From solvability and storage stability, preferred 200～1000 μ m of the median size of enzyme granulate, more preferably 300～700 μ m.The mensuration of median size is carried out according to the method that embodiment described later put down in writing.

From the viewpoint of washing (-)off properties, preferred 0.1～5 quality % of use level of the total amount enzyme granulate of relative granular detergent composition, more preferably 0.2～2 quality %.

(2) bleach particle

Be by hydrogen peroxide or produce that the superoxide of hydrogen peroxide forms when being dissolved in water as bleach particle, usually, use in SPC-D, the Sodium peroxoborate one or two.Particularly, from the viewpoint of long-time stability, preferred SPC-D.Be the particle surface prevent that these superoxide from forming at this superoxide, contact to produce with other detergent composition etc. of moisture agent and decompose, can use to apply the form that bag is waited processing.Apply the oxygen class SYNTHETIC OPTICAL WHITNER of the particle form of bag quilt, proposed all schemes, for example can enumerate the bleach particle of putting down in writing in No. 2918991 communique of patent.This bleach particle is spray respectively in the sodium percarbonate granules that keeps flow state boric acid aqueous solution and silicate base aqueous metal salt, the dry granulation thing that forms.Except that above-mentioned, also can be with stabilization agent and coating agent and usefulness such as previously known sequestrants.Stability and deliquescent viewpoint from sodium percarbonate granules, bag is preferred 100～2000 μ m by the median size of the sodium percarbonate granules of crossing, more preferably 200-1000 μ m, further preferred 300～800 μ m can enumerate the SPC-D that Mitsubishi's gas chemistry (strain) is made as such particle.

From the viewpoint of bleachability and efficient, with respect to the granular detergent composition total amount, preferred 0.5～30 quality % of the use level of bleach particle, more preferably 1～20 quality %.

(3) bleach activator particles

Bleach-activating agent in the bleach activator particles can be enumerated the alkanoyloxy Phenylsulfonic acid of tetra acetyl ethylene diamine, carbonatoms 8～12, the alkanoyloxy phenylformic acid of carbonatoms 8～12 or their salt; wherein; preferred 4-caprinoyl aminobenzoic acid, 4-dodecane acyl-oxygen base benzene sulfonic acid sodium salt, 4-acyloxy in ninth of the ten Heavenly Stems benzene sulfonic acid sodium salt; particularly from this point of bleaching effect, preferred 4-caprinoyl aminobenzoic acid, 4-acyloxy in ninth of the ten Heavenly Stems benzene sulfonic acid sodium salt.

Bleach-activating agent is at PEG#3000～#20000, the normal temperature such as polyoxyethylene glycol of preferred PEG#4000～#6000 are down for after being dispersed in the powder of tensio-active agents such as bleach-activating agent and sulfonated alkene, alkylbenzene sulfonate, alkyl sulfuric ester salt wherein in the solid binder substance heating and melting process, extrude and make the bleach-activating agent granulation thing that diameter is the noodles shape about 1mm, then, preferably pulverizing gently is to cooperate about 0.5～3mm again.As the powder of tensio-active agent, the alpha-olefins sulfonate of preferred alkyl chain length 14.

The use level of the SYNTHETIC OPTICAL WHITNER in the granulation thing, preferred 30～95 quality %, more preferably 50～90 quality %.Use level then is difficult to fully to obtain granulation and gets effect outside this scope.

The use level of above-mentioned tackiness agent is 0.5～30 quality % in the granulation thing, preferred 1～20 quality %, more preferably 5～20 quality %, preferred 0～50 quality % of the use level of above-mentioned surfactant powder in the granulation thing, more preferably 3～40 quality %, preferred especially 5～30 quality %.

The median size of bleach activator particles, from the viewpoint of solvability and storage stability, preferred 200～1500 μ m, more preferably 300～1000 μ m.

With respect to the total amount of granular detergent composition, preferred 0.1～15 quality % of the use level of bleach activator particles, preferred especially 0.3～10 quality %.

Can carry out with particle, enzyme granulate, bleach particle and the bleach activator particles that dyestuff or pigment contain tensio-active agent to (a) surface-treated particle of water-soluble inorganic compound, (b) re-using after painted.At this moment painted used dyestuff, pigment have used when clean and the clothing class have not been produced painted dyestuff and pigment.74260), red No. 102 of food dye, matching stain " acid is yellow " (Acid Yellow) 141 etc. as such dyestuff, pigment, can enumerate ultramarine, coranylgreen CG-130 (CI numbering:.After these dyestuffs, pigment are made the aqueous solution and dispersion liquid, can with (b) on one side contain the same stirring granulating machine of the prilling granulator of tensio-active agent and rotate in the tablets press above-mentioned particle is rotated, undertaken painted by interpolation.Have again, also can in the process that above-mentioned particle is carried with rotary conveyor, carry out painted the above-mentioned aqueous solution and the dispersion liquid of above-mentioned particle spraying.As colo(u)r pick-up, for colored particles, preferred 0.001～1 quality %.

In addition; can be after to (a) surface-treated particle of water-soluble inorganic compound and (b) containing side in the particle of tensio-active agent or both sides with spices and composing perfume (or spice); mix each particle; after also (a) surface-treated particle of water-soluble inorganic compound and the particle that (b) contains tensio-active agent can being mixed, compose fragrant again.Spices as using can use the spy to open the composition of putting down in writing in 2002-146399 communique and the Te Kai 2003-89800 communique.Have, spices is the mixture that fragrance component, solvent, spices stablizer etc. are made again.In the granular detergent composition of the present invention, preferred 0.001～10 quality % of the use level of spices, more preferably 0.01～5 quality %.Have, spices has more than the spices that is defined among the embodiment again.

The physical property values of granular detergent composition of the present invention, though be not particularly limited, loose density is generally 0.3g/cm ³Or higher, preferred 0.5～1.2g/cm ³, more preferably 0.6～1.1g/cm ³In addition, preferred 200～1500 μ m of median size, more preferably 250～1000 μ m, preferred especially 280～700 μ m.As median size less than 200 μ m, dust takes place easily, the processing property variation on the other hand, as surpassing 1500 μ m, is difficult to obtain the solvability as the object of the invention.Further, the flowability of granular detergent composition is 60 ° or lower as the slope of repose, preferred 50 ° or lower.From the viewpoint of using, the flowability of preferred further storage back (in the high medium-term and long-term occasion of preserving of container of water vapour permeabilitys such as paper container etc.), preferred 60 ° or lower, more preferably 50 ° or lower as the slope of repose.

Granular detergent composition of the present invention can be filled in the proper container granulated detergent articles for use as the container of packing into.As the material of container, consider storage stability, preferred Water Vapour Permeability is 30g/m ²24 hours (40 ℃, 90%RH) or lower, more preferably 25g/m ²24 hours (40 ℃, 90%RH).This can realize by the combination of general wrapping material and the variation of thickness.Have, the Water Vapour Permeability among the present invention is measured with the method for stipulating among the JIS Z0208-1976 again.

Granular detergent composition of the present invention further, can mix the back compressed moulding with disintegrating agent etc., uses as compression washing composition such as detergent tablet and pie washing composition.

Granular detergent composition of the present invention, because can simultaneously fully keep flowability and solidified nature after dissolution in low temperature simultaneously improves prolonged preservation, being particularly suitable for short period of time washing procedure washing uses, weak current program washing usefulness, the purposes or the purpose of the use in washing machine of washing composition input port used and had to cold water washing.

Washing methods

Washing methods of the present invention is, contain useful organic or inorganic water-soluble high-molecular compound particle of water-soluble inorganic compound is carried out surface treatment, further, the water insoluble chemical compound is handled the washing bath and the washes of the surface-treated particle of water-soluble inorganic compound that obtains again to its surface treated, with bath raio 7～15L/kg, and preferred 8～15L/kg, more preferably 10～13L/kg, 5～12 ℃ of wash temperatures, preferred 7～12 ℃, more preferably 10～12 ℃ of washing methodss that carried out.With the bath raio of above-mentioned scope, the occasion that wash temperature is washed, more highlight out what is called under the state of low water temperature and low whipping force, even if the wetting effect that does not also form condensation product.

If according to the present invention; although the wetting agglutinator that also do not form under the state of low water temperature and low whipping force; and be in the suds and shown outstanding solvability; good fluidity; in the time of can preventing to make to the surface-treated particle of water-soluble inorganic compound of the tack of tablets press; cooperate this particle, the flowability after the prolonged preservation, the powder detergent composition that non-solidified nature is good can be provided.

Below, according to embodiment and comparative example the present invention is described more specifically, but the present invention is not limited to these examples.In addition, in the following Example, composition in the occasion of not writing exactly especially, " % " is quality %, the amount of each composition in the table, the particulate that contains tensio-active agent about (b) of (a) surface-treated particle of water-soluble inorganic compound of table 1～4 and table 5 is formed, and expression is as the use level of pure composition, and other table represents to put down in writing the use level of composition.

Embodiment and comparative example

[embodiment a1～a28, comparative example a29～a35]

The manufacture method 1 of surface-treated particle of water-soluble inorganic compound (stirring-granulating 1)

The 1st operation

Water-soluble inorganic compound nuclear particle in forming shown in following table 1～4 put into possess tine shape scoop, space between scoop and wall is in the plough blade mixer (Pacific Ocean machine worker (strain)) of 5mm, (filling ratio 30 volume %), begin to stir (cutting knife rotating speed: 1015 rev/mins, blade end speed (circumferential speed) 6.9m/s) with 150 rev/mins on main shaft.Stir beginning and added the water-soluble high-molecular compound aqueous solution (concentration is recorded in the raw material hurdle of back book, below identical) 180 seconds with pressurized nozzles (flat burner) spraying of spray angle 115 degree after 10 seconds, carry out granulation, wrap and be operated.Have, the water-soluble high-molecular compound aqueous solution is preserved in advance according to table 1～4 temperature of being put down in writing and was re-used in 10 days again.In addition, the amount of moisture of synthetic particle full dose surpasses 10% occasion in respect to the 1st operation, pours warm air drying in said apparatus into, amount of moisture is adjusted into the amount of table 1～4.

The 2nd operation

Then continue the stirring of plough blade mixer, the spraying interpolation, the bag that carried out 180 seconds with the pressurized nozzles (wholecircle taper (full cone) nozzle) of spray angle 60 degree are operated.Add fine powder at last as required, continue stirring and obtained particle in 30 seconds.Have, the particle temperature when finishing for bag is operated is adjusted into table 1～4 temperature of being put down in writing again, and will suitably feed warm water and carry out above-mentioned bag and be operated in the 1st operation and the whole process of the 2nd operation in the chuck of mixing tank.

The 3rd operation

Then, particles filledly advance fluidized-bed ((strain) POWREX makes for Glatt-POWREX, model FD-WRT-20), fill in the backward current bed and send 15 ℃ wind (air), carry out the particulate cooling operation, obtain being cooled to 20 ℃ particle what obtain.While confirming that the fluidization state is adjusted into the wind speed in the fluidized-bed in the scope of 0.2～10.0m/s.With the particle that obtains screen sizing, obtain surface-treated particle of water-soluble inorganic compound (median size, slope of repose, loose density are documented in table 1～4) by mesh perforate 2000 μ m sieve with mesh perforate 2000 μ m.

The manufacture method 2 of surface-treated particle of water-soluble inorganic compound (stirring-granulating 2)

The 1st operation

In the moiety shown in the following table 1～4, the water-soluble inorganic compound nuclear particle that will be equivalent to volume 10L drops into Forberg mixing tank (F-20 type, Japan's Pneumatic industry (strain) manufacturing) in (filling ratio 50 volume %), begins to stir (stopping cutting knife) with paddle circumferential speed 1.4m/s.Stir beginning after 5 seconds, add the water-soluble polymer aqueous solution with the 100g/min spraying, carry out the granulation bag and be operated with the hollow wholecircle awl of 2 fluids of spray angle 70 degree (hollow full cone) nozzle.

The 2nd operation

Then continue the stirring operation of Forberg mixing tank, add the slightly water-soluble compound shown in table 1～4 with the 100g/min spraying, wrap and be operated with the hollow wholecircle of 2 same fluids awl nozzle.At last, add fine powder as required, continue stirring and obtained particle in 30 seconds.

The 3rd operation

After the 2nd operation finishes, by with the same operation of the 3rd operation of the manufacture method 1 of above-mentioned surface-treated particle of water-soluble inorganic compound, obtain surface-treated particle of water-soluble inorganic compound (median size, slope of repose, loose density are documented in table 1～4).

The manufacture method 3 of surface-treated particle of water-soluble inorganic compound (rotation granulation)

The 1st operation

Water-soluble inorganic compound nuclear particle in forming shown in following table 1～4 is put into the horizontal circle tubular rotate mixing machine (drum diameter 585mm, the long 490mm of cylinder, container is in the inner wall of the rotating cylinder of 131.7L, the baffle plate that the gap 20mm of two pieces of high 45mm and inner wall is arranged) (filling ratio 20 volume %) begin rotating operation with 22 rev/mins rotating speed.Stir beginning after 30 seconds, the water-soluble high-molecular compound aqueous solution is added the water-soluble polymer aqueous solution with the hollow wholecircle awl of 2 fluids of spray angle 70 degree nozzle with the 100g/min spraying, carry out the granulation bag and be operated.

The 2nd operation

Then continue the horizontal circle tubular and rotate the stirring operation of mixing machine, with the slightly water-soluble compound shown in 100g/min spraying interpolation table 1～4, wrap and be operated with the hollow wholecircle awl of 2 same fluids nozzle.At last, add fine powder as required, be rotated further operation and obtained particle in 60 seconds.

The 3rd operation

Then, be filled into fluidized-bed (Glatt-POWREX, model FD-WRT-20 (strain) POWREX makes), fill in the backward current bed and send 15 ℃ wind (air), carry out the particulate cooling operation.While confirming that the fluidization state is adjusted into the wind speed in the fluidized-bed in the scope of 0.2～10.0m/s.Like this, obtain being cooled to 20 ℃ particle.The particle that obtains is used the screen sizing of mesh perforate 250 μ m and mesh perforate 2000 μ m, obtain can't pass mesh perforate 250 μ m, by the surface-treated particle of water-soluble inorganic compound (median size, slope of repose, loose density are documented in table 1～4) of 2000 μ m mesh sieves.

The manufacture method 4 of surface-treated particle of water-soluble inorganic compound (thermopnore granulation)

The 1st operation

Water-soluble inorganic compound nuclear particle in forming shown in following table 1～4 is added in the fluidized-bed ((strain) POWREX makes, Glatt-POWREX, model FD-WRT-20), and the powder layer thickness when making it static is 200mm.Fill in the backward current bed and send 50 ℃ wind (air), confirm flow of powderization after, to the powder bed of fluidization from the top spray water soluble macromolecular aqueous solution.While confirming that the fluidization state is adjusted into the wind speed in the fluidized-bed in the scope of 0.2～10.0m/s, carries out the granulation bag and is operated.Be the spray water soluble macromolecular aqueous solution, used the hollow wholecircle awl of the 2 fluids nozzle of spray angle 70 degree.Spray velocity is about 100g/min.

The 2nd operation

Continue on one side to keep the fluidization state in the thermopnore, on one side with the hollow wholecircle awl of 2 same fluids nozzle with the slightly water-soluble compound shown in 100g/min spraying interpolation table 1～4, wrap and be operated.

At this moment, for the powder of moisture above 10 quality %, continue to thermopnore in give 50 ℃ wind (air) on one side, till one side makes flow of powder be 8 quality % to moisture.

At last, in the occasion of adding fine powder as required, from the thermopnore exhaust particulate matter, in rotating cylinder (diameter 0.6m, long 0.48m are equipped with 4 pieces on the baffle plate of thick 1mm * wide 12cm * long 48cm, 20 rev/mins of rotating speeds), particulate matter and fine powder mixed 60 seconds.

The 3rd operation

After the 2nd operation finishes, by with the same operation of the 3rd operation of the manufacture method 1 (stirring-granulating 1) of above-mentioned surface-treated particle of water-soluble inorganic compound, obtain surface-treated particle of water-soluble inorganic compound (median size, slope of repose, loose density are documented in table 1～4).

The manufacture method 5 of surface-treated particle of water-soluble inorganic compound (make by stirring-granulating+rotation Grain)

The 1st operation

Water-soluble inorganic compound nuclear particle in forming shown in following table 1～4 put into possess tine shape scoop, space between scoop and wall is Leodige mixing tank ((strain) Matsubo manufacturing of 5mm, the M20 type) in (filling ratio 30 volume %), begins to stir (cutting knife stops) with 200 rev/mins on main shaft.Stir beginning and added the water-soluble high-molecular compound aqueous solution 30 seconds after 10 seconds, carry out granulation, bag is operated.

The 2nd operation

The particulate matter that obtains is discharged from the Leodige mixing tank, put into the horizontal circle tubular and rotate mixing machine (drum diameter 585mm, the long 490mm of cylinder, container is in the inner wall of the rotating cylinder of 131.7L, the baffle plate that the gap 20mm of two pieces of high 45mm and inner wall is arranged), begin rotating operation with 22 rev/mins rotating speed.Rotate beginning after 30 seconds, the hollow wholecircle awl of the 2 fluids nozzle of spending with spray angle 70 adds the slightly water-soluble compound shown in table 1～4 with the 100g/min spraying, wraps to be operated.

At last, add fine powder as required, be rotated further operation and obtained surface-treated particle of water-soluble inorganic compound in 60 seconds.

The 3rd operation

Next, by with the same operation of the 3rd operation of the manufacture method 3 (rotation granulation) of above-mentioned surface-treated particle of water-soluble inorganic compound, obtain surface-treated particle of water-soluble inorganic compound (median size, slope of repose, loose density are documented in table 1～4).

Have, in any one method of the manufacture method 1～5 of above-mentioned surface-treated particle of water-soluble inorganic compound, the slightly water-soluble compound adds under its liquid state more than fusing point again.In addition; coarse particles Fitz pulverizer (Hosokawa Micro (strain) manufacturing of not using that produces in the classification operation of the manufacture method 1～5 of above-mentioned surface-treated particle of water-soluble inorganic compound as surface-treated particle of water-soluble inorganic compound; DKA-3) pulverize (mesh size 1.2mm; 4700 rev/mins of rotating speeds), when next granulation and surface-treated particle of water-soluble inorganic compound drop into tablets press together and utilize again.Have, according to progressive operation, the undersized microparticle that uses as surface-treated particle of water-soluble inorganic compound does not drop into tablets press with water-soluble inorganic compound during together in next granulation yet and utilizes when producing again.

Have again, do not add the slightly water-soluble compound among comparative example a30, a31, the a33, do not add water-soluble high-molecular compound among a32, a34, the a35.Have again, comparative example a29 promptly do not add water-soluble high-molecular compound do not add yet the slightly water-soluble compound the two, directly used the yellow soda ash (particulate state) of raw material.

About the surface-treated particle of water-soluble inorganic compound that obtains, the solution heat of each surface treating part and the wetting thermal value of surface-treated particle of water-soluble inorganic compound and the wetting speed on surface treating part surface mensuration, evaluation have been carried out according to following method.Its result is in the lump as shown in table 1～4.

(1) dissolving of surface treating part disperses heat determination

When weighing up surface-treated particle of water-soluble inorganic compound (comparative example a29 is a sodium carbonate particle) that 0.1g obtains and it is enclosed internal diameter 1cm, being about in the peace bottle pipe of 4cm, the peace bottle pipe of a sky is also sealed as blank.

They are arranged in the double type calorimetric measurement instrument ((strain) Tokyo science and engineering is made for multi-microcalorimeter, MMC-5111 type),, under 25 ℃ of temperature, 60 rev/mins agitation condition, make its thermal equilibriumization at the cell that injects 25mL water.After confirming baseline stability, to pacify bottle to break with the hammer in the device it is contacted with water, mensuration is followed the dissolving dispersive thermal change of surface-treated particle of water-soluble inorganic compound, the thermal value (Q) the when dissolving that obtains surface-treated particle of water-soluble inorganic compound disperses.

Equally, measure the thermal value (Q of water-soluble inorganic compound nuclear particle _A), the thermal value (Q of the 1st surface treating part just _B).So-called the 1st surface treating part to the heating in the water dissolution dispersion process refers to satisfy Q _B-Q _A＜0 handling part.So-called the 2nd surface treating part to the heat absorption in the water dissolution decomposition course refers to satisfy Q-Q _B＞0 handling part.In addition, the heat absorption in all dissolving dispersion process of so-called surface treating part refers to Q-Q _A＞0 state.Q, Q are arranged again _AAnd Q _BIt all is heating (that is negative value).

(2) mensuration of wetting thermal value

In the glass filter that has the hole ware of internal diameter 3cm, high 5cm, put into the surface-treated particle of water-soluble inorganic compound (comparative example a29 is a sodium carbonate particle) that 10g obtains, then, after putting banded temperature sensor well, put into the 10g test portion again.It is arranged on two mouthfuls of flask upper interface places, connects a vent fan at lateral interface.In strainer, add the water of 25 ℃ of 10g, reduced pressure 10 seconds, water is all passed through, make the surface-treated particle of water-soluble inorganic compound moistened surface at once.Thereafter, the time of measuring the detected temperature of temperature sensor changes, and tries to achieve because the top temperature that hydration reaction produces.The thermal value of wetting generation, temperature before wetting (the surface-treated particle of water-soluble inorganic compound temperature before wetting) and wetting after maximum temperature, try to achieve maximum temperature rising degree according to following formula.

Maximum temperature rising degree (℃)=(maximum temperature after wetting (℃))-(temperature before wetting (℃))

Caloric receptivity (the Q-Q when dissolving of the surface treating part of the surface-treated particle of water-soluble inorganic compound that obtains disperses _A) and the relation of the maximum temperature rising degree that obtains according to the mensuration of wetting thermal value, visible correlationship shown in the 1st figure.This thing has shown that dissolving and heat absorbing amount Gao Ze is suppressed from wetting thermal value.Though the maximum temperature rising degree of the sodium carbonate particle of comparison test example a29 is 31.6 ℃, and the surface-treated particle of water-soluble inorganic compound of dissolving heat in the scope of 30～80J/g of surface treating part, its temperature rising degree is suppressed in 15 ℃～6 ℃.

According to following benchmark the temperature rising degree that obtains is estimated.

＜metewand 〉

◎: maximum ascending temperature is 9～12 ℃

Zero: maximum ascending temperature is 6～9 ℃ or 12～15 ℃

△: maximum ascending temperature is 6 ℃ of less thaies

*: maximum ascending temperature is more than 15 ℃

(3) evaluation of the wetting speed on surface-treated particle of water-soluble inorganic compound surface (Washburn method)

With screening is that to be filled into the bottom be in the graduated Glass tubing of 1cm with the internal diameter of glass filter for surface-treated particle of water-soluble inorganic compound (among the comparative example a29 for the sodium carbonate particle) 0.5g of 355～500 μ m, begin till the high 0.6cm from the lowest part of having filled surface-treated particle of water-soluble inorganic compound, allow behind 5 ℃ the water retting, measure the time of water saturates till the upper end of the surface-treated particle of water-soluble inorganic compound of filling.The penetration period that obtains is according to following benchmark evaluation.

＜metewand 〉

◎: penetration period is 300～400 minutes

Zero～◎: penetration period is 200～300 minutes

Zero: penetration period is 100～200 minutes

*: penetration period less than 100 minutes or above 400 minutes

(4) device tack evaluation

Behind the modulation surface-treated particle of water-soluble inorganic compound, estimate in formation situation the dirt settling of the device inwall of this grain granulation according to following benchmark.

＜metewand 〉

◎: almost do not have dirt settling

Zero: though dirt settling is arranged in no problem level

Zero: dirt settling is remarkable

*: almost dirt settling is all arranged on full surface.

Have again, in table 1～4, except above-mentioned evaluation result, the temperature of the surface-treated particle of water-soluble inorganic compound after the 2nd operation finishes in temperature and each manufacture method when also having charged to the use of the water-soluble inorganic compound nuclear particle that uses, water-soluble high-molecular compound, slightly water-soluble compound together, manufacture method when modulating each surface-treated particle of water-soluble inorganic compound.

[table 1]

Form [%]		Embodiment
		Embodiment										a1	a2	a3	a4	a5	a6	a7	a8	a9	a10
		The water-soluble inorganic compound nuclear particle	Yellow soda ash	93.0	92.0	91.0	90.0	89.0	87.5	90.0	88.0	a1	a2	a3	a4	a5	a6	a7	a8	a9	a10	85.0	84.0
Salt of wormwood	-		Yellow soda ash	93.0	92.0	91.0	90.0	89.0	87.5	90.0	88.0	-	-	-	-	-	-	-	-	-		85.0	84.0
Salt of wormwood	-		Two yellow soda ash	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Sodium sesquicarbonate	-		Two yellow soda ash	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Sodium sesquicarbonate	-		Water-soluble high-molecular compound	HPC	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
MA1	1.5	1.5		HPC	-	-	-	-	-	-	-	1.5	1.5	1.5	2.5	3.0	3.0	3.0	3.0		-	-	-
MA1	1.5	1.5		MA2	-	-	-	-	-	-	-	1.5	1.5	1.5	2.5	3.0	3.0	3.0	3.0	-	-	-
MA3	-	-		MA2	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
MA3	-	-		PAS	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
AG	-	-		PAS	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
AG	-	-		CMC	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
PAP	-	-		CMC	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
PAP	-	-		Silicate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
SRC	-	-		Silicate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
SRC	-	-		The slightly water-soluble compound	Lauric acid	3.0	4.0	5.0	6.0	7.0	6.0	-	-	-	-	-	-	-	-	2.0	4.0	7.0	8.0
Tetradecanoic acid	-	-	-		Lauric acid	3.0	4.0	5.0	6.0	7.0	6.0	-	-	-	-	-	-	-		2.0	4.0	7.0	8.0
Tetradecanoic acid	-	-	-		Palmitinic acid	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Stearic acid	-	-	-		Palmitinic acid	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Stearic acid	-	-	-		Methyl palmitate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Hexanodioic acid	-	-	-		Methyl palmitate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Hexanodioic acid	-	-	-		Stearyl alcohol	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Fine powder	Talcum	-	-		Stearyl alcohol	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
	Talcum	-	-	A type zeolite	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-		-
	Moisture and other compositions		Nubbin	A type zeolite	-	-	-	-	-	-	-	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	-	-	-	Nubbin	Nubbin
Add up to			Nubbin	100.0										Nubbin	Nubbin	Nubbin	Nubbin	Nubbin				Nubbin	Nubbin
Add up to		Manufacture method		100.0										1	2	1	1	1	1	1	1	1	1
Water-soluble inorganic compound nuclear particle temperature (℃)		Manufacture method		45	45	45	45	45	45	45	45	45	45	1	2	1	1	1	1	1	1	1	1
		The water-soluble high-molecular compound temperature (℃)		45	45	45	45	45	45	45	45	45	45	50	50	50	49	50	51	50	50	51	50
The slightly water-soluble compound temperature (℃)		The water-soluble high-molecular compound temperature (℃)		50	50	51	50	50	52	49	50	50	50	50	50	50	49	50	51	50	50	51	50
The slightly water-soluble compound temperature (℃)		The temperature of the surface-treated particle of water-soluble inorganic compound after the 2nd operation finishes (℃)		50	50	51	50	50	52	49	50	50	50	50	50	50	52	53	53	52	55	55	58
The maximum temperature rising degree of wetting thermal value				◎	◎	◎	◎	○	○	◎	◎	◎	◎	50	50	50	52	53	53	52	55	55	58
		Washburn method penetration period [branch]		◎	◎	◎	◎	○	○	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	○	◎	◎	◎
Tack to device		Washburn method penetration period [branch]		◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	○	◎	◎	◎
Tack to device		Particulate median size [μ m]		◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	325	330	330	330	330	330	340	330	330	330
The particulate slope of repose [°]		Particulate median size [μ m]		35	30	30	30	30	30	35	30	30	30	325	330	330	330	330	330	340	330	330	330
The particulate slope of repose [°]		Particulate loose density (g/cm ³)		35	30	30	30	30	30	35	30	30	30	1.13	1.15	1.15	1.15	1.15	1.15	1.14	1.15	1.15	1.15

[table 2]

Form [%]		Embodiment
		Embodiment										a11	a12	a13	a14	a15	a16	a17	a18	a19	a20
		The water-soluble inorganic compound nuclear particle	Yellow soda ash	82.0	82.0	84.0	84.0	84.0	87.0	81.0	82.0	a11	a12	a13	a14	a15	a16	a17	a18	a19	a20	83.0	80.0
Salt of wormwood	-		Yellow soda ash	82.0	82.0	84.0	84.0	84.0	87.0	81.0	82.0	-	-	-	-	-	-	-	-	-		83.0	80.0
Salt of wormwood	-		Sodium bicarbonate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Sodium sesquicarbonate	-		Sodium bicarbonate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Sodium sesquicarbonate	-		Water-soluble high-molecular compound	HPC	-	-	1.0	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
MA1	3.0	3.0		HPC	-	-	1.0	-	-	-	-	-	-	-	-	-	-	-	-		-	-	-
MA1	3.0	3.0		MA2	-	-	-	3.0	-	-	-	-	-	-	-	-	-	-	-	-	-	-
MA3	-	-		MA2	-	-	-	3.0	-	-	-	-	-	3.0	-	-	-	-	-	-	-	-
MA3	-	-		PAS	-	-	-	-	-	3.0	-	-	-	3.0	-	-	-	-	-	-	-	-
AC	-	-		PAS	-	-	-	-	-	3.0	-	-	-	-	-	0.5	-	-	-	-	-	-
AC	-	-		CMC	-	-	-	-	-	-	-	-	-	-	-	0.5	-	-	-	1.0	-	-
PAP	-	-		CMC	-	-	-	-	-	-	-	-	-	-	-	-	-	3.0	-	1.0	-	-
PAP	-	-		Silicate	-	-	-	-	-	-	-	-	-	-	-	-	-	3.0	-	-	-	-
SRC	-	-		Silicate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	3.0	-	-	-
SRC	-	-		The slightly water-soluble compound	Lauric acid	-	6.0	3.0	-	5.0	5.0	-	-	-	-	-	-	-	3.0	6.0	5.0	-	5.0
Tetradecanoic acid	6.0	-	-		Lauric acid	-	6.0	3.0	-	5.0	5.0	-	-	-	-	-	-	-		6.0	5.0	-	5.0
Tetradecanoic acid	6.0	-	-		Palmitinic acid	-	-	-	5.0	-	-	-	-	-	-	-	-	-	-	-	-	-
Stearic acid	-	-	-		Palmitinic acid	-	-	-	5.0	-	-	-	-	-	-	-	5.0	-	-	-	-	-
Stearic acid	-	-	-		Methyl palmitate	-	-	-	-	-	-	-	-	-	-	-	5.0	-	-	-	-	-
Hexanodioic acid	-	-	-		Methyl palmitate	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Hexanodioic acid	-	-	-		Stearyl alcohol	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Fine powder	Talcum	3.0	-		Stearyl alcohol	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
	Talcum	3.0	-	A type zeolite	-	3.0	4.0	-	-	-	4.0	-	-	-	-	-	-	-	4.0	4.0	4.0		-
	Moisture and other compositions		Nubbin	A type zeolite	-	3.0	4.0	-	-	-	4.0	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	4.0	4.0	4.0	Nubbin	Nubbin
Add up to			Nubbin	100.0										Nubbin	Nubbin	Nubbin	Nubbin	Nubbin				Nubbin	Nubbin
Add up to		Manufacture method		100.0										1	3	4	4	4	5	4	4	2	5
Water-soluble inorganic compound nuclear particle temperature (℃)		Manufacture method		55	44	45	60	44	46	44	44	70	45	1	3	4	4	4	5	4	4	2	5
		The water-soluble high-molecular compound temperature (℃)		55	44	45	60	44	46	44	44	70	45	45	51	45	50	50	50	50	50	65	50
The slightly water-soluble compound temperature (℃)		The water-soluble high-molecular compound temperature (℃)		60	51	50	63	60	61	58	57	70	60	45	51	45	50	50	50	50	50	65	50
The slightly water-soluble compound temperature (℃)		The temperature of the surface-treated particle of water-soluble inorganic compound after the 2nd operation finishes (℃)		60	51	50	63	60	61	58	57	70	60	60	50	52	65	54	56	55	54	80	54
The maximum temperature rising degree of wetting thermal value				◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	60	50	52	65	54	56	55	54	80	54
		Washburn method penetration period [branch]		◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	◎	○	◎	◎	◎	○	◎	◎	◎
Tack to device		Washburn method penetration period [branch]		◎	◎	○	◎	○	○	◎	◎	○	○	◎	◎	○	◎	◎	◎	○	◎	◎	◎
Tack to device		Particulate median size [μ m]		◎	◎	○	◎	○	○	◎	◎	○	○	340	340	400	400	380	385	550	500	420	580
The particulate slope of repose [°]		Particulate median size [μ m]		40	40	45	35	30	30	45	45	45	45	340	340	400	400	380	385	550	500	420	580
The particulate slope of repose [°]		Particulate loose density (g/cm ³)		40	40	45	35	30	30	45	45	45	45	1.07	1.07	1.03	1.05	1.08	1.07	0.92	0.94	1.00	0.90

[table 3]

Form [%]		Embodiment
		Embodiment										a21	a22	a23	a24	a25	a26	a27		a28
		The water-soluble inorganic compound nuclear particle	Yellow soda ash	76.0	45.0	45.0	45.0	84.0	61.0	84.0		a21	a22	a23	a24	a25	a26	a27		a28		85.0
Salt of wormwood	-		Yellow soda ash	76.0	45.0	45.0	45.0	84.0	61.0	84.0		40.0	-	-	-	-	-		-			85.0
Salt of wormwood	-		Sodium bicarbonate	-	-	40.0	-	-	-	-		40.0	-	-	-	-	-		-		-
Sodium sesquicarbonate	-		Sodium bicarbonate	-	-	40.0	-	-	-	-		-	-	40.0	-	-	-		-		-
Sodium sesquicarbonate	-		Water-soluble high-molecular compound	HPC	-	-	-	-	-	-	-		-	40.0	-	-	-		-		-
MA1	6.0	3.0		HPC	-	-	-	-	-	-	-		3.0	3.0	3.0	-	3.0		3.0		-
MA1	6.0	3.0		MA2	-	-	-	-	-	-	-		3.0	3.0	3.0	-	3.0		3.0		-
MA3	-	-		MA2	-	-	-	-	-	-	-		-	-	-	-	-		-		-
MA3	-	-		PAS	-	-	-	-	-				-	-	-	-	-		-		-
AG	-	-		PAS	-	-	-	-	-				-	-	-	-	-		-		-
AG	-	-		CMC	-	-	-	-	-	-	-		-	-	-	-	-		-		-
PAP	-	-		CMC	-	-	-	-	-	-	-		-	-	-	-	-		-		-
PAP	-	-		Silicate	-	-	-	-	-	25.0	-		-	-	-	-	-		-		-
SRC	-	-		Silicate	-	-	-	-	-	25.0	-		-	-	-	-	-		-		-
SRC	-	-		The slightly water-soluble compound	Lauric acid	6.0	7.0	7.0	7.0	-	6.0	-		-	-	-	-		-		-
Tetradecanoic acid	-	-	-		Lauric acid	6.0	7.0	7.0	7.0	-	6.0	-		-	-	-	-		-		-
Tetradecanoic acid	-	-	-		Palmitinic acid	-	-	-	-	-	-	-		-	-	-	-		-		-
Stearic acid	-	-	-		Palmitinic acid	-	-	-	-	-	-	-		-	-	-	-		-		-
Stearic acid	-	-	-		Methyl palmitate	-	-	-	-	4.0	-	-		-	-	-	-		-		-
Hexanodioic acid	-	-	-		Methyl palmitate	-	-	-	-	4.0	-	-		-	-	-	-		3.0		-
Hexanodioic acid	-	-	-		Stearyl alcohol	-	-	-	-	-	-	4.0		-	-	-	-		3.0		-
Fine powder	Talcum	-	-		Stearyl alcohol	-	-	-	-	-	-	4.0		-	-	-	-	-		-
	Talcum	-	-	A type zeolite	4.0	-	-	-	4.0	-	4.0		4.0		-	-	-	-		-
	Moisture and other compositions		Nubbin	A type zeolite	4.0	-	-	-	4.0	-	4.0		4.0		Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin		Nubbin
Add up to			Nubbin	100.0											Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin		Nubbin
Add up to		Manufacture method		100.0										2	1	1	1	3	4		3		4
Water-soluble inorganic compound nuclear particle temperature (℃)		Manufacture method		45	45	45	45	40	60		60		45	2	1	1	1	3	4		3		4
		The water-soluble high-molecular compound temperature (℃)		45	45	45	45	40	60		60		45	45	45	45	45	45	45		45		50
The slightly water-soluble compound temperature (℃)		The water-soluble high-molecular compound temperature (℃)		55	52	52	52	40	50		70		160	45	45	45	45	45	45		45		50
The slightly water-soluble compound temperature (℃)		The temperature of the surface-treated particle of water-soluble inorganic compound after the 2nd operation finishes (℃)		55	52	52	52	40	50		70		160	53	50	50	50	42	60		67		85
The maximum temperature rising degree of wetting thermal value				◎	◎	◎	◎	◎	◎		◎		○	53	50	50	50	42	60		67		85
		Washburn method penetration period [branch]		◎	◎	◎	◎	◎	◎		◎		○	◎	◎	◎	◎	○	○		○		○
Tack to device		Washburn method penetration period [branch]		○	◎	◎	◎	○	○		○		○	◎	◎	◎	◎	○	○		○		○
Tack to device		Particulate median size [μ m]		○	◎	◎	◎	○	○		○		○	600	480	420	300	350	600		345		370
The particulate slope of repose [°]		Particulate median size [μ m]		35	35	35	35	50	50		50		50	600	480	420	300	350	600		345		370
The particulate slope of repose [°]		Particulate loose density (g/cm ³)		35	35	35	35	50	50		50		50	0.95	1.20	1.08	1.16	1.05	0.86		1.04		1.03

[table 4]

Form [%]		Embodiment
		Embodiment							a29	a30	a31	a32	a33	a34	a35
		The water-soluble inorganic compound nuclear particle	Yellow soda ash	100.0	94.0	92.0	97.0	64.0	a29	a30	a31	a32	a33	a34	a35	95.0	92.0
Salt of wormwood	-		Yellow soda ash	100.0	94.0	92.0	97.0	64.0	-	-	-	-	-	-		95.0	92.0
Salt of wormwood	-		Sodium bicarbonate	-	-	-	-	-	-	-	-	-	-	-	-	-
Sodium sesquicarbonate	-		Sodium bicarbonate	-	-	-	-	-	-	-	-	-	-	-	-	-
Sodium sesquicarbonate	-		Water-soluble high-molecular compound	HPC	-	-	-	-	-	-	-	-	-	-	-	-	-
MA1	-	1.5		HPC	-	-	-	-	3.0	-	-	-	-		-	-	-
MA1	-	1.5		MA2	-	-	-	-	3.0	-	-	-	-	-	-	-
MA3	-	-		MA2	-	-	-	-	-	-	-	-	-	-	-	-
MA3	-	-		PAS	-	-	-	-	-	-	-	-	-	-	-	-
AG	-	-		PAS	-	-	-	-	-	-	-	-	-	-	-	-
AG	-	-		CMC	-	-	-	-	-	-	-	-	-	-	-	-
PAP	-	-		CMC	-	-	-	-	-	-	-	-	-	-	-	-
PAP	-	-		Silicate	-	-	-	-	-	-	-	-	-	28.0	-	-
SRC	-	-		Silicate	-	-	-	-	-	-	-	-	-	28.0	-	-
SRC	-	-		The slightly water-soluble compound	Lauric acid	-	-	-	-	-	-	-	-	2.0	-	4.0	7.0
Tetradecanoic acid	-	-	-		Lauric acid	-	-	-	-	-	-	-		2.0	-	4.0	7.0
Tetradecanoic acid	-	-	-		Palmitinic acid	-	-	-	-	-	-	-	-	-	-	-
Stearic acid	-	-	-		Palmitinic acid	-	-	-	-	-	-	-	-	-	-	-
Stearic acid	-	-	-		Methyl palmitate	-	-	-	-	-	-	-	-	-	-	-
Hexanodioic acid	-	-	-		Methyl palmitate	-	-	-	-	-	-	-	-	-	-	-
Hexanodioic acid	-	-	-		Stearyl alcohol	-	-	-	-	-	-	-	-	-	-	-
Fine powder	Talcum	-	-		Stearyl alcohol	-	-	-	-	-	-	-	-	-	-	-	-
	Talcum	-	-	A type zeolite	-	-	-	-	-	-	-	-	-	-	-		-
	Moisture and other compositions		-	A type zeolite	-	-	-	-	Nubbin	Nubbin	Nubbin	Nubbin	-	-	-	Nubbin	Nubbin
Add up to			-	100.0							Nubbin	Nubbin				Nubbin	Nubbin
Add up to		Manufacture method		100.0							-	1	1	1	4	1	1
Water-soluble inorganic compound nuclear particle temperature (℃)		Manufacture method		-	45	45	45	45	45	45	-	1	1	1	4	1	1
		The water-soluble high-molecular compound temperature (℃)		-	45	45	45	45	45	45	-	45	45	-	45	-	-
The slightly water-soluble compound temperature (℃)		The water-soluble high-molecular compound temperature (℃)		-	-	-	52	-	52	52	-	45	45	-	45	-	-
The slightly water-soluble compound temperature (℃)		The temperature of the surface-treated particle of water-soluble inorganic compound after the 2nd operation finishes (℃)		-	-	-	52	-	52	52	-	48	49	50	58	52	55
The maximum temperature rising degree of wetting thermal value				×	×	×	◎	×	○	×	-	48	49	50	58	52	55
		Washburn method penetration period [branch]		×	×	×	◎	×	○	×	×	×	×	×	×	×	×
Tack to device		Washburn method penetration period [branch]		-	△	×	○	△	○	○	×	×	×	×	×	×	×
Tack to device		Particulate median size [μ m]		-	△	×	○	△	○	○	320	340	340	330	620	335	340
The particulate slope of repose [°]		Particulate median size [μ m]		40	60	85	40	50	35	30	320	340	340	330	620	335	340
The particulate slope of repose [°]		Particulate loose density (g/cm ³)		40	60	85	40	50	35	30	1.07	0.99	0.95	1.07	0.85	1.14	1.16

[modulating routine b1～b7]

According to following manufacture method, obtain containing the particle b1～b7 of tensio-active agent.

The particulate modulator approach 1 that contains tensio-active agent

According to forming shown in the following table 5, modulation contains the particle b1 of tensio-active agent in the following sequence.At first, the water injection is possessed in the tempering tank that has chuck of whipping appts, temperature is adjusted into 60 ℃.Remove α-SF-Na and nonionogenic tenside to wherein adding, reach PEG#6000, stirred 10 minutes.Then, add MA1 (vinylformic acid/maleic acid sodium salt) and fluorescent agent.Further stir after 10 minutes, add the part of powders A type zeolite and (remove 2.0% a great deal of (each particle relatively, below identical) add when mediating and use, 3.2% a great deal of is for pulverizing auxiliary usefulness, 1.5% for a great deal of for pan coating with each A type talcum), yellow soda ash, salt of wormwood agent S-WAT.Further stir be modulated into moisture 38% in 20 minutes spraying drying with slurry after, with convection type spray-drying tower spraying drying under the condition of 280 ℃ of hot blast temperatures, obtain median size 320 μ m, loose density 0.30g/cm ³, the spray-dried granules of moisture 5%.

On the other hand, in the water paste (moisture concentration 25%) of α-SF-Na that the fatty acid ester sulfonation of raw material, neutralization obtain, add nonionogenic tenside a part (with respect to α-SF-Na 25%), being evaporated to moisture with the film type drying machine is 11%, obtains the mixing enriched material of α-SF-Na and nonionogenic tenside.

With above-mentioned spray-dried granules, this mix enriched material, 2.0% a great deal of A type zeolite, remove 0.5% a great deal of spraying add the remaining nonionogenic tenside of usefulness and water and drop into kneader continuously ((strain) trembles this ironworker manufacturing, the KRC-S4 type), at the ability of kneading 120kg/hr, mediate under the condition that temperature is 60 ℃, obtain containing the thing that mixes of tensio-active agent.((strain) Fuji Paudal makes with the two stamping machines (Pelleter Double) that possess aperture 10mm punch die with this thing that mixes that contains tensio-active agent, the EXDFJS-100 type) extrudes on one side, on one side cut off (cutting knife circumferential speed 5m/s), obtain the forming composition that particulate state about long 5～30mm contains tensio-active agent with cutting knife.

Then, contain the particulate state A type zeolite (median size 180 μ m) that auxiliary is pulverized in the conduct of adding 3.2% a great deal of in the forming composition of tensio-active agent in the particulate state that obtains, in (10 ℃ in cold wind, 15m/s) (Hosokawa Micron (strain) makes with the Fitz grinding machine that is provided as 3 sections of series connection down in coexistence, DKA-3) pulverize (mesh size: the 1st section/the 2nd section/the 3rd section=12mm/6mm/3mm, rotating speed: the 1st section/the 2nd section/the 3rd section all is 4700 rev/mins).At last, rotate mixing machine (drum diameter 585mm with horizontal round shape, the long 490mm of cylinder in the inner wall of the rotating cylinder of volume 131.7L, has the baffle plate of the gap 20mm of two pieces of high 45mm and inner wall), at filling ratio 30 volume %, 22 rev/mins of rotating speeds under 25 ℃ the condition, add the fine powder A type zeolite of 1.5% a great deal of, nonionogenic tenside and spices that 0.5% a great deal of is sprayed on one side rotate simultaneously and obtained surface modified granules in 1 minute.

For making a particulate part that obtains painted, the particle that will contain tensio-active agent is on one side transferred (the particle floor height 30mm that contains tensio-active agent on the rotary conveyor with rotary conveyor with the speed of 0.5m/s, the wide 300mm of layer), one side is at 20% aqueous dispersions of its surface spray pigment, obtain containing particle b1 (median size 550 μ m, the loose density 0.84g/cm of tensio-active agent ³).

Same with the modulator approach of the particle b1 that contains tensio-active agent, obtain containing particle b2, the b3 (median size, loose density are recorded in the table 5) of tensio-active agent.

Close the particulate modulator approach 2 of tensio-active agent

According to the composition shown in the following table 5, modulation contains the particle b4 of tensio-active agent in the following sequence.Below in the composition shown in the table 5, to possess space between tine shape scoop, scoop and wall be that ((strain) Matsubo makes for the Leodige mixing tank of 5mm with removing tensio-active agent, pan coating outer whole composition (25 ℃ of the temperature) input of P type zeolite, pigment, spices with 5.0% a great deal of, the M20 type) in (filling ratio 50 volume %), with 200 rev/mins on main shaft, cutting knife begins for 200 rev/mins to stir.Stirring beginning and added surfactant mixture (nonionogenic tenside and anion surfactant are heated to 60 ℃ of mixed uniformly mixtures in advance) and water (60 ℃ of temperature) with 2 minutes after 30 seconds, is that continuation stirring-granulating to median size is 400 μ m under 30 ℃ the condition at jacket temperature.At last, the P type zeolite that adds 5.0% a great deal of stirred 30 seconds, carried out surface modification, obtained particle.

For making a particulate part that obtains painted, with and contain 20% aqueous dispersions of the same method spraying pigment of the particulate modulator approach 1 of tensio-active agent, obtain containing particle b4 (median size 400 μ m, the loose density 0.80g/cm of tensio-active agent ³).

The particulate modulator approach 3 that contains tensio-active agent

According to the composition shown in the following table 5, modulation contains the particle b5 of tensio-active agent in the following sequence.Below in the composition shown in the table 5, to remove a part (2.0% a great deal of (each particle relatively of nonionogenic tenside, powders A type zeolite (zeolite A), below identical) add when mediating and use, 3.2% a great deal of is used for pulverizing auxiliary, 1.5% a great deal of is except each A type talcum of using of pan coating), pigment, the outer composition of spices dissolves in water or disperse to be modulated into the slurry of moisture 38% after, with convection type spray-drying tower spraying drying under the condition of 300 ℃ of hot blast temperatures, obtain median size 330 μ m, loose density 0.30g/cm ³, the spray-dried granules of moisture 3%.With this dried particles together, the nonionogenic tenside of usefulness and water are added in the A type zeolite of 2.0% a great deal of, the spraying of removing 0.5% a great deal of to be dropped into kneader continuously ((strain) trembles this ironworker manufacturing, the KRC-S4 type), at the ability of kneading 120kg/hr, mediate under the condition that temperature is 60 ℃, obtain containing the thing that mixes of tensio-active agent.

((strain) Fuji Paudal makes with the two stamping machines (Pelleter Double) that possess aperture 10mm punch die with this thing that mixes that contains tensio-active agent, the EXDFJS-100 type) extrudes on one side, on one side cut off (cutting knife circumferential speed 5m/s), obtain the forming composition that particulate state about long 5～30mm contains tensio-active agent with cutting knife.

Then, with the particulate state that obtains contain the tensio-active agent forming composition with and the same method of particulate modulator approach 1 that contains tensio-active agent pulverize, surface modification obtains particle then.For making a particulate part that obtains painted, with and contain 20% aqueous dispersions of the same method spraying pigment of the particulate modulator approach 1 of tensio-active agent, obtain containing particle b5 (median size 540 μ m, the loose density 0.77g/cm of tensio-active agent ³).

Same with the modulator approach of the particle b5 that contains tensio-active agent, obtain containing the particle b7 (median size, loose density is recorded in the table 5) of tensio-active agent.

The particulate modulator approach 4 that contains tensio-active agent

According to forming shown in the following table 5, modulation contains the particle b6 of tensio-active agent in the following sequence.At first, the water injection is possessed in the tempering tank that has chuck of whipping appts, temperature is adjusted into 50 ℃.To wherein adding sodium sulfate and fluorescent agent, stirred 10 minutes.Then, add yellow soda ash after, add PAS (polyacrylic acid sodium salt), further stir 10 minutes after, a part of adding sodium-chlor and powders A type zeolite.Further stir and be modulated into the spraying drying slurry in 30 minutes.The spraying drying that obtains is 50 ℃ with the temperature of slurry.This slurry is carried out spraying drying with the convection type spray drying unit that possesses pressure nozzle, obtain moisture 3%, loose density 0.50g/cm ³, the spray-dried granules of median size 250 μ m.

Additionally, nonionogenic tenside, PEG#6000, anion surfactant are mixed under 80 ℃ temperature condition, be modulated into the surfactant composition of water content 10%.LAS-Na is to use with aqueous sodium hydroxide solution neutral solution state.

Then, the space that the spray-dried granules input that obtains is possessed between tine shape scoop, scoop and wall is Leodige mixing tank ((strain) Matsubo manufacturing of 5mm, the M20 type) in (filling ratio 50 volume %), the flow that divides with 10L/ in chuck flows into 80 ℃ warm water on one side, Yi Bian start the stirring of main shaft (150 rev/mins), cutting knife (4000 rev/mins).Added the above-mentioned surfactant composition that modulate with 2 minutes this moment, stir 5 minutes then after, the part (10% a great deal of) of input layered silicate (SKS-6, median size 5 μ m) and powders A type zeolite stirred 2 minutes, obtained particle.

The part (2% a great deal of) of the particle that obtains and powders A type zeolite is mixed with the V-type mixing tank, after the spray perfume, for making a particulate part that contains tensio-active agent painted, with with 20% aqueous dispersions of the same method spraying pigment of the particulate modulator approach 1 that contains tensio-active agent, obtain containing particle b6 (median size 300 μ m, the loose density 0.75g/cm of tensio-active agent ³).

[table 5]

Form [%]			b1	b2	b3	b4	b5	b6	b7
Form [%]			b1	b2	b3	b4	b5	b6	b7	Tensio-active agent	α-SF-Na		10.0	10.0	10.0	3.0	-	-	-
LAS-K		8.0	8.0	3.0	-	15.0	-	-			α-SF-Na		10.0	10.0	10.0	3.0	-	-	-
LAS-K		8.0	8.0	3.0	-	15.0	-	-	LAS-Na		-	-	-	-	-	12.0	13.0
AOS-K		1.0	-	-	-	10.0	-	-	LAS-Na		-	-	-	-	-	12.0	13.0
AOS-K		1.0	-	-	-	10.0	-	-	AS-Na		-	-	-	-	-	1.0	7.0
Soap		9.0	9.0	7.0	1.0	3.0	3.0	2.0	AS-Na		-	-	-	-	-	1.0	7.0
Soap		9.0	9.0	7.0	1.0	3.0	3.0	2.0	Nonionogenic tenside A		-	-	-	20.0	-	11.0	0.5
Nonionogenic tenside B		4.0	5.0	6.0	-	3.0	-	-	Nonionogenic tenside A		-	-	-	20.0	-	11.0	0.5
Nonionogenic tenside B		4.0	5.0	6.0	-	3.0	-	-	Water-soluble high-molecular compound	Ma1		3.0	3.0	1.0	3.0	-	-	3.0
PAS		-	-	-	-	-	6.0	-		Ma1		3.0	3.0	1.0	3.0	-	-	3.0
PAS		-	-	-	-	-	6.0	-		PEG#6000		0.2	0.2	-	1.0	-	0.2	0.2
Mineral compound	A type zeolite		20.0	20.0	25.0	-	20.0	20.0		PEG#6000		0.2	0.2	-	1.0	-	0.2	0.2	10.0
	A type zeolite		20.0	20.0	25.0	-	20.0	20.0	P type zeolite		-	-	-	25.0	-	-	-		10.0
	Salt of wormwood		10.0	9.0	9.0	2.0	10.0	-	P type zeolite		-	-	-	25.0	-	-	-	-
	Salt of wormwood		10.0	9.0	9.0	2.0	10.0	-	Layered silicate		-	-	-	8.0	-	8.0	12.0	-
	S-WAT		2.0	-	2.0	-	-	-	Layered silicate		-	-	-	8.0	-	8.0	12.0	-
	S-WAT		2.0	-	2.0	-	-	-	Sodium-chlor		-	-	-	3.0	-	5.0	-	-
	Sodium sulfate		-	-	-	-	-	10.0	Sodium-chlor		-	-	-	3.0	-	5.0	-	20.0
	Sodium sulfate		-	-	-	-	-	10.0	Moisture (%)			6.0	5.0	6.0	8.0	5.0	6.0	20.0	5.5
Pigment		Kind	A	A	A	A	C	B	Moisture (%)			6.0	5.0	6.0	8.0	5.0	6.0	B	5.5
		Kind	A	A	A	A	C	B	Amount	0.02	0.02	0.02	0.02	0.02	0.02	0.02		B
		Spices		Kind	A	B	C	-	Amount	0.02	0.02	0.02	0.02	0.02	0.02	0.02	D	A	B
Amount	0.2			Kind	A	B	C	-	0.2	0.2	-	0.2	0.2	0.2			D	A	B
Amount	0.2			Fluorescent agent			0.10	0.05	0.2	0.2	-	0.2	0.2	0.2	0.01	-	0.05	0.10	0.10
Yellow soda ash			Nubbin	Fluorescent agent			0.10	0.05	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	0.01	-	0.05	0.10	0.10
Yellow soda ash			Nubbin	Add up to			100.0	100.0	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	Nubbin	100. 0	100.0	100.0	100.0	100.0
Median size [μ m]			550	Add up to			100.0	100.0	550	540	400	540	300	400	100. 0	100.0	100.0	100.0	100.0
Median size [μ m]			550	Loose density (g/cm3)			0.84	0.84	550	540	400	540	300	400	0.86	0.80	0.77	0.75	0.80

[the modulation example of granular activated bleaching agent thing]

The modulator approach of granular activated bleaching agent thing A

As activated bleaching agent; ratio in the AOS-Na powder of the PEG#6000 of the 4-decanoyl oxybenzoic acid (4-decanoyloxybenzoic acid) (Mitsui Chemicals (strain) manufacturing) of 70 mass parts, 20 mass parts, 5 mass parts is supplied with extruding mixing machine (Extrude-O-Mix) the EM-6 type that Hosokawa Micron (strain) makes; mix and extrude (60 ℃ of the temperature of mixing), obtain the extrusion pin of the line thigh shape of diameter 0.8mm φ.This extrusion pin (being cooled to 20 ℃ by cold wind) is imported in the Fitz grinding machine DKA-3 type of Hosokawa Micron (strain) manufacturing, also same A type zeolite powder 5 mass parts of supplying with as auxiliary, pulverize, obtain the activated bleaching particulate matter A of the about 700 μ m of median size.

The modulator approach of granular activated bleaching agent thing B

Except that with 4-dodecanoyl oxybenzoic acid sodium sulfonate (sodium4-dodecanoyloxybenzene-sulfonate) as the bleach activator and modulation activated bleaching particulate matter A modulate activated bleaching particulate matter B equally.

The modulator approach of granular activated bleaching agent thing C

Except that with 4-nonanoyl oxybenzoic acid sodium sulfonate (sodium4-nonanoyloxybenzene-sulfonate) as the bleach activator and modulation activated bleaching particulate matter A modulate activated bleaching particulate matter C equally.

[embodiment 1～35, comparative example 1～4]

According to the composition of record in following table 6～10, modulate granular constituent with following method, estimated solvability (low temperature aggegation rate), solidified nature (curing degree), flowability.The result is recorded in table together

In 6～10.

The modulation of granular detergent composition

Rotate mixing machine (drum diameter 585mm with horizontal round shape, the long 490mm of cylinder, volume is in the inner wall of the rotating cylinder of 131.7L, the baffle plate that the gap 20mm of two pieces of high 45mm and inner wall is arranged), at filling ratio 30 volume %, 22 rev/mins of rotating speeds, under 25 ℃ the condition, with (b) of record in (a) surface-treated particle of water-soluble inorganic compound of table 1～4 kind of record, the table 5 contain surfactant granules, and other composition mixed 5 minutes according to the composition shown in table 6～10, obtain granular detergent composition.The median size agent loose density of the granular detergent composition that obtains is recorded in table 6～10.

(1) evaluation of solvability (low temperature aggegation rate)

The culture dish that the 5g granular detergent composition is injected lightly the 80mL water that fills 5 ℃ left standstill 5 minutes.After leaving standstill, the sieve by sieve aperture 3360 μ m together with culture dish and water, residual detergent composition was 60 ℃ of dryings 2 hours on the sieve.Measure dried quality and obtain low temperature aggegation rate % with following formula.

The relation of above-mentioned low temperature aggegation rate of trying to achieve and usability is as follows.If consider the usability in the family, as the preferred low temperature aggegation of washing composition rate less than 20%.

Good: low temperature aggegation rate less than 5%

Common: low temperature aggegation rate 5～less than 20%

Difference: low temperature aggegation rate 20～less than 40%

Non-constant: low temperature aggegation rate is more than 40%

(2) evaluation of solidified nature (curing degree)

With beginning from skin by carton box plate (basic weight: 350g/m ²), wax lining paper (wax-sandwiched paper) (basic weight: 30g/m ²), kraft paper (basic weight: 70g/m ²) paper container (the water vapour permeability 25g/m of three layers of formation ²24 hours (40 ℃ 90%RH), are made the chest of growth 15cm * wide 9.3cm * high 18.5cm.Granular detergent composition 1.2kg is put into this case, in the circulation thermostatic constant wet chamber of 25 ℃ (65%RH, 8 hours), 45 ℃ (85%RH, 16 hours), preserved 30 days, obtain through the time solidified nature test sample.Through the time preserve after, washing composition moved on on the sieve that sieve aperture is 4mm gently solidifies, the quality of the washing composition that weighing is residual is obtained curing degree by following formula.

The relation of above-mentioned curing degree of trying to achieve and usability as shown below.If consider the usability in the family, as detergent composition, preferred consolidation rate less than 20%.

Good: curing degree less than 5%

Common: curing degree 5～less than 20%

Difference: curing degree 20～less than 40%

Non-constant: curing degree is more than 40%

(3) Liu Dongxing evaluation

With the above-mentioned granular detergent composition that is cured after type is estimated, measure the slope of repose according to the measuring method at slope of repose described later.The result is with following metewand evaluation.If consider the usability in the family, as the preferred slope of repose of washing composition below 60 °.

＜metewand 〉

Zero: the slope of repose is below 50 °

△: the slope of repose surpasses 50 ° below 60 °

*: the slope of repose is above 60 °

Median size among the present invention, loose density and slope of repose are measured with following method.

(4) mensuration of median size

About each sample and composition thereof, be that 9 sections sieve and the pallet of 1680 μ m, 1410 μ m, 1190 μ m, 1000 μ m, 710 μ m, 500 μ m, 350 μ m, 250 μ m, 149 μ m carries out progressive operation with sieve aperture.Progressive operation is piled up sieve in pallet by the little order that is sieved to the big sieve of sieve aperture of sieve aperture, above the sieve of 1680 μ m of topmost, put into the basic sample of 100g at every turn, close the lid and place it in rotap shaker ((strain) meal field making manufacturing, knock: 156 times/minute, wave: 290 times/minute) on, vibrate after 10 minutes, every kind of sieve is reclaimed sample residual on each sieve and the pallet, the working sample quality.

Quality frequency integrating with pallet and each sieve, the quality frequency of integrating, with 50% or the sieve aperture of higher initial sieve be a μ m, sieve aperture with the sieve bigger a section than a μ m is b μ m, integrating with the quality frequency till the sieve from pallet to a μ m is c%, with the quality frequency on the sieve of a μ m is d%, can try to achieve median size (weight 50%) according to following formula.

Median size (weight 50%)=10 ^{(50-(c-d/ (logb-loga) * logb))/(d/ (logb-loga))}

(5) mensuration of loose density

Loose density is measured according to JIS K3362-1998.

(6) mensuration at slope of repose

Learn apparatus (strain) manufacturing with tube well physics and chemistry, turntable-type slope of repose tester is measured the slope of repose.

[table 6]

Form [%]		Embodiment
		Embodiment							1	2	3	4	5	6	7
		The a particle	Kind	a9	a9	a9	a9	a9	1	2	3	4	5	6	7	a9	a5
Use level	5.0		Kind	a9	a9	a9	a9	a9	10.0	15.0	20.0	30.0	40.0	50.0		a9	a5
Use level	5.0		The b particle	b1[％]	93.8	88.8	83.8	78.8	10.0	15.0	20.0	30.0	40.0	50.0	68.8	58.8	48.8
b2[％]	-	-		b1[％]	93.8	88.8	83.8	78.8	-	-	-	-	-		68.8	58.8	48.8
b2[％]	-	-		b3[％]	-	-	-	-	-	-	-	-	-	-	-	-
b4[％]	-	-		b3[％]	-	-	-	-	-	-	-	-	-	-	-	-
b4[％]	-	-		b5[％]	-	-	-	-	-	-	-	-	-	-	-	-
b6[％]	-	-		b5[％]	-	-	-	-	-	-	-	-	-	-	-	-
b6[％]	-	-		b7[％]	-	-	-	-	-	-	-	-	-	-	-	-
Enzyme granulate A		1.0		b7[％]	-	-	-	-	1.0	1.0	1.0	1.0	1.0	-	-	-	1.0
Enzyme granulate A		1.0	Enzyme granulate B		0.2	0.2	0.2	0.2	1.0	1.0	1.0	1.0	1.0	0.2	0.2	0.2	1.0
SPC-D		-	Enzyme granulate B		0.2	0.2	0.2	0.2	-	-	-	-	-	0.2	0.2	0.2	-
SPC-D		-	The granular activated bleaching agent thing	Kind	-	-	-	-	-	-	-	-	-	-	-	-	-
Use level	-	-		Kind	-	-	-	-	-	-	-	-	-	-	-	-
Use level	-	-		Add up to (%)		100.0							-
Median size [μ m]		538	527	Add up to (%)		100.0							516	505	483	461	439
Median size [μ m]		538	527	Loose density [g/cm ³]		0.86	0.87	0.89	0.90	0.93	0.96	0.99	516	505	483	461	439
Low temperature aggegation rate [%]		0	0	Loose density [g/cm ³]		0.86	0.87	0.89	0.90	0.93	0.96	0.99	0	0	0	0	0
Low temperature aggegation rate [%]		0	0	Curing degree [%]		0	0	0	0	0	2	7	0	0	0	0	0
Mobile		○	○	Curing degree [%]		0	0	0	0	0	2	7	○	○	○	○	△

[table 7]

Form [%]		Embodiment
		Embodiment							8	9	10	11	12	13	14
		The A particle	Kind	a9	a9	a9	a9	a9	8	9	10	11	12	13	14	a6	a6
Use level	10.0		Kind	a9	a9	a9	a9	a9	15.0	20.0	30.0	40.0	10.0	20.0		a6	a6
Use level	10.0		The B particle	b1[％]	-	-	-	-	15.0	20.0	30.0	40.0	10.0	20.0	-	-	-
b2[％]	83.8	78.8		b1[％]	-	-	-	-	73.8	63.8	53.8	83.8	73.8		-	-	-
b2[％]	83.8	78.8		b3[％]	-	-	-	-	73.8	63.8	53.8	83.8	73.8	-	-	-
b4[％]	-	-		b3[％]	-	-	-	-	-	-	-	-	-	-	-	-
b4[％]	-	-		b5[％]	-	-	-	-	-	-	-	-	-	-	-	-
b6[％]	-	-		b5[％]	-	-	-	-	-	-	-	-	-	-	-	-
b6[％]	-	-		b7[％]	-	-	-	-	-	-	-	-	-	-	-	-
Enzyme granulate A		0.2		b7[％]	-	-	-	-	0.2	0.2	0.2	0.2	0.2	-	-	-	0.2
Enzyme granulate A		0.2	Enzyme granulate B		1.0	1.0	1.0	1.0	0.2	0.2	0.2	0.2	0.2	1.0	1.0	1.0	0.2
SPC-D		4.0	Enzyme granulate B		1.0	1.0	1.0	1.0	4.0	4.0	4.0	4.0	4.0	1.0	1.0	1.0	4.0
SPC-D		4.0	The granular activated bleaching agent thing	Kind	A	A	A	A	4.0	4.0	4.0	4.0	4.0	A	C	C	4.0
Use level	1.0	1.0		Kind	A	A	A	A	1.0	1.0	1.0	1.0	1.0	A	C	C
Use level	1.0	1.0		Add up to (%)		100.0							1.0
Median size [μ m]		538	527	Add up to (%)		100.0							516	494	472	538	516
Median size [μ m]		538	527	Loose density [g/cm ³]		0.87	0.88	0.90	0.93	0.96	0.87	0.90	516	494	472	538	516
Low temperature aggegation rate [%]		0	0	Loose density [g/cm ³]		0.87	0.88	0.90	0.93	0.96	0.87	0.90	0	0	0	0	0
Low temperature aggegation rate [%]		0	0	Curing degree [%]		0	0	0	0	5	0	0	0	0	0	0	0
Mobile		○	○	Curing degree [%]		0	0	0	0	5	0	0	○	○	○	○	○

[table 8]

Form [%]		Embodiment
		Embodiment							15	16	17	18	19	20	21
		The a particle	Kind	a4	a4	a4	a8	a8	15	16	17	18	19	20	21	a8	a7
Use level	10.0		Kind	a4	a4	a4	a8	a8	20.0	30.0	10.0	20.0	30.0	10.0		a8	a7
Use level	10.0		The b particle	b1[％]	-	-	-	-	20.0	30.0	10.0	20.0	30.0	10.0	-	-	-
b2[％]	-	-		b1[％]	-	-	-	-	-	-	-	-	-		-	-	-
b2[％]	-	-		b3[％]	-	-	-	-	-	-	-	-	-	-	-	-
b4[％]	-	-		b3[％]	-	-	-	-	-	-	-	-	-	-	-	-
b4[％]	-	-		b5[％]	-	-	-	-	-	-	-	-	-	-	-	81.8
b6[％]	83.8	73.8		b5[％]	-	-	-	-	63.8	-	-	-	-	-	-	81.8
b6[％]	83.8	73.8		b7[％]	-	-	-	75.8	63.8	-	-	-	-	65.8	55.8	-
Enzyme granulate A		0.2		b7[％]	-	-	-	75.8	0.2	0.2	0.2	0.2	0.2	65.8	55.8	-	0.2
Enzyme granulate A		0.2	Enzyme granulate B		1.0	1.0	1.0	1.0	0.2	0.2	0.2	0.2	0.2	1.0	1.0	1.0	0.2
SPC-D		4.0	Enzyme granulate B		1.0	1.0	1.0	1.0	4.0	4.0	10.0	10.0	10.0	1.0	1.0	1.0	6.0
SPC-D		4.0	The granular activated bleaching agent thing	Kind	B	B	B	C	4.0	4.0	10.0	10.0	10.0	C	C	A	6.0
Use level	1.0	1.0		Kind	B	B	B	C	1.0	3.0	3.0	3.0	1.0	C	C	A
Use level	1.0	1.0		Add up to (%)		100.0							1.0
Median size [μ m]		331	332	Add up to (%)		100.0							335	449	437	430	536
Median size [μ m]		331	332	Loose density [g/cm ³]		0.78	0.83	0.87	0.82	0.86	0.90	0.80	335	449	437	430	536
Low temperature aggegation rate [%]		0	0	Loose density [g/cm ³]		0.78	0.83	0.87	0.82	0.86	0.90	0.80	0	0	0	0	5
Low temperature aggegation rate [%]		0	0	Curing degree [%]		10	10	10	15	15	15	0	0	0	0	0	5
Mobile		○	○	Curing degree [%]		10	10	10	15	15	15	0	○	△	○	○	○

[table 9]

Form [%]		Embodiment
		Embodiment							22	23	24	25	26	27	28
		The a particle	Kind	a10	a10	a9	a9	a9	22	23	24	25	26	27	28	a9	a9
Use level	10.0		Kind	a10	a10	a9	a9	a9	20.0	20.0	20.0	20.0	20.0	20.0		a9	a9
Use level	10.0		The b particle	b1[％]	-	-	-	-	20.0	20.0	20.0	20.0	20.0	20.0	-	-	-
b2[％]	-	-		b1[％]	-	-	-	-	63.8	-	-	-	-		-	-	-
b2[％]	-	-		b3[％]	-	-	-	-	63.8	-	-	-	-	-	63.8	-
b4[％]	83.8	73.8		b3[％]	-	-	-	-	10.0	10.0	15.0	10.0	23.0	-	63.8	-
b4[％]	83.8	73.8		b5[％]	-	-	-	-	10.0	10.0	15.0	10.0	23.0	-	-	50.0
b6[％]	-	-		b5[％]	-	-	-	-	-	63.8	-	-	-	-	-	50.0
b6[％]	-	-		b7[％]	-	-	-	-	-	63.8	-	-	-	58.8	-	-
Enzyme granulate A		1.0		b7[％]	-	-	-	-	1.0	0.2	0.2	0.2	0.2	58.8	-	-	1.0
Enzyme granulate A		1.0	Enzyme granulate B		0.2	0.2	1.0	1.0	1.0	0.2	0.2	0.2	0.2	1.0	1.0	1.0	1.0
SPC-D		4.0	Enzyme granulate B		0.2	0.2	1.0	1.0	4.0	4.0	4.0	4.0	4.0	1.0	1.0	1.0	4.0
SPC-D		4.0	The granular activated bleaching agent thing	Kind	C	C	A	B	4.0	4.0	4.0	4.0	4.0	C	A	A	4.0
Use level	1.0	1.0		Kind	C	C	A	B	1.0	1.0	1.0	1.0	1.0	C	A	A
Use level	1.0	1.0		Add up to (%)		100.0							1.0
Median size [μ m]		413	406	Add up to (%)		100.0							500	342	406	495	476
Median size [μ m]		413	406	Loose density [g/cm ³]		0.83	0.87	0.89	0.84	0.87	0.91	0.85	500	342	406	495	476
Low temperature aggegation rate [%]		0	5	Loose density [g/cm ³]		0.83	0.87	0.89	0.84	0.87	0.91	0.85	0	0	0	0	0
Low temperature aggegation rate [%]		0	5	Curing degree [%]		0	0	0	0	5	0	5	0	0	0	0	0
Mobile		○	○	Curing degree [%]		0	0	0	0	5	0	5	○	○	△	○	○

[table 10]

Form [%]			Embodiment							Comparative example
			Embodiment							Comparative example				29	30	31	32	33	34	35	1	2	3	4
			The a particle	Kind		a17	a18	a19	a25	a26	a27	a28	a29	29	30	31	32	33	34	35	1	2	3	4	a31	a32	a33
Use level		20.0		Kind		a17	a18	a19	a25	a26	a27	a28	a29	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0		a31	a32	a33
Use level		20.0		The b particle	b1[％]		-	-	-	-	-	-	-	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0	78.8	78.8	78.8	78.8
b2[％]		-	-		b1[％]		-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-		78.8	78.8	78.8	78.8
b2[％]		-	-		b3[％]		-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
b4[％]		-	-		b3[％]		-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
b4[％]		-	-		b5[％]		-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
b6[％]		-	-		b5[％]		-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
b6[％]		-	-		b7[％]		78.8	78.8	78.8	78.8	78.8	78.8	78.8	-	-	-	-	-	-	-	-	-	-	-	-	-
Enzyme granulate A			1.0		b7[％]		78.8	78.8	78.8	78.8	78.8	78.8	78.8	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	-	-	-	-	1.0
Enzyme granulate A			1.0	Enzyme granulate B			0.2	0.2	0.2	0.2	0.2	0.2	0.2	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	0.2	0.2	0.2	0.2	1.0
SPC-D			-	Enzyme granulate B			0.2	0.2	0.2	0.2	0.2	0.2	0.2	-	-	-	-	-	-	-	-	-	0.2	0.2	0.2	0.2	-
SPC-D			-	The granular activated bleaching agent thing		Kind	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Use level						Kind
Use level	Add up to (%)					100.0 100.0
Median size [μ m]				431	421	100.0 100.0											405	391	441	390	395	503	507	505	563
Median size [μ m]			Loose density [g/cm ³]			0.82	0.83	0.84	0.85	0.81	0.85	0.85	0.89	0.88	0.89	0.84	405	391	441	390	395	503	507	505	563
Low temperature aggegation rate [%]			Loose density [g/cm ³]			0.82	0.83	0.84	0.85	0.81	0.85	0.85	0.89	0.88	0.89	0.84	0	0	0	0	0	10	0	70	45	55	50
Low temperature aggegation rate [%]			Curing degree [%]				0		10	10	0	10	50	0	35	40	0	0	0	0	0	10	0	70	45	55	50
Mobile			Curing degree [%]				0		10	10	0	10	50	0	35	40	△	△	△	△	△	△	△	×	△	○	△

[embodiment 36～52]

The spices of spraying during for the modulation that in embodiment 1～17, contains surfactant granules, any one of nonionogenic tenside or both, in that surface-treated particle of water-soluble inorganic compound, the particle that contains tensio-active agent and other particulate component are sprayed during powder mixes, obtain granular detergent composition (embodiment 36～52) in the horizontal circle tubular is rotated mixing machine.This granular detergent composition has also obtained the evaluation result same with embodiment 1～17.

[embodiment 53～69]

The pigment aqueous dispersions of spraying when modulating for the particle that contains tensio-active agent among the embodiment 1～17, with surface-treated particle of water-soluble inorganic compound, the particle that contains tensio-active agent and other particulate component in the horizontal circle tubular is rotated mixing machine after the powder mixes, according to the modulator approach 1 that contains surfactant granules in the same method of the method spraying of record, obtain granular detergent composition (embodiment 53～69).This granular detergent composition has also obtained the evaluation result same with embodiment 1～17.

[embodiment 70～83]

Except that the a9 particle as surface-treated particle of water-soluble inorganic compound among the embodiment 4 being changed to a1～a3, a12, each particle of a16 particulate, modulation obtains granular detergent composition (embodiment 70～74) similarly to Example 4.This granular detergent composition has also obtained the evaluation result same with embodiment 4.

Have again, except that the a18 particle as surface-treated particle of water-soluble inorganic compound among the embodiment 30 being changed to a11, a13～a15, a20～each particle of a24 particulate, modulation obtains granular detergent composition (embodiment 75～83) similarly to Example 30.This granular detergent composition has also obtained the evaluation result same with embodiment 30.

The granular detergent composition 40g of the granular detergent composition of embodiment 4 and comparative example 2 is placed the part of 1 periphery of the fan-shaped recess that automatic washing machine " MAW-V8TP " that Mitsubishi Electric's (strain) makes cuts apart near 6 of agitator with cone shape Set Status.Under the situation of the state of the detergent composition that do not crumble, dress material 3kg (cotton system underwear 50 quality %, polyester/cotton blended shirt 50 quality %) is dropped into washing machine.Not directly with water under the situation of middle washing composition, the flow that divides with 10L/ injects 10 ℃ tap water 38L.Short period of time washing procedure washing with so-called " washing fast " program.Washing procedure (3 minutes) finishes the back draining, with the state of detergent composition residual in Visual Confirmation dress material and the Wash tub.Agglutinator with respect to detergent composition in the comparative example 2 is residual in a large number, and washing composition does not have residual among the embodiment 4.

The granular detergent composition of the granular detergent composition of embodiment 4 and comparative example 340g is placed automatic washing machine " ASW-ZR750 " that Sanyo Electric (strain) the makes part of periphery that is divided into 5 parts 1 of fan-shaped recess near agitator with cone shape Set Status.Under the situation of the state of the detergent composition that do not crumble, dress material 3kg (cotton system underwear 50 quality %, polyester/cotton blended shirt 50 quality %) is dropped into washing machine.Not directly with water under the situation of middle detergent composition, the flow that divides with 10L/ injects 10 ℃ tap water 39L.Washing procedure washing with the weak weak current of the whipping force of so-called " weak washing procedure ".Washing procedure (8 minutes) finishes the back draining, with the state of detergent composition residual in Visual Confirmation dress material and the Wash tub.Agglutinator with respect to detergent composition in the comparative example 3 is residual in a large number, and washing composition does not have residual among the embodiment 4.

About the granular detergent composition of embodiment 4 and the granular detergent composition of comparative example 3, use has tumbling-box washing machine (Sharp's (strain) manufacturing of washing composition input port, ES-E61), in the input port, drop into the 40g granular detergent composition, with standard program washing (10 ℃ of water temperatures, water yield 30L, dress material 3kg (cotton system underwear 50 quality %, polyester/cotton blended shirt 50 quality %)).This washing when carrying out 30 days repeatedly, remains in input port (about 10g) with respect to the not molten residue of detergent composition in the comparative example 3 once a day, and detergent composition does not have residual among the embodiment 4.

Raw materials used as follows among the embodiment.

(water-soluble inorganic compound nuclear particle)

Yellow soda ash: the particle ashes (make, median size 320 μ m, loose density 1.07g/cm by Asahi Glass (strain) ³)

Sodium sesquicarbonate: (U.S. FMC Corp. makes Sesqui TM Sodium Sesquicarbonate, median size 290 μ m, loose density 0.75g/cm ³)

Salt of wormwood: salt of wormwood (powder) (make, median size 490 μ m, loose density 1.30g/cm by Asahi Glass (strain) ³)

Sodium bicarbonate: sodium bicarbonate industry heavy duty is (Asahi Glass (strain) manufacturing) not

Sodium sulfate: neutral five water saltcake (Japanese chemical industry (strain) manufacturing)

S-WAT: anhydrous sodium sodium sulphate (Divine Land chemistry (strain) manufacturing)

Sodium-chlor: day smart roasting salt C (Japanese salt manufacturing (strain) manufacturing)

Layered silicate: the crystallinity laminar silicic acid is received, SKS-6 (Clariant (strain) manufacturing)

(water-soluble high-molecular compound)

HPC: (Japanese Cao Da (strain) makes HPC to hydroxypropylcellulose, and SSLType) being diluted with water to pure composition is 5%

MA1: vinylformic acid/maleic acid sodium salt, Aqualic TL-400 (Japanese catalyzer (strain) manufacturing) (aqueous solution of pure composition 40%)

MA2: vinylformic acid/maleic acid sodium salt: it is 20% that Aqualic TL-400 (Japanese catalyzer (strain) manufacturing) is diluted with water to pure composition

MA3: vinylformic acid/maleic acid sodium salt: it is 20% that Sokalan CP45 (BASF AG's manufacturing) is diluted with water to pure composition

PAS: polyacrylic acid sodium salt: the pure composition of Aqualic DL-40 (Japanese catalyzer (strain) manufacturing) is 40% the aqueous solution

AG: sodiun alginate; The pure composition of Duckalgin NSPLL (the civilian Food Chemifa of (strain) discipline makes) is 4% the aqueous solution

CMC: Xylo-Mucine, the pure composition of CMC Daicel 1105 (Daicel chemical industry (strain) manufacturing) are 5% the aqueous solution

PVA: polyvinyl alcohol, the pure composition of Kuraray Poval PVA-105 ((strain) Kuraray manufacturing) are 5% the aqueous solution

PAP: poly (sodium aspartate), Baypure DS100/40% (Bayer makes, and pure composition is 40% the aqueous solution)

Silicate: Japanese chemical industry is made No. 1 sodium silicate (45% aqueous solution)

PEG#6000:Lion (strain) makes polyoxyethylene glycol, trade(brand)name PEG#6000M

SRC:Clariant Japan (strain) soil release polymer (soil releasepolymer), Texcare SRN-325,25% aqueous solution

(slightly water-soluble compound)

Lauric acid: Japanese grease (strain) is made, NAA-122,43 ℃ of fusing points

Tetradecanoic acid: new Japanese physics and chemistry (strain) is made, tetradecanoic acid, 52 ℃ of fusing points

Palmitinic acid: new Japanese physics and chemistry (strain) is made, palmitinic acid P, 58 ℃ of fusing points

Stearic acid: new Japanese physics and chemistry (strain) is made, Seichin stearic acid 5000,65 ℃ of fusing points

Uniphat A60: Lion (strain) makes, Pastell M-16,30 ℃ of fusing points

Hexanodioic acid: Sumitomo Chemical (strain) is made, 151 ℃ of fusing points

Stearyl alcohol: new Japanese physics and chemistry (strain) is made, Conol 30SS, 57 ℃ of fusing points (fine powder)

A type zeolite: Silton B (marshy land chemistry (strain) is made, pure composition 80%)

P type zeolite: DOUCIL A24 (manufacturing of INEOS Silicas company)

Talcum: Micro Ace LG (Japanese talcum (strain) manufacturing)

(tensio-active agent)

α-F-Na: carbonatoms 14: carbonatoms 16=18: the sodium salt of 82 alpha-sulfo fatty acid methyl ester (Lion (strain) makes, and AI=70%, lingering section are unreacted fatty acid methyl ester, sodium sulfate, methyl-sulfate, hydrogen peroxide, water etc.)

LAS-K: straight chained alkyl (carbonatoms 10～14) Phenylsulfonic acid (by modulation during surfactant composition with 48% potassium hydroxide aqueous solution in and Lipon LH-200 (Lion (strain) manufacturing) the pure composition 96% of LAS-H) prepare).Use level in the table 5 is represented the quality % as LAS-K.

LAS-Na: straight chained alkyl (carbonatoms 10～14) Phenylsulfonic acid (by modulation during surfactant composition with 48% aqueous sodium hydroxide solution in and Lion (strain) manufacturing LiponLH-200 (the pure composition 96% of LAS-H) prepare).Use level in the table 5 is represented the quality % as LAS-Na.

AOS-K: α-alkene potassium sulfonate (potassium α-olefinsulfonate) (Lion (strain) manufacturing) with alkyl of carbonatoms 14～18

AOS-Na: the α of the alkyl of the carbonatoms 14-alkene sodium sulfonate (powder of sodium α-olefinsulfonate) (trade(brand)name Lipolan PJ-400, Lion (strain) makes)

Soap: the sodium soap of carbonatoms 12～18 (Lion (strain) makes, pure composition: 67%, and titre (titre): 40～45 ℃, lipid acid is formed: C ₁₂: 11.7%, C ₁₄: 0.4%, C ₁₆: 29.2%, C ₁₈F0 (stearic acid): 0.7%, C ₁₈F1 (oleic acid): 56.8%, C ₁₈F2 (linolic acid): 1.2%, molecular weight: 289)

AS-Na: alkylsurfuric acid sodium salt (Sanyo changes into the Sandet LNM that industry (strain) is made) with alkyl of carbonatoms 10～18

The average 8mol addition compound (pure composition 90%) of the oxyethane of nonionogenic tenside A:Diadol 13 (Mitsubishi Chemical's (strain) manufacturing)

The average 15mol addition compound (pure composition 90%) of the oxyethane of nonionogenic tenside B:ECOROL26 (alcohol of the alkyl that ECOGREEN company makes) with carbonatoms 12～16

(pigment)

Pigment A: ultramarine (big Japan refine industry (strain) manufacturing, Ultramarine Blue)

Pigment B:Pigment Green 7 (big Japan refine industry (strain) make)

Pigment C: by with vinyl cyanide/styrene/acrylic as constituting monomer, the median size that obtains by the free radical emulsion polymerization in the aqueous dispersion is the C.I.BASICRED-1 that adds in the polymer resin suspension that constitutes of the spherical resin particle of 0.35 μ m with respect to resin part about 1%, and heat treated can obtain the high-visibility pigment water dispersion of peachiness.

(spices)

Spices A: the spy opens flavor compositions A shown in 2002-146399 communique [table 11]～[table 18]

Spices B: the spy opens flavor compositions B shown in 2002-146399 communique [table 11]～[table 18]

Spices C: the spy opens flavor compositions C shown in 2002-146399 communique [table 11]～[table 18]

Spices D: the spy opens flavor compositions D shown in 2002-146399 communique [table 11]～[table 18]

(enzyme)

The mixture of enzyme granulate A:Kannase 12T (manufacturing of Novozymes company)/LIPEX50T (manufacturing of Novozymes company)/Termamyl 60T (manufacturing of Novozymes company)/Celluzyme 0.7T (manufacturing of Novozymes company)=5/2/1/2 (mass ratio)

The mixture of enzyme granulate B:Everlase 8T (manufacturing of Novozymes company)/LIPEX50T (manufacturing of Novozymes company)/Termamyl 60T (manufacturing of Novozymes company)/Celluzyme 0.7T (manufacturing of Novozymes company)=5/2/1/2 (mass ratio)

(other)

The mixture of fluorescent agent: Tinopal CBS-X (Ciba Specialty Chemicals manufacturing)/Tinopal AMS-GX (Ciba Specialty Chemicals manufacturing)=3/1 (mass ratio)

SPC-D: Mitsubishi's gas chemistry (strain) is made, SPC-D, available oxygen content 13.2%, median size 760 μ m

Claims

1. surface-treated particle of water-soluble inorganic compound, it is characterized by the organic or inorganic water-soluble high-molecular compound that is used as the 1st surface treatment agent the water-soluble inorganic compound nuclear particle is carried out surface treatment, further, this processed surface is used as the slightly water-soluble compound of the 2nd surface treatment agent and handles and form, and described water-soluble inorganic compound nuclear particle is selected from yellow soda ash, salt of wormwood, sodium sulfate, vitriolate of tartar, tripoly phosphate sodium STPP, sodium bicarbonate and concentrated crystal soda; Described organic or inorganic water-soluble high-molecular compound is selected from compound, hydroxypropylcellulose and the water glass with carboxyl; Described slightly water-soluble compound is selected from the lipid acid of carbon number 8～18, the higher alcohols of carbon number 12～22, the methyl esters of palmitinic acid, tetradecanoic acid, stearic acid, eicosanoic acid, docosoic acid or ethyl ester; The amount of above-mentioned the 1st surface treatment agent, when being the organic water-soluble macromolecular compound, with respect to the water-soluble inorganic compound nuclear particle is 0.1～10 quality %, when being inorganic water-soluble high-molecular compound, is 1～30 quality % with respect to the water-soluble inorganic compound nuclear particle; The amount of above-mentioned the 2nd treatment agent is 0.1～10 quality % with respect to carried out surface-treated water-soluble inorganic compound nuclear particle with the 1st surface treatment agent.

2. the surface-treated particle of water-soluble inorganic compound put down in writing of claim 1, its have the water-soluble inorganic compound nuclear particle and on part or all surface on this nuclear particle surface formed contain the 1st surface treatment of organic or inorganic water-soluble high-molecular compound and on lip-deep part or all surface of the 1st surface treatment formed the 2nd surface treatment that contains the slightly water-soluble compound, described water-soluble inorganic compound nuclear particle is selected from yellow soda ash, salt of wormwood, sodium sulfate, vitriolate of tartar, tripoly phosphate sodium STPP, sodium bicarbonate and concentrated crystal soda; Described organic or inorganic water-soluble high-molecular compound is selected from compound, hydroxypropylcellulose and the water glass with carboxyl; Described slightly water-soluble compound is selected from the lipid acid of carbon number 8～18, the higher alcohols of carbon number 12～22, the methyl esters of palmitinic acid, tetradecanoic acid, stearic acid, eicosanoic acid, docosoic acid or ethyl ester.

3. the manufacture method of surface-treated particle of water-soluble inorganic compound is characterized by and comprises following the 1st operation and the 2nd operation,

The 1st operation: in the water-soluble inorganic compound nuclear particle, add the organic or inorganic water-soluble high-molecular compound aqueous solution, the water-soluble inorganic compound nuclear particle is carried out the surface-treated operation with water-soluble high-molecular compound; Described water-soluble inorganic compound nuclear particle is selected from yellow soda ash, salt of wormwood, sodium sulfate, vitriolate of tartar, tripoly phosphate sodium STPP, sodium bicarbonate and concentrated crystal soda; Described organic or inorganic water-soluble high-molecular compound is selected from compound, hydroxypropylcellulose and the water glass with carboxyl; When water-soluble high-molecular compound is the organic water-soluble macromolecular compound, its addition is 0.1～10 quality % with respect to the water-soluble inorganic compound nuclear particle, when water-soluble high-molecular compound was inorganic water-soluble high-molecular compound, its addition was 1～30 quality % with respect to the water-soluble inorganic compound nuclear particle;

The 2nd operation: the lipid acid that is selected from carbon number 8～18 of molten state is added in dropping or spraying in the 1st operation treated water dissolubility mineral compound nuclear particle, the higher alcohols of carbon number 12～22, palmitinic acid, tetradecanoic acid, stearic acid, eicosanoic acid, the slightly water-soluble compound of the methyl esters of docosoic acid or ethyl ester, above-mentioned particle is carried out the surface-treated operation, and the addition of described slightly water-soluble compound is that the temperature of the surface-treated particle of water-soluble inorganic compound after 0.1～10 quality % and the 2nd operation one finish is more than the fusing point of slightly water-soluble compound with respect to treated water dissolubility mineral compound nuclear particle in the 1st operation.

4. the manufacture method put down in writing of claim 3 is characterized in that, is dripping or spraying when adding the slightly water-soluble compound, and the temperature that makes water-soluble inorganic compound nuclear particle surface-treated in the 1st operation is more than the fusing point of slightly water-soluble compound.

5. granular detergent composition, it is characterized by contain (a) claim 1 or 2 surface-treated particle of water-soluble inorganic compound of being put down in writing and, (b) contain the particle of tensio-active agent, this particle contains 10～50 quality % tensio-active agent and inorganic components.