KR101134997B1 - High bulk density granular detergent composition and method for producing same - Google Patents

Abstract

This invention contains 10% or more and 50% or less of (A) nonionic surfactant and less than 45% of water-soluble inorganic compounds which improved the solubility to water, especially the solubility in low temperature, and the average particle diameter is 200-1000 Nonionic surfactant-containing particles having a bulk density of 650 g / L or more, and (B) anionic surfactants containing 10 to 40%, and having an average particle diameter of 200 to 1000 µm and a bulk density of 650 g / L or more. (C) A high bulk density detergent composition containing a particle mixture of active agent-containing particles and a method for producing the same.

Surfactant, detergent, bulk density, low temperature solubility

Description

High bulk density granular detergent composition and manufacturing method thereof {HIGH BULK DENSITY GRANULAR DETERGENT COMPOSITION AND METHOD FOR PRODUCING SAME}

The present invention relates to a high bulk density granular detergent composition for use in garments and the like and a method for producing the same.

In general, high bulk density granular detergent compositions are required to have high solubility in water, particularly low temperature water, as compared to low bulk density granular detergent compositions. On the other hand, various high bulk density granular detergent compositions have been proposed so far.

For example, Patent Document 1 discloses a coarse particle, a non-ionic surfactant-containing particle having excellent fluidity, low solidification resistance, and a high bulk density detergent using the same. Patent Document 2 discloses a high bulk density granular detergent containing surfactant particles containing a specific anionic surfactant at a high concentration of 50% by weight or more. These detergents have improved fluidity and are not described for improving solubility. Patent Document 3 describes a method for producing a powder detergent composition having a high bulk density with excellent solubility, but the bulk density of the obtained granular detergent composition is 630 g / L or less, and neither of high bulk density nor excellent low temperature solubility is satisfactory. . Patent Document 4 also describes a granular detergent having a reduced phosphate without fat contamination cleaning power and fluid paper container expansion, but the bulk density of the granular detergent is also only 550 g / L. In the cited documents 5 and 6, detergent compositions containing nonionic surfactant-containing particles and anionic surfactant-containing particles have been proposed, but are still aimed at stabilizing enzymes, solidifying resistance during storage and preventing recontamination. It is not possible to obtain a high bulk density granular detergent composition having satisfactory solubility in water or in particular having low temperature solubility.

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-100498

[Patent Document 2] Japanese Patent Application Laid-Open No. 10-95997

[Patent Document 3] Japanese Unexamined Patent Publication No. 61-26698

[Patent Document 4] Japanese Patent Application Laid-Open No. 62-158800

[Patent Document 5] Japanese Patent Application Laid-Open No. 6-192697

[Patent Document 6] Japanese Patent Application Laid-Open No. 3-265699

Therefore, an object of this invention is to improve the solubility of water in granular detergent composition, especially solubility in low temperature.

That is, this invention contains the nonionic surfactant containing particle | grains (A) which contain 10-50% of nonionic surfactants and less than 45% of water-soluble inorganic compounds, and have an average particle diameter of 200-1000 micrometers and a bulk density of 650 g / L or more, ,

(B) 10 to 40% of anionic surfactant, an average particle diameter of 200 to 1000 µm and a bulk mixture of anionic surfactant-containing particles having a particle density of 650 g / L or more.

(C) Provides a high bulk density detergent composition.

The present invention also includes (A) nonionic surfactant-containing particles having 10 to 50% of nonionic surfactant and less than 45% of water-soluble inorganic compounds, having an average particle diameter of 200 to 1000 µm and a bulk density of 650 g / L or more,

(B) containing anionic surfactant, and mixing the anionic surfactant containing particle | grains whose average particle diameter is 200-1000 micrometers, and bulk density is 650g / L or more,

(C) It provides the manufacturing method of the high bulk density granular detergent composition which improved low temperature solubility.

According to the present invention, it is possible to provide a granular detergent composition having high bulk density and improved solubility in low temperature water. According to this invention, the granular detergent composition of the high bulk density which is hard to solidify also under high humidity conditions, and has high fluidity is obtained.

(A) Nonionic surfactant containing particle

As a nonionic surfactant which can be used in this invention, the following are mentioned.

(1) polyoxyalkylene alkyl (or eggs) in which an average of 3 to 30 mol, preferably 5 to 20 mol of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Kenyl) ether

Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. As an aliphatic alcohol used here, a primary alcohol and a secondary alcohol are mentioned. The alkyl group may also have a branched chain. As aliphatic alcohol, primary alcohol is preferable.

(2) polyoxyethylene alkyl (or alkenyl) phenyl ethers

(3) Fatty acid alkyl ester alkoxylate represented by the following general formula (1), in which alkylene oxide is added between ester bonds of long chain fatty acid alkyl ester.

R^OneCO (OA)_nOR² (One)

Wherein R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide or propylene oxide. N represents the average added mole number of alkylene oxide, and is 3-30, Preferably it is the number of 5-20. R <^2> is the lower (C1) which may have a substituent of C1-C3. 4) alkyl group)

(4) polyoxyethylene sorbitan fatty acid ester

(5) polyoxyethylene sorbitan fatty acid ester

(6) polyoxyethylene fatty acid ester

(7) polyoxyethylene hardened castor oil

(8) glycerin fatty acid ester

Among the above nonionic surfactants, the nonionic surfactant of (1) described above is preferable, and in particular, polyoxyalkyl in which an average of 5 to 20 mol of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 8 to 18 carbon atoms. Preferred are alkylene (or alkenyl) ethers. Polyoxyethylene alkyl (or alkenyl) ethers having a HLB of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers at a melting point of 50 ° C. or lower, and fatty acid methyl esters in which ethylene oxide is added to fatty acid methyl esters. Fatty acid methyl ester ethoxy propoxylate in which ethylene oxide and propylene oxide are added to oxylate and fatty acid methyl ester are also preferably used.

In addition, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types.

The fatty acid alkyl ester alkoxylate represented by said formula (1) is also preferable. In particular, the polyoxyalkylene alkyl (or alkenyl) ether which added 5-20 mol of C2-C4 alkylene oxides to C8-C18 aliphatic alcohol on average is preferable.

In addition, HLB of a nonionic surfactant in this specification is a value calculated | required by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka co-editing, "New Surfactant Handbook", KKK, 1991) , See page 234).

In addition, melting | fusing point in this specification is a value which can be measured by the melting point measuring method described in JISK0064-1992 "Method of melting | fusing point and melting range of a chemical product."

The nonionic surfactant containing particle | grains of this invention contain the said nonionic surfactant and water-soluble inorganic compound.

As a preferable water-soluble inorganic compound, what is generally used as a washing builder is mentioned. Examples of such compounds include carbonates, bicarbonates and sesquicarbonates, sulfates and sulfites, phosphates and polycondensed phosphates, silicates, nitrates and nitrites, chlorides and the like. Among these, carbonates, sulfates, polycondensed phosphates and the like are more preferable, and sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium tripolyphosphate and the like are particularly preferable, and sodium carbonate, potassium carbonate and sodium sulfate are most preferred.

It is preferable that the nonionic surfactant containing particle | grains of this invention contain an aluminosilicate. Preferred aluminosilicates include the following general formula (I):

x ¹ (M ₂ O)? Al ₂ O ₃ ? y ¹ (SiO ₂ )? w ¹ (H ₂ O) (I)

Wherein M is an alkali metal atom such as sodium or potassium, x ¹ , y ¹ And w ¹ represents the mole number of each component, in general, x ¹ represents 0.7 to 1.5, y ¹ represents a number of 0.8 to 6, w ¹ represents an arbitrary integer)

Crystalline aluminosilicate represented by the following general formula (II) or (III):

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

Wherein M is an alkali metal atom such as sodium or potassium, x ² , y ² And w ² represents the number of moles of each component, generally x ² represents 0.7 to 1.2, y ² represents 1.6 to 2.8, w ² represents 0 or an arbitrary integer)

x ³ (M ₂ O)? Al ₂ O ₃ ? y ³ (SiO ₂ )? z ³ (P ₂ O ₅ )? w ³ (H ₂ O) (III)

(Wherein, M is an alkali metal atom such as sodium, potassium, x ^3, y ³ , z ³ and w ³ represents the number of moles of each component, in general, x ³ is 0.2 to 1.1, y ³ is 0.2 to 4.0 , z ³ represents 0.001 to 0.8, w ³ represents 0 or an arbitrary integer)

Amorphous aluminosilicate etc. which are represented by these are mentioned. Among these, those represented by the formula (I) are preferable, and A-type zeolites and P-type zeolites are particularly preferable.

The nonionic surfactant containing particle | grains of this invention may also contain other additive as needed. Examples of such other additives include those which can be incorporated into the (B) anionic surfactant-containing particles described later.

The nonionic surfactant containing particle | grains which can be used by this invention stir a water-soluble inorganic compound, an aluminosilicate, and other components as needed, add a nonionic surfactant to it, and it is stirred for a predetermined time at predetermined temperature ( It can manufacture by i).

The nonionic surfactant-containing particles of the present invention contain 10 to 50%, preferably 10 to 40%, and more preferably 10 to 30% of the nonionic surfactant with respect to the total amount of the particles. By containing a nonionic surfactant in this range, since washing | cleaning power, a dissolving power, solidification property, a spreading property, and fluidity | liquidity become favorable, it is preferable.

The nonionic surfactant containing particle | grains of this invention contain less than 45% of water-soluble inorganic compounds with respect to the said particle whole quantity, Preferably it contains 1 to 20%. By containing a water-soluble inorganic compound in such a range, since solidification becomes favorable, it is preferable.

The nonionic surfactant-containing particles of the present invention contain more than 20% and less than 85%, preferably 30 to 60%, of aluminosilicate relative to the total amount of the particles. It is preferable to contain aluminosilicate within such a range, since the bleeding properties and fluidity become good.

The average particle diameter of the nonionic surfactant containing particle | grains which can be used by this invention is 200-1000 micrometers, Preferably it is 250-700 micrometers, More preferably, it is 300-600 micrometers.

The bulk density of the nonionic surfactant containing particle | grains which can be used by this invention is 650 g / L or more, Preferably it is 700-1000 g / L, More preferably, it is 750-950 g / L.

It is preferable that the angle of repose of the nonionic surfactant containing particle | grains which can be used by this invention is 60 degrees or less, More preferably, it is 45 degrees or less.

If the average particle diameter, bulk density and angle of repose are within these ranges, the handleability, solubility and usability will be good, which is preferable.

In the granular detergent composition of the present invention, the (A) nonionic surfactant-containing particles are preferably blended in an amount of 5 to 95% with respect to the total amount of the composition, more preferably 10 to 50%, particularly preferably It is preferable to mix | blend in the quantity of 10-30%.

(B) anionic surfactant-containing particles

The anionic surfactant is not particularly limited as long as it is conventionally used as a detergent, and various anionic surfactants can be used. For example, the following are mentioned.

(1) straight or branched chain alkylbenzenesulfonates having alkyl groups of 8 to 18 carbon atoms (LAS)

(2) Alkyl sulfates or alkenyl sulfates having 10 to 20 carbon atoms

(3) α-olefin sulfonates (AOS) having 10 to 20 carbon atoms

(4) Alkanesulfonates having 10 to 20 carbon atoms

(5) Alkyl ether sulfate (AES) having a straight or branched chain alkyl group or alkenyl group having 10 to 20 carbon atoms and added ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with an average added mole number of 10 mol or less; Alkenyl ether sulfate

(6) Alkyl ether carboxylates or alkenyls having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and added ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with an average added mole number of 10 mol or less. Ether carboxylate

(7) Alkyl polyhydric alcohol ether sulfates, such as C10-C20 alkyl glyceryl ether sulfonic acid

(8) higher fatty acid salts with 10 to 20 carbon atoms

(9) Saturated or unsaturated α-sulfo fatty acids (α-SF) salts having 8 to 20 carbon atoms or their methyl, ethyl or propyl esters;

Examples of the anionic surfactant include alkali metal salts of linear alkylbenzenesulfonic acid (LAS) (for example, sodium or potassium salts), alkali metal salts of AOS, α-SF, AES (for example, sodium or potassium salts), Alkali metal salts of higher fatty acids (eg sodium or potassium salts, etc.) are preferred. These anionic surfactants can be used individually by 1 type or in combination of 2 or more types.

Among these, LAS which has a C10-15 alkyl group, C10-20 higher fatty acid salt, and C12-18 alpha-SF are preferable.

The anionic surfactant containing particle | grains of this invention contain the said anionic surfactant, the said water-soluble inorganic compound, and the said aluminosilicate.

The anionic surfactant containing particle | grains of this invention may contain other additives as needed. In addition, although a water-soluble inorganic compound is an essential component, it overlaps below and is described in more detail.

(1) cleaning builder

Examples of cleaning builders include inorganic and organic builders.

(1-1) weapon builder

As an inorganic builder, For example, alkaline salts, such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium seskicarbonate, sodium silicate, crystalline sodium silicate, amorphous sodium silicate, neutral salts, such as sodium sulfate, orthophosphate, Phosphates such as pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, and amorphous aluminosilicates. Among the inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate and sodium aluminosilicate are preferable.

(1-2) Organic Builder

As an organic builder, For example, aminocarboxylates, such as nitrilo triacetate, ethylenediamine tetraacetate, (beta) -alanine diacetate, aspartic acid diacetate, methylglycine diacetate, and imino disuccinate; Hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate, hydroxyethyl ethylenediamine triacetate, and dihydroxyethylglycine salt; Hydroxycarboxylates such as hydroxyacetate, tartarate, citrate, and gluconate; Cyclocarboxylates such as pyromellitate, benzopolycarboxylate and cyclopentane tetracarboxylate; Ether carboxylates such as carboxymethyl tartrate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono or disuccinate; Polymers or copolymers such as itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid and aspartic acid; Polysaccharide oxides such as starch, cellulose, amylose and pectin, and polysaccharides such as carboxymethyl cellulose.

Among these organic builders, citrates, aminocarboxylates, hydroxyaminocarboxylates, polyacrylates, acrylic acid-maleic acid copolymers, and polyacetalcarboxylates are preferred, and in particular, hydroxyiminodisuccinates and weight average molecular weights. Salts of the acrylic acid-maleic acid copolymer of 1000 to 80000, polyacrylates and polyacetals such as polyglyoxylic acid having a weight average molecular weight of 800 to 1000000, preferably 5000 to 200000, as described in JP-A-54-52196 Carboxylates are preferred. Content of an organic builder becomes like this. Preferably it is 0.5-20 mass%, More preferably, it is 1-10 mass% in nonionic surfactant containing particle | grains and anionic surfactant containing particle | grains. An organic builder can be used individually by 1 type or in combination of 2 or more types.

In addition, organic builders and zeolites such as citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer, polyacetal carboxylate, etc., in order to improve the cleaning power and the dispersibility of contamination in the washing liquid. It is preferable to use inorganic builders, such as these.

(2) dissolution accelerator

Examples of dissolution accelerators include benzene sulfonates and benzoic acids having short-chain alkyl having 1 to 5 carbon atoms, such as inorganic ammonium salts such as potassium carbonate, ammonium sulfate and ammonium chloride, sodium p-toluene sulfonate, sodium xylene sulfonate and sodium cumene sulfonate. Water-soluble substances, such as sodium, sodium benzene sulfonate, sodium chloride, citric acid, D-glucose, urea, and sucrose, are mentioned, These can be used individually by 1 type or in combination of 2 or more types as appropriate.

Among these, potassium carbonate, sodium chloride, and sodium cumene sulfonate are preferable, and potassium carbonate is particularly preferable for the balance between solubility improvement effect and cost.

(3) Swellable Water Insoluble Materials

Examples of the swellable water-insoluble substance include powdered cellulose, crystalline cellulose, bentonite, and the like.

(4) Fluorescent agent: Bis (triadinyl amino stilbene) disulfonic acid derivative (tinopal AMS-GX), bis (sulphostyryl) biphenyl salt [tinopal CBS-X], etc.

(5) Antistatic agents: Cationic surfactants, such as a dialkyl type quaternary ammonium salt.

(6) Recontamination inhibitor: Cellulose derivatives, such as carboxymethylcellulose.

(7) Extenders: sodium sulfate, potassium sulfate and the like.

(8) reducing agents: sodium sulfite, potassium sulfite and the like.

(9) spices

(10) pigment

(11) Bleaching Activation Catalyst

Bleaching activating catalysts include a complex of transition metal atoms and ligands such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, molybdenum and the like via a nitrogen atom or an oxygen atom. As a transition metal to be formed, cobalt, manganese, etc. are preferable, and manganese is especially preferable.

The anionic surfactant containing particle | grains which can be used by this invention can be obtained by the following granulation method. The raw material powder and the binder component (surfactant, water, liquid polymer component, etc.) of the detergent component are kneaded and kneaded, and then extruded and granulated by extrusion and granulation, and the obtained solid detergent is crushed and granulated after kneading and kneading. Pulverization and crushing granulation method, stirring granulation method which adds a binder component to raw material powder and stirs with stirring blades, rolling granulation method which sprays and assembles a binder component while rolling raw material powder, and liquid binder while fluidizing raw material powder The fluidized bed granulation method etc. which spray and granulate are mentioned. The specific apparatus, conditions, etc. which can be used by these assembling methods are as described in Unexamined-Japanese-Patent No. 2003-105400, the Japan Powder Technology Association edition, the assembly handbook 1st edition, etc.

The anionic surfactant-containing particles of the present invention contain 10 to 40% of anionic surfactant, preferably 15 to 30%, based on the total amount of the particles.

The anionic surfactant-containing particles of the present invention contain 10 to 40%, preferably 20 to 40%, of water-soluble inorganic compounds based on the total amount of the particles.

The anionic surfactant-containing particles of the present invention contain aluminosilicate in an amount of 0 to 40%, preferably 10 to 40%, and more preferably 15 to 35%, based on the total amount of the particles.

By containing anionic surfactant, a water-soluble inorganic compound, and an aluminosilicate as needed in the said range, since washing | cleaning power, solidification, and solubility become favorable, it is preferable.

The average particle diameter of the anionic surfactant containing particle | grains which can be used by this invention is 200-1000 micrometers, Preferably it is 250-700 micrometers, More preferably, it is 300-600 micrometers.

The bulk density of the anionic surfactant containing particle | grains which can be used by this invention is 650 g / L or more, Preferably it is 700-1000 g / L, More preferably, it is 750-950 g / L.

It is preferable that the angle of repose of the anionic surfactant containing particle | grains which can be used by this invention is 60 degrees or less, More preferably, it is 45 degrees or less.

When average particle diameter, bulk density, and angle of repose are in the said range, since handleability, solubility, and usability become favorable, it is preferable.

In the granular detergent composition of the present invention, the (B) anionic surfactant-containing particles are preferably blended in an amount of 5 to 95% with respect to the total amount of the composition, and more preferably in an amount of 50 to 90%. It is preferable.

In the granular detergent composition of this invention, it is preferable to use together (A) nonionic surfactant containing particle | grains and (B) anionic surfactant containing particle | grains in the range of 5 / 95-95 / 5 by mass ratio, It is more preferable to use together in the range of -80/20, and it is still more preferable to use together in the range of 10 / 90-50 / 50. When mass ratio exists in the said range, since solubility, solidification, and bleeding property become favorable, it is preferable.

(D) coated inorganic particles

The high bulk density granular detergent composition of the present invention may also contain coated inorganic particles. The coated inorganic particles can be obtained by applying organic or inorganic water-soluble polymers and poorly water-soluble compounds to the inorganic particles serving as nuclei as coating agents.

As an inorganic particle used as a nucleus, the water-soluble inorganic compound used as a washing builder generally mentioned above can be used. Among them, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium tripolyphosphate and the like are particularly preferable, and sodium carbonate and potassium carbonate are most preferred.

The organic water-soluble high molecular compound, which is a coating agent used for surface treatment of the water-soluble inorganic compound, is a polymer which is mixed with water uniformly at a concentration of 0.1 g or more, preferably 0.2 g or more, and more preferably 2 g or more with respect to 100 g of water at 40 ° C. Compound. It will not specifically limit, if it is such an organic water-soluble high molecular compound, It can use individually by 1 type or in combination of 2 or more types.

As an organic water-soluble high molecular compound, a natural high molecular compound, a semisynthetic high molecular compound, a synthetic high molecular compound, etc. are mentioned. Specifically, vinyl polymer compounds, polysaccharides, polyether polymer compounds, polyester polymer compounds, peptide polymer compounds, polyurethanes and derivatives thereof can be used. Among these, it is preferable to use individually 1 type selected from a vinyl type high molecular compound, a polysaccharide, its derivatives, and a polyester type high molecular compound individually or in combination of 2 or more types.

Examples of the vinyl polymer compound include vinyl polycarboxylates (acrylic acid polymer compounds), vinyl polysulfonic acid salts, polyvinylpyridine salts, polyvinylimidazolium salts, and the like. As the polysaccharide, various natural or synthetic polysaccharides can be used.

As a polyester type high molecular compound, the copolymer, terpolymer, etc. of a terephthalic acid, ethylene glycol, and / or a propylene glycol unit are mentioned, for example. Examples of these include commercially available Texcare 4291 (manufactured by Clariant), Texcare SRN-300 (manufactured by Clariant).

Specific examples of the peptide-based high molecular compound or its derivatives include gelatin, casein, albumin, collagen, polyglutamate, polyasparaginate, polylysine, polyarginine and derivatives thereof.

As polyurethane, a water-soluble polyurethane etc. are mentioned, for example. Moreover, other water-soluble high molecular compounds, such as polyethyleneglycol, can also be used.

In particular, since the water-soluble inorganic compound is easily hydrated, it is preferable that the water-soluble inorganic compound be exerted in the initial stage of contact with water in the state of being surface-treated with the water-soluble organic high molecular compound. As a water-soluble organic high molecular compound which has such a characteristic, what has hydrophilic functional groups, such as anionic, amphoteric, and nonionic, is mentioned.

As a water-soluble organic high molecular compound which has an anionic group, the high molecular compound which has a carboxy group, a sulfo group, and the water-soluble polysaccharide which has an anionic group are mentioned, for example.

As a water-soluble organic high molecular compound which has a carboxy group, For example, the polymer and its salt which polymerize monomers, such as acrylic acid, maleic acid, itaconic acid, aconic acid, methacrylic acid, fumaric acid, 2-hydroxyacrylic acid, a citraconic acid, And vinyl polycarboxylic acids (salts) such as copolymers of these polymers with other vinyl monomers and salts thereof.

As a water-soluble high molecular compound which has a sulfo group, For example, the polymer obtained by superposing | polymerizing monomers, such as acrylamide propanesulfonic acid, methacrylamide propanesulfonic acid, and styrene sulfonic acid, its salt, a copolymer of these polymers, and other vinyl type polymers, Vinyl polysulfonic acid (salt), such as the salt, etc. are mentioned.

Examples of the water-soluble polysaccharide having an anionic group include polyuronic acid salts, alginate salts, polyasparaginate salts, carrageenan salts, hyaluronic acid salts, chondroitin sulfate salts, and carboxymethyl cellulose.

As an amphoteric water-soluble high molecular compound, the copolymer of the vinyl monomer which has an anionic group, and the vinyl monomer which has a cationic group, the vinyl-type amphoteric polymer which has a carboxybetaine group or a sulfobetaine group is mentioned, for example, As an acrylic acid / dimethylamino ethyl methacrylic acid copolymer, an acryl / diethylamino ethyl methacrylic acid copolymer, etc. are mentioned.

As a nonionic water-soluble high molecular compound, synthetic high molecular compounds, such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ethyl ether, polyethyleneglycol, hydroxyethyl cellulose, guar gum, dextran, flu Polysaccharides, such as a column, are mentioned.

Among these, the compound which is excellent in the immersion action in the initial stage of contact with water and generates heat when dissolved or dispersed in water is preferable. In consideration of this point, it is preferable to use a vinyl polymer having a carboxyl group or a sulfo group, and in particular, vinyl polycarboxylic acids having a high anionic group content per unit mass are preferable.

Specifically, polyacrylate, acrylic acid / maleic acid copolymer salt, acrylic acid / itaconic acid copolymer salt, alkyl acrylate copolymer salt, derivatives thereof, and the like are optimal.

It is preferable that the weight average molecular weight of the organic water-soluble high molecular compound of this invention is 500 or more, More preferably, it is 1,000-1,000,000, More preferably, it is 1,000-200,000. In addition, the average molecular weight of polyethyleneglycol in this invention shows the average molecular weight of a cosmetic raw material reference | standard (2nd edition note) base material. In addition, the weight average molecular weight of the organic water-soluble high molecular compound in this invention is a measured value by the gel permeation chromatography which makes polyethyleneglycol a standard substance.

The method of surface-treating a water-soluble inorganic compound with an organic water-soluble high molecular compound is not specifically limited. For example, the method of adding, mixing, or coating an organic water-soluble high molecular compound to a water-soluble inorganic compound is mentioned. It is preferable to use an organic water-soluble high molecular compound for surface treatment as an aqueous solution. It is preferable to add this aqueous solution dropwise or spray to a water-soluble inorganic compound in a stirred fluidized state.

Inorganic Water Soluble High Polymer Compound

On the other hand, the inorganic water-soluble high molecular compound is a compound which is mixed with water uniformly at a concentration of 0.1 g or more, preferably 0.2 g or more, and more preferably 2 g or more with respect to 100 g of water at 40 ° C. It will not specifically limit, if it is such an inorganic water-soluble high molecular compound, It can use individually by 1 type or in combination of 2 or more types. As an inorganic water-soluble high molecular compound, what is obtained by hydrolysis-condensation polymerization reaction of the solution containing the precursor compound of a metal alkoxide is preferable, and a silicate is especially preferable.

Silicates are traditionally formulated in soaps, known as waterglasses, and can be classified according to their structure according to their classification by the form of anions (Friedrich Liebau, “Structural Chemistry of Silicates” p72, Springer-Verlag, 1985). ).

In detail, it can classify into the crosslinked oxygen number (Si-O-Si) of the oxygen couple | bonded with Si, The crosslinked oxygen number corresponding to 4, 3, 2, 1, 0, respectively, Q4, Q3, Q2, Q1, Q0 units (Y. Tsunawaki, N. Iwamoto, T. Hattori and A. Mitsuishi, J. Non-Cryst. Solids, vol 44, p369 (1981)).

Examples of silicate, in order to achieve the processing effect sufficiently, and including Q2 unit and / or Q3 units, SiO ₂ / M ₂ O molar ratio (wherein, M represents an alkali metal) of 1.6 to 4, preferably from 2 to 3.5 Alkali metal silicates having a salt are preferred, and sodium silicate is particularly preferred.

The method of surface-treating a water-soluble inorganic compound with an inorganic water-soluble high molecular compound is not specifically limited. For example, the method of adding, mixing, or coating an inorganic water-soluble high molecular compound to a water-soluble inorganic compound is mentioned. It is preferable to use an inorganic water-soluble high molecular compound for surface treatment as an aqueous solution. It is preferable to add this aqueous solution dropwise or spray to a water-soluble inorganic compound in a stirred fluidized state.

Water solubility  compound

A poorly water-soluble compound that can be used as a coating agent is a compound having a solubility in water at 20 ° C. of less than 2 g / 100 g, preferably less than 1 g / 100 g, more preferably less than 0.1 g / 100 g, in contact with water. It is preferable to have a water repellent action at. Moreover, the organic compound which has melting | fusing point of 200 degrees C or less, Preferably it is 0-160 degreeC, More preferably, it is 20-80 degreeC, More preferably, it is 40-60 degreeC. A poorly water-soluble compound can be used individually by 1 type or in combination of 2 or more types.

Examples of poorly water-soluble compounds include higher fatty acid dicarboxylic acids, higher alcohols, HLB5 or less, preferably 3 or less higher alcohols or alkylene oxide adducts of higher fatty acids, higher fatty acid esters, glycerides that are higher fatty acids, and the like. Can be.

The higher alcohol preferably has a carbon chain length of 12 to 22, more preferably 14 to 18 carbon atoms, and specific examples thereof include dodecanol, tetradecanol, hexadecanol, and octadecanol.

As alkylene oxide adduct of HLB5 or less, preferably 3 or less higher alcohol or higher fatty acid, C16-22 alcohol or fatty acid 1-3 mol ethylene oxide adduct is preferable, Specifically, 1 mol of hexadecanol Ethylene oxide adducts, 3 mol ethylene oxide adducts of octadecanol, 1 mol ethylene oxide adducts of palmitic acid, and the like.

As the higher fatty acid ester, methyl esters such as palmitic acid, myristic acid, stearic acid, arachidic acid, behenic acid or ethyl ester are preferable.

As glyceride of a higher fatty acid, mono, di, or triglycerides, such as lauric acid, palmitic acid, stearic acid, are preferable.

In addition, it is preferable to use an anionic surfactant acid precursor as a poorly water-soluble compound in that it is endothermic during initial wetting to control the heat generation of the water-soluble inorganic compound, and when washed, the water is gradually water-soluble by neutralization reaction with the water-soluble inorganic compound. desirable.

As the anionic surfactant acid precursor, an acid precursor of any anionic surfactant can be preferably used. As acid precursors of the anionic surfactants, saturated or unsaturated fatty acids (average carbon chain length 8-22), straight or branched chain alkyl (average carbon chain length 8-18) benzenesulfonic acid, long chain alkyl (average carbon chain length 10- Sulfonic acid, long chain olefins (average carbon chain length 10-20) Sulfonic acid, long chain monoalkyl (average carbon chain length 10-20) sulfate esters, polyoxyethylene (average degree of polymerization 1-10) long chain alkyl (average carbon Chain length 10-20) ether sulfate ester, polyoxyethylene (average degree of polymerization 3-30) alkyl (average carbon chain length 6-12) phenylether sulfate ester, α-sulfo fatty acid (average carbon chain length 8-22), long Chain monoalkyl, dialkyl or seskialkyl phosphoric acid, polyoxyethylene monoalkyl, dialkyl or seskialkyl phosphoric acid, and the like.

As the anionic surfactant acid precursor, saturated or unsaturated fatty acid (average carbon chain length 8 to 22) is preferable, and it is more preferable to have a carbon chain length of 8 to 18 carbon atoms. Specific examples thereof include saturated fatty acids such as capric acid, lauric acid, myristic acid and palmitic acid, and unsaturated fatty acids such as olefinic acid. Among these, saturated fatty acids having 12 to 18 carbon atoms are preferred for storage stability, and lauric acid is more preferable in view of manufacturability.

The method of further surface-treating the surface-treated water-soluble inorganic compound with a poorly water-soluble compound is not particularly limited. For example, the method of adding, mixing, or coating a poorly water-soluble compound to the surface-treated water-soluble inorganic compound is mentioned. A method of melting a poorly water-soluble compound into a liquid phase and dropping or spraying the liquid onto a surface-treated water-soluble inorganic compound in a stirred or flow state is preferable.

It is preferable that the average particle diameter of the coated inorganic particle which can be used by this invention is 100-1500 micrometers, More preferably, it is 200-1000 micrometers, More preferably, it is 250-700 micrometers.

The bulk density of the coated inorganic particle which can be used by this invention becomes like this. Preferably it is 650 g / L or more, More preferably, it is 700-1200 g / L.

It is preferable that the angle of repose of the coated inorganic particle which can be used by this invention is 60 degrees or less, More preferably, it is 45 degrees or less.

If average particle diameter, bulk density, and angle of repose are in the said range, since manufacture property, solubility, and usability become favorable, it is preferable.

The application amount of each component in the coated inorganic particle which can be used by this invention is shown below.

It is preferable to use 60-99.8 mass% with respect to the whole quantity of a coating inorganic particle, and, as for a water-soluble inorganic compound, 70-97 mass% is especially preferable. If the water-soluble inorganic compound is less than 60% by mass, the alkali agent may be insufficient. On the other hand, if the water-soluble inorganic compound is more than 99.8%, the amount of the treatment agent may be too small to allow sufficient surface treatment.

It is preferable to use an organic water-soluble high molecular compound at 0.1-10 mass%, especially 0.5-8 mass% with respect to the water-soluble inorganic compound used as a nucleus. If it is less than 0.1 mass%, the effect of surface treatment may not be acquired, and when it exceeds 10 mass%, the compounding quantity of an inorganic compound may become too small.

It is preferable to use an inorganic water-soluble high molecular compound at 1-30 mass%, especially 10-28 mass% with respect to a water-soluble inorganic compound. If it is less than 1 mass%, the effect of surface treatment may not be acquired, and when it exceeds 30 mass%, the compounding quantity of an inorganic compound may become too small.

It is preferable to use a poorly water-soluble compound in 0.1-10 mass%, especially 2-8 mass% with respect to a coating inorganic particle. If it is less than 0.1 mass%, the effect of surface treatment may not be acquired, and when it exceeds 10 mass%, the compounding quantity of an inorganic compound may become too small.

(C) high bulk density granular detergent composition

The high bulk density granular detergent composition of this invention can be manufactured by mixing the said (A) nonionic surfactant containing particle | grains and (B) anionic surfactant containing particle | grains.

The average particle diameter of the high bulk density granular detergent composition of this invention is 200-1000 micrometers, Preferably it is 250-700 micrometers, More preferably, it is 300-600 micrometers.

It is preferable that the bulk density of the granular detergent composition of the high bulk density of this invention is 650 g / L or more, More preferably, it is 700-1000 g / L.

When average particle diameter and bulk density exist in the said range, since handleability, solubility, and usability become favorable, it is preferable.

It is preferable that the low temperature aggregation rate% calculated | required by following formula (1) of the composition of this invention to water at low temperature is less than 20%, It is more preferable that it is less than 10%, It is most preferable that it is less than 5%.

Here, the low temperature aggregation rate can be measured as follows. That is, 5 g of the granular detergent composition of the present invention is carefully poured into a 9.3 cm inner chalet containing 80 mL of 5 ° C. water and left for 5 minutes. After standing, it was passed through an eye size sieve of 3360 μm, and the detergent composition remaining on the sieve was dried at 60 ° C. for 2 hours. The mass after drying was measured and the low temperature aggregation rate% was calculated | required using the following formula.

[Equation 1]

Low temperature coagulation rate (%) = dry mass of the detergent composition remaining on the sieve / granular detergent composition mass x 100 put in a sieve

It is preferable that the solidification rate calculated | required by following formula (2) is less than 20%, and, as for the solidification of the composition of this invention, it is more preferable that it is less than 5%.

Here, the solidification rate can be measured as follows. That is, three layers of paper (moisture permeability: 25 g / m) of cardboard (weight: 350 g / m ² ), wax sand (weight: 30 g / m ² ) and graft pulp (weight: 70 g / m ² ) coated from the outside 1.2 kg of the granular detergent composition of this invention is put into the box of length 15cm x width 9.3cm x height 18.5cm manufactured using m <^2> -24 hours (40 degreeC, 90% RH)). It is stored for 30 days in a recycled constant temperature and humidity room at 25 ° C. (65% RH, 8 hours) and 45 ° C. (85% RH, 16 hours) to obtain a sample for the test of solidification with time. After preservation with time, the detergent was carefully transferred to a 4 mm eye sieve, the mass of the detergent remaining solidified on the sieve was determined, and the solidification rate was calculated by the following equation.

[Equation 2]

Solidification rate (%) = mass of the detergent composition remaining on the sieve / mass of the granular detergent composition in the box × 100

Moreover, as an arbitrary component, you may include normally the component contained in a granular detergent composition in the range which does not inhibit the effect of this invention.

Moreover, in the granular detergent composition of this invention, you may mix | blend the component which immobilizes nonionic surfactant, such as an oil absorption carrier, a clay mineral, or a nonionic gelling agent, as needed.

The oil-absorbing carrier used in the present invention is added to improve the problem that the stickiness and masking properties of the intermediate product or the final product deteriorate with time as described above. As such an oil-absorbing carrier, a substance whose oil absorption amount represented by the JIS-K5101 test method is 100 ml / 100 g or more, preferably 150 ml / 100 g or more, and more preferably 200 ml / 100 g or more is suitably used. As such an oil-absorbing carrier, for example, as a silicate compound, Tokusil N (manufactured by Tokuyama Co., Ltd., oil absorption amount 280 ml / 100 g), nipsil NS-K (manufactured by Nippon Silica Co., Ltd., oil absorption amount 320 ml / 100 g), between Spherical porous functions such as amorphous hydrous silicic acid, such as Lysia # 310 (manufactured by Fuji Syria Chemical Co., Ltd., oil absorption amount 340ml / 100g), and Sildex H-52 (products of Asahigarasu Corporation, oil absorption amount 260ml / 100g) Amorphous anhydrous amorphous silicic acid such as amorphous silicic acid, aerodil # 300 (Nihon Aerosil Co., Ltd., oil absorption 350ml / 100g), flow light R (Tokuyama Co., Ltd., oil absorption 600ml / 100g) Needle-shaped calcium crystalline silicate, amorphous aluminosilicate (Mizusawa Chemical Co., Ltd. product, oil absorption 170ml / 100g) such as petal-type hydrous amorphous calcium silicate, zonothorite (product of Ubegaku Co., Ltd., oil absorption 220ml / 100g) ), Magnesium silicate (absorption amount 180ml / 100g) and the like. As the carbonate compound, magnesium carbonate (manufactured by Tokuyama Co., Ltd., oil absorption 150ml / 100g), calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., oil absorption 110ml / 100g), and other compounds include ultra-fine particle spinel (Sumitomo Cement Co., Ltd.). Product, oil absorption 600ml / 100g), ultra fine particle cordierite (Sumitomo Cement Co., Ltd., oil absorption 600ml / 100g), ultrafine particle Merite (product of Sumitomo Cement Co., oil absorption 560ml / 100g), processed starch fine flow S (matsu Tanigagaku Co., Ltd., oil absorption amount 130ml / 100g), etc. are mentioned. In addition, these oil absorption carriers can also be used as a mixture.

As the clay mineral used in the preferred embodiment of the present invention, it is particularly belonging to the smectite group, and the crystal structure preferably has a dioctahedral three-layer structure or a trioctahedral three-layer structure. These clay minerals are grainy and form a layered structure. This clay mineral has a small oil absorption amount compared with the oil absorption carrier. In addition, clay minerals have the property of forming a chemical adsorption of a nonionic surfactant by hydrogen bonding between crystal layers and immobilizing the inside of the clay mineral. In addition, clay minerals have a property of being swollen by maintaining a nonionic surfactant therein. The clay mineral which can be preferably used in the present invention is preferably an oil absorption amount of less than 80 ml / 100 g, more preferably 30 to 70 ml / 100 g.

Specific examples of such clay minerals include, for example, montmorillonite (absorption amount: 50 ml / 100 g), nontronite (absorption amount: 40 ml / 100 g), and bidelite (absorption amount: 62 ml) as a clay mineral having a dioctahedral three-layer structure. / 100g), pyrophyllite (oil absorption amount: 70ml / 100g) and the like. On the other hand, as a clay mineral having a trioctahedral three-layer structure, saponite (oil absorption: 73 ml / 100 g), hectorite (oil absorption: 72 ml / 100 g), Stevensight (oil absorption: 30 ml / 100 g), talc (oil absorption: 70 ml / 100g) and the like. Although these clay minerals generally have two types, such as a thing produced naturally and an artificial hydrothermal synthesis, they are not specifically limited.

Such clay minerals can be used without particular limitation as long as peaks derived from the distribution of the clay layer detected by X-ray diffraction analysis at 10 to 20 Hz and peaks derived from the three-layer structure of clay detected at 4 to 5 Hz are developed. . On the other hand, clay minerals, especially in the case of natural products, may contain a large amount of impurities such as quartz, cristobalite, calcite, opal and feldspar, and many of these impurities do not apply to the present invention, and the purity is at least 60%, more preferably. Preferably use more than 70%, best 100%. Particularly preferable clay minerals which can be used are Na type montmorillonite, Ca type montmorillonite, activated bentonite (Na / Ca type montmorillonite), Na type hectorite and Ca type hectorite.

The nonionic gelling agent used in the present invention has a property of gelling a nonionic surfactant and immobilizing and maintaining the nonionic surfactant in a granular detergent. By using this nonionic gelling agent, especially when it contains 15 weight% or more of nonionic surfactants, the fluidity | liquidity and cake resistance under the high temperature of detergent particle | grains are improved significantly. Therefore, as long as the nonionic gelling agent having such a function, various nonionic gelling agents can be used. As the nonionic gelling agent used in the present invention, the same ones used as conventional oil gelling agents can be used. Among these nonionic gelling agents, when a specific nonionic surfactant is gelled with the nonionic gelling agent, the maximum compressive stress is 30 g / cm ² at 40 ° C. It is preferable to use the above. This maximum compressive stress is a non-ionic gelling agent of non-ionic gelling agent and weight ratio of 5/1, which is a common detergent, and an alcoholic ethoxylate-type nonionic surfactant (carbon chain length 12, average added mole number of ethylene oxide 9, melting point 20 DEG C) to be measured. After mixing at 70 DEG C, cooling to 20 DEG C, and then standing at 20 DEG C for 3 hours, a rectangular test piece having a length of 5 cm x 5 cm x 1 cm was prepared, and then a cylindrical jig having a cross-section diameter of 1.5 cm. The maximum compressive stress at the time of pressurization at 40 degreeC on the conditions of 20 mm / min of compression rate is measured.

In the present invention, when the maximum compressive stress of the nonionic gelling agent under the above conditions is less than 30 g / cm ² , the fluidity under high temperature of the detergent particles obtained tends to be insufficient. Moreover, preferable maximum compressive stress is 50-2000g / cm <^2> , Especially preferable maximum compressive stress is 100-1500g / cm <^2> . Preferred nonionic gelling agents which can be used in the present invention include, for example, 12-hydroxystearic acid (maximum compressive stress 520 g / cm ² ) (KF Trading Products Hydroxystealine (trade name)), dibenzylidene sorbitol ( Maximum compressive stress 30 g / cm ² ) (New Nippon Seishi gelol D (brand name)), lithium stearate (maximum compressive stress 50 g / cm ² ) (KF trading product Li-ST (brand name)), aluminum palmitate (maximum Compressive stress 50g / cm ² ) (KF Trading Product AL-PL (trade name)), lithium 2-ethylhexanoate (maximum compressive stress 66g / cm ² ) (KF Trading product Li-2EH (brand name)), 12-hydroxy Aluminum stearate (maximum compressive stress 126 g / cm ² ) (KF Trading Co. Al-OHST (brand name)), lauroylglutamic acid dibutylamide (maximum compressive stress 200 g / cm ² ) (azinomoto Co. 1 (brand name)), lauroyl glutamic acid stearylamide (maximum compressive stress 53g / cm ² ) (product of Ajinomoto), (maximum compressive stress 183g / cm ² ) (made by Ajinomoto), dicaproyridinlaurylamide (maximum compressive stress 45g / cm ² ) (made by Ajinomoto), lauroylphenylalaninelaurylamide (maximum compressive stress 37g / cm ² ) (Ajinomoto), polystyrene polybutadiene block copolymer (molecular weight: 200,000, composition: styrene / butadiene = 40/60) (maximum compressive stress 60 g / cm ² ) (KF trading product KF21 (trade name)), polyacrylic Amide (molecular weight: 100,000) -isoparaffin mixture (maximum compressive stress 83g / cm ² ) (Soragum SD401 (trade name) manufactured by Relief Corporation), block copolymer of polystyrene block and polybutadiene block (molecular weight: 100,000, composition: Styrene / butadiene = 30/70 (maximum compressive stress 48 g / cm ² ) (KF trading product), dextrin palmitic acid ester (maximum compressive stress 80 g / cm ² ) (chiba powder product Leopard KL (trade name)), Or mixtures thereof. By mixing these nonionic gelling agents, the desired maximum compressive stress can be provided.

The nonionic surfactant-containing particles of the present invention preferably contain an oil absorption carrier in an amount of 0.1 to 20%, particularly preferably 0.1 to 10% based on the total amount of the particles, and preferably 0.1 to 40% of clay minerals. Especially preferably, it contains 1 to 20%, Preferably it contains 0.1 to 30%, More preferably, it contains 0.5 to 20%.

By blending an oil absorbent carrier, a clay mineral, and a nonionic gelling agent in such a range, it is preferable because of its bleeding property and fluidity. In particular, oil-absorbing carriers and clay minerals are preferable.

Preferable examples are shown below.

(A) Polyoxyalkylene alkyl ether which averaged 3-30 mol of C2-C4 alkylene oxides to a C6-C22 aliphatic alcohol, and following formula (1):

R^OneCO (OA)_nOR² (One)

(Wherein R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, OA represents an additional unit of an alkylene oxide having 2 to 4 carbon atoms, n represents an average added mole number of alkylene oxide and is a number of 3 to 30). R ² represents a lower alkyl group)

10-50% of nonionic surfactants selected from the group consisting of fatty acid alkyl ester alkoxylates,

Nonionic with less than 1-20% of water-soluble inorganic compounds selected from the group consisting of sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate and sodium tripolyphosphate, with an average particle diameter of 200-1000 μm and a bulk density of 700-1000 g / L Surfactant-containing particles,

(B) the following groups:

Alkali metal salts of linear or branched alkylbenzene sulfonic acids having an alkyl group having 8 to 18 carbon atoms (LAS);

Alkali metal salts of alpha -olefin sulfonic acids having 10 to 20 carbon atoms (AOS);

Alkali metal salts of alkylethersulfuric acid (AES) having ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having 10 to 20 carbon atoms, or a linear or branched alkyl group or alkenyl group, and an average added mole number of 10 mol or less;

Alkali metal salts of higher fatty acids having 10 to 20 carbon atoms; And

Alkali metal salts of saturated or unsaturated α-sulfo fatty acids (α-SF) having 8 to 20 carbon atoms,

10 to 40% of anionic surfactant selected from the group consisting of: a particle mixture with anionic surfactant-containing particles having an average particle diameter of 200 to 1000 µm and a bulk density of 700 to 1000 g / L,

(C) High bulk density detergent composition.

(D) It is preferable to contain sodium carbonate and enzyme particles coated with lauric acid and maleic / acrylic acid copolymer sodium salt.

In the following examples, "%" in the composition when not specifically indicated indicates mass%, and in the amounts of the respective components in the table, the compositions in Tables 1 to 3 represent pure blend amounts, and Table 4 is the base component. It was represented by the compounding quantity of.

By the following production method, nonionic surfactant-containing particles (a1 to a4) were obtained.

Nonionic  Method for producing surfactant-containing particles 1

According to the composition shown in following Table 1, the nonionic surfactant containing particle | grains (a1) were manufactured in the following procedure. Among the components shown in Table 1 below, all components except for the surfactant (temperature 25 ℃), has a sputum-shaped shovel, the clearance between the shovel-wall surface is 5mm Readygei Mixer Co., Ltd. M20 type) was charged (charge rate of 50% by volume), and stirring was started at a main shaft of 200 rpm and a chopper of 200 rpm. 30 seconds after the start of the stirring, the surfactant (the nonionic surfactant was previously heated to 60 ° C. and uniformly mixed) and water (temperature 60 ° C.) were added for 2 minutes, and stirring granulation was continued under the condition of the jacket temperature of 30 ° C. To obtain particles having an average particle diameter of 1000 µm.

In the same manner as the method for producing the surfactant-containing particles (a1), the surfactant-containing particles (a2, a3, a4) (average particle diameter and bulk density are shown in Table 1) were obtained.

By the following manufacturing method, anionic surfactant containing particle | grains (b1-b3) were obtained.

Anionic  Method for producing surfactant-containing particles 1

According to the composition shown in Table 2 below, anionic surfactant-containing particles (b1) were prepared in the following order. First, water was put into the mixing tank with a jacket provided with a stirring apparatus, and temperature was adjusted to 60 degreeC. Surfactant except alpha-SF-Na and nonionic surfactant was added here, and it stirred for 10 minutes. Subsequently, MA1 (acrylic acid / maleic acid copolymer sodium salt) and a fluorescent agent were added. After stirring for 10 minutes, a portion of the powder A-type zeolite (approximately 2.0% equivalent (in comparison with each particle, below) is added for nitrification, 3.2% equivalent grinding aid, 1.5% equivalent each surface A) Sodium carbonate, potassium carbonate and sodium sulfite were added. After stirring for 20 minutes to prepare a spray drying slurry having a moisture content of 38%, using a countercurrent spray drying tower, spray drying under conditions of a hot air temperature of 200 ° C., an average particle diameter of 320 μm, and a bulk density of 0.30 g / cm ³ And spray dried particles having a moisture of 5% were obtained.

On the other hand, a part of the nonionic surfactant (25% relative to α-SF-Na) is added to the aqueous slurry of α-SF-Na (25% water content) obtained by sulfonating and neutralizing the fatty acid ester as a raw material. The mixture was concentrated under reduced pressure with a thin film dryer until moisture reached 11%, thereby obtaining a mixed concentrate of α-SF-Na and a nonionic surfactant.

The above-mentioned spray dried particles, this mixed concentrate, 2.0% equivalent of A-type zeolite, 0.5% equivalent of non-ionic surfactant and water except for spray addition, and continuous kneader (Kurimoto Teksho Co., Ltd.), KRC- S4), and it was kneaded on the conditions of 120 kg / hr of kneading capacity and the temperature of 60 degreeC, and obtained surfactant containing kneaded material. The surfactant-containing kneaded material was cut with a cutter while extruded using a pellet double (provided by Fuji Powder Co., Ltd., EXDFJS-100 type) equipped with a die having a diameter of 10 mm (the cutter circumferential speed was 5 m / s), A pellet-shaped surfactant-containing molded article having a length of about 5 to 30 mm was obtained.

Subsequently, 3.2% of the particulate A-type zeolite (average particle diameter 180 mu m) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded article, and the fits mill was arranged in three stages under coexistence with cold air (10 ° C, 15 m / s). (The screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, the number of revolutions: 1st stage / 2nd stage / 3rd stage, 4700rpm) using (The Hosokawa Micron Co., Ltd. product, DKA-3) ). Finally, with a horizontal cylindrical electric mixer (cylinder diameter 585mm, cylinder length 490mm, container 131.7L, the inner wall of the drum has 20 mm clearance with the inner wall, two baffles of 45mm height), filling rate 30% by volume, the number of revolutions 1.5% equivalence of finely divided A-type zeolite was added at 22 rpm and 25 ° C, and 0.5% equivalence of nonionic surfactant and fragrance were sprayed for 1 minute, followed by surface modification to obtain particles.

In order to color a part of the obtained particles, the surface containing 20% aqueous dispersion of the pigment on the surface while transferring the surfactant-containing particles at a speed of 0.5 m / s on the belt conveyor (30 mm height of the surfactant-containing particle layer on the belt conveyor, 300 mm width) Was sprayed to obtain a surfactant-containing particle (b1) (average particle size 550 µm, bulk density 0.84 g / cm ³ ).

In the same manner as the method for producing the surfactant-containing particles (b1), the surfactant-containing particles (b3 and b4) (average particle diameter and bulk density are shown in Table 2) were obtained.

Anionic  Method 2 for producing surfactant-containing particles

According to the composition shown in following Table 2, surfactant containing particle | grains (b2) were manufactured in the following procedure. First, water was put into the mixing tank with a jacket provided with a stirring apparatus, and the temperature was adjusted to 50 degreeC. Sodium sulfate and fluorescent agent were added here, and it stirred for 10 minutes. Subsequently, after adding sodium carbonate, MA2 (acrylic acid / maleic acid copolymer sodium salt) was added and after further stirring for 10 minutes, a part of powder A zeolite was added. Furthermore, it stirred for 30 minutes and manufactured the slurry for spray drying.

The temperature of the obtained spray drying slurry was 50 degreeC. This slurry was spray-dried by the countercurrent spray drying apparatus provided with a pressure spray nozzle, and spray drying particle | grains of 3% of water, 0.50 g / cm <^{3> of} bulk density, and 250 micrometers of average particle diameters were obtained.

Separately, nonionic surfactants and anionic surfactants were mixed at a temperature of 80 ° C. to prepare a surfactant composition having a water content of 10%. LAS-Na was used as a neutralized solution in sodium hydroxide aqueous solution.

The spray-dried particles thus obtained were introduced into a ready-mixed mixer (Matsubo Co., Ltd., M20 type) having a sputum-shaped shovel and having a clearance between the shovel and the wall surface of 5 mm (filling rate of 50% by volume), and a jacket The stirring of the main shaft (150 rpm) and the chopper (4000 rpm) was started, flowing 80 degreeC hot water at the flow volume of 10 L / min. The prepared surfactant composition was added thereto over 2 minutes, followed by stirring for 5 minutes, followed by the addition of a layered silicate (SKS-6, an average particle diameter of 5 µm) and a part of the powder A-type zeolite (equivalent to 10%). The particles were obtained by stirring for 2 minutes.

The obtained particles and a part (2% equivalent) of the powder A-type zeolite were mixed in a V blender, sprayed with a perfume, and then the same as in the preparation method 1 of the anionic surfactant-containing particles in order to color a part of the surfactant-containing particles. The 20% aqueous dispersion of pigment | dye was sprayed by the method, and surfactant-containing particle | grains (b2) (an average particle diameter of 300 micrometers and a bulk density of 0.78 g / cm <^3> ) were obtained.

The coated inorganic particle was obtained by the following manufacturing method.

Method for producing coated inorganic particles

Among the compositions shown in Table 3, sodium carbonate was added to a ready-to-use mixer (Matsubo Co., Ltd., M20 type) having a shovel in the shape of a sputum and having a clearance between the shovel and the wall (5% by filling rate, 30% by volume), Stirring of the spindle 200 rpm was started (chopper stopped). 10 seconds after the start of stirring, a water-soluble polymer compound aqueous solution (manufactured by MA) was added for 30 seconds, and granulation and coating operations were performed.

Subsequently, the water-soluble compound (lauric acid) shown in Table 3 was added and coated for 30 seconds, continuing stirring with a reggae mixer.

[Example of Preparation of Bleach Activator Granules]

Bleach activator Assembly  Manufacturing method

As a bleach activator, 70 parts by weight of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals Co., Ltd.), 20 parts by mass of PEG # 6000, and 5 parts by mass of AOS-Na powdered product are manufactured by Hosokawa Micron Co., Ltd. Furthermore, it fed to Ohmic EM-6 type and knead | mixed extrusion (kneading temperature 60 degreeC), and the noodle-shaped extruded product of 0.8 mm diameter was obtained. This extruded product (cooled at 20 ° C. by cold air) was introduced into a Pitsmill DKA-3 type manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of the A-type zeolite powder was supplied in the same manner as a preparation and ground to have an average particle diameter of about 700. A μm bleach activator granule (A) was obtained.

Preparation of Granular Detergent Composition

Filling rate: 30% by volume, 22 rpm, 25 rpm in horizontal cylindrical electric mixer (cylinder diameter 585mm, cylinder length 490mm, 20mm clearance with inner wall on the inner wall of the drum 131.7L) The composition which showed (a) nonionic surfactant containing particle | grains of Table 1, (b) anionic surfactant containing particle | grains of Table 2, the coating inorganic particle of Table 3, and other components on condition of ° C was shown in Table 4. The mixture was mixed for 5 minutes to obtain a granular detergent composition. The average particle diameter and bulk density of the obtained granular detergent composition are shown in Table 4.

(1) Evaluation of solubility (low temperature aggregation rate)

5 g of the granular detergent composition was carefully placed in a 9.3 cm inner chalet having 80 mL of 5 ° C water, and left for 5 minutes. After standing, it was passed through a sieve having an eye of 3360 μm, and the detergent composition remaining on the sieve was dried at 60 ° C. for 2 hours. The mass after drying was measured, and the low-temperature aggregation percentage was calculated | required using the following formula.

The relationship between the obtained low temperature aggregation rate and usability is shown below. In consideration of usability at home, as the detergent composition, a low temperature aggregation rate of less than 20% is preferable.

A: low temperature aggregation rate is less than 5%

B: low temperature aggregation rate is 5% or more but less than 10%

C: low temperature aggregation rate is 10% or more but less than 20%

D: low temperature aggregation rate is 20% or more but less than 40%

E: Low temperature coagulation rate is 40% or more

[Equation 3]

Low temperature coagulation rate (%) = dry mass of the detergent composition remaining on the sieve / granular detergent composition mass x 100 put in a sieve

(2) Evaluation of high flammability (solidification rate)

3 layers of paper (moisture permeability 25g / m ² ?) Coated from the outside with cardboard (weight: 350 g / m ² ), wax sand (weight: 30 g / m ² ), graft pulp (weight: 70 g / m ² ); Using 24 hours (40 degreeC, 90% RH), the box of length 15cm x width 9.3cm x height 18.5cm was manufactured. 1.2 kg of the granular detergent composition was placed in this box, stored for 30 days in a recycled constant temperature and humidity room at 25 ° C. (65% RH, 8 hours) and 45 ° C. (85% RH, 16 hours). A sample was obtained. After storage, the detergent was carefully transferred to a 4 mm eye sieve, and the mass of the detergent remaining solidified on the sieve was measured, and the solidification rate was determined by the following equation.

[Equation 4]

Solidification rate (%) = mass of the detergent composition remaining on the sieve / granular detergent composition mass x 100 put in a box

The relationship between the obtained solidification rate and usability is shown below. In consideration of usability at home, as the detergent composition, a solidification rate of less than 20% is preferable.

◎: less than 5% solidification rate

○: more than 5% solidification rate less than 20%

△: more than 20% solidification rate less than 40%

×: more than 40% solidification rate

(3) liquidity evaluation

The angle of repose was measured by the measuring method of the angle of repose mentioned later using the granular detergent composition after performing the said solidification evaluation. The result was evaluated by the following evaluation criteria. In consideration of usability at home, as the detergent composition, an angle of repose of 60 ° or less is preferable.

<Evaluation Criteria>

◎: Angle of repose below 45 °

○: angle of repose 45 ° or more 60 ° or less

△: angle of repose more than 60 °

The average particle diameter, bulk density, and angle of repose of the present invention were measured by the following method.

(4) Measurement of average particle diameter

Each sample and its mixture were classified by using a sieve and a receiving bowl having nine stages of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 149 μm. . The sorting is piled up in order from small sieve to large sieve, and put 100 g / time base sample from the top of 1680 micrometers, and put a lid on the receiving bowl, and it is a low-tap sieve shaker (note) Seisakusho product, tapping: 156 times / minute, rolling: 290 times / minute), vibrating for 10 minutes, and then collecting the samples remaining on each sieve and the receiving vessel for each sieve, and mass of the sample Measured.

Calculating the cumulative mass frequency of the bowl and each sieve, the eye of the first sieve whose cumulative mass frequency is 50% or more is called aµm, and the eye of the sieve one step larger than aµm is bµm. The average particle diameter (weight 50%) was calculated | required by the following formula, making c% the integration of the mass frequency from a vessel into the sieve of amicrometer, and making the mass frequency on the sieve of amicrometer into d%.

[Equation 5]

Mean particle diameter (weight ^{50%) = 10 (50 (} cd / (logb - loga) × logb)) / (d / (logb - loga))

(5) Bulk density measurement

The bulk density was measured according to JIS K3362-1998.

(6) measurement of angle of repose

The angle of repose was measured using a turntable type angle measuring instrument, manufactured by Tsui Chemical Co., Ltd.

(7) measurement of smearing

1.2 kg of the high bulk density granular detergent composition adjusted by the above method was stored in the same container as used in the evaluation of solidification, stored for one month under the same conditions as those used in the evaluation of solidification, and taken out, and the degree of bleeding of the bottom was removed. Was visually judged according to the following criteria. The results are shown in Table 1 and Table 2.

◎: no bleeding was observed

○: Smears slightly observed on the outer surface of the container

×: smear was observed on the outer surface of the container

The raw material used in the Example is shown below.

Sodium carbonate: granular (Asahigarasu Co., Ltd., average particle diameter 320㎛, bulk density 1.07 g / cm ³ )

? Potassium carbonate, potassium carbonate (powder) (Asahi Glass Co., Ltd. products, the average particle size 490㎛, a bulk density of 1.30g / cm ³⁾

Sodium sulfate: Neutral anhydrous sodium sulfate (manufactured by Nihon Chemical Co., Ltd.)

Sodium sulfite: Sodium sulfite anhydrous (product of Senjugaku Co., Ltd.)

MA1: Acrylic acid / maleic acid copolymer Na salt, Aquaric TL-400 (product of Nihon Shokubai Co., Ltd.) (40% pure component aqueous solution)

MA2: Acrylic acid / maleic acid copolymer Na salt: Sokalan CP45 (BASF Co., Ltd.) diluted with water to 40% pure component.

Lauric acid: Nippon Yuji Co., Ltd. product, NAA-122, melting point 43 ℃

Zeolite A: Silton B (Mizusawa Chemical Co., Ltd., pure ingredient 80%)

P-type zeolite: DOUCIL A24 (manufactured by Ineos Silica)

α-SF-Na: Sodium salt of α-sulfo fatty acid methyl ester having 14 carbon atoms: 16 carbon atoms = 18:82 (Lion Co., Ltd. product, AI = 70%, remainder unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate , Hydrogen peroxide, water, etc.)

LAS-K: Linear alkyl (C10-C14) benzenesulfonic acid (Lyphon LH-200 (product of Lion Co., Ltd.) LAS-H pure component 96%) was prepared with 48% potassium hydroxide solution in preparation of the surfactant composition. Neutralization). The compounding quantity of Table 5 shows the mass% as LAS-K.

LAS-Na: Neutralize linear alkyl (C10-C14) benzenesulfonic acid (Lion-LH-200 (96% LAS-H pure component) manufactured by Lion Co., Ltd.) with 48% aqueous sodium hydroxide solution in preparation of surfactant composition. ). The compounding quantity of Table 5 shows the mass% as LAS-Na.

Soap: 12 to 18 fatty acid sodium (from Lion Co., Ltd., pure component: 67%, titer: 40 to 45 ° C, fatty acid composition: C ₁₂ : 11.7%, C ₁₄ : 0.4%, C ₁₆ : 29.2 %, C ₁₈ F0 (stearic acid): 0.7%, C ₁₈ F1 (olefinic acid): 56.8%, C ₁₈ F2 (linoleic acid): 1.2%, molecular weight: 289)

Nonionic Surfactant A: Ethylene oxide 15 mole adduct (90% pure component) of ECOROL 26 (an alcohol having an alkyl group having 12 to 16 carbon atoms manufactured by ECOGREEN)

Nonionic surfactant B: Ethylene oxide average 15 mole adduct of pastel M-181 (product made by Lion Oreo Chemical Co., Ltd.)

Pigment A: Gun Office (Daiichi Seika Kogyo Co., Ltd., Ultramarine Blue)

Pigment B: Pigment Green 7 (product of Daiichi Seikagyo Co., Ltd.)

Fragrance A: Fragrance composition A of Unexamined-Japanese-Patent No. 2002-146399 [Table 11]-[Table 18]

Fragrance B: Fragrance composition B of JP 2002-146399 A [Table 11]-[Table 18]

Fragrance C: Fragrance composition C of JP 2002-146399 A [Table 11]-[Table 18]

Fragrance D: Fragrance composition D of JP 2002-146399 A [Table 11]-[Table 18]

Enzyme particles: Savinase 12T (product of Novozymes) / LIPEX50T (product of Novozymes) / Tamamil 60T (product of Novozymes) / Celzyme 0.7T (product of Novozymes) = 5/2/1/2 Mixture of (mass ratio)

Phosphor: Mixture of Tinopal CBS-X (Chiba Specialty Chemicals) / Tinopal AMS-GX (Chiba Specialty Chemicals) = 3/1 (mass ratio)

Sodium percarbonate: Mitsubishi Gas Chemical Co., Ltd., SPC-D, effective oxygen amount 13.2%, average particle diameter 760㎛

White carbon: Tokusil N (Tokuyama Co., Ltd.)

Cellulose: J. RETTENMIER & SOEHNE, ARBOCEL FD-600 / 30, average fiber length: 45 µm, average fiber thickness (diameter): 25 µm

TABLE 1 Nonionic Surfactant-Containing Particles

Nonionic granules a1 a2 a3 a4 Nonionic surfactant
Nonionic Surfactant A 27 23 10 Nonionic Surfactant B 45 Aluminosilicate P-type zeolite 60 65 Zeolite A 47 35 Water soluble inorganic compounds Sodium carbonate 15 5 5 Sodium sulfate 3 α-SF-Na 3 cellulose 3 White carbon 5 water Remainder Remainder Remainder Remainder Particle size [㎛] 1000 550 850 400 Bulk Density [g / L] 800 900 650 700 Repose angle [°] 65 45 60 65

TABLE 2 Anionic Surfactant-Containing Particles

Negative ion particles b1 b2 b3 b4 α-SF-Na 10 10 10 LAS-Na 2 5 One LAS-k 6 7 2 soap 9 5 8 8 Nonionic Surfactant A 4 9 6 6 Zeolite A 21 25 31 25 MA1 3 MA2 2.5 Sodium sulfite 2 One 2 2 Sodium carbonate 27 29 27 18 Potassium carbonate 9 9 9 9 Sodium sulfate 5 Fluorescent 0.15 0.1 0.2 0.2 Spice A 0.15 Spice B 0.1 Spice C 0.1 Spice D 0.1 0.1 Pigment A 0.015 0.015 0.015 Pigment B 0.015 moisture Remainder Remainder Remainder Remainder Particle size [㎛] 500 300 500 500 Bulk Density [g / L] 850 780 850 800 Repose angle [°] 40 35 40 40 Anionic Surfactant [%] 27 17 18 21

Table 3 Covered Inorganic Particles

Coated inorganic particles Sodium carbonate 85 Lauric acid 7 MA1 3 water Remainder Particle size [㎛] 350 Bulk Density [g / L] 1150 Repose angle [°] 30

TABLE 4 Granular detergent composition

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 A) nonionic granules a1 10                a2 5 10 25 50 94                a3 10                a4 B) anionic granules b1 94 89 74 49 6 69 69                b2                b3                b4 D) coated inorganic particles 20 20 Sodium percarbonate Bleach Activator Assembly Enzyme particles One One One One One One One A / B mixing rate 5/94 10/89 25/74 50/49 94/5 10/69 10/69 Average particle diameter [㎛] 500 500 510 520 540 520 500 Bulk Density [g / L] 840 840 850 870 890 900 880 Amount of surfactant in granular detergent composition [%] 30 30 29 27 23 26 27 Solubility C B B B B A A High Mars ◎ ◎ ◎ ○ ○ ○ ◎ Smear ◎ ◎ ◎ ◎ ○ ◎ ○ liquidity ◎ ◎ ◎ ◎ ◎ ◎ ◎

TABLE 5 Continuation of Table 4: Granular Detergent Composition

Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 A) nonionic granules a1                a2 20 10 10 70 10                a3                a4 10 B) anionic granules b1 69 59 29                b2 69                b3 63                b4 63 D) coated inorganic particles 20 20 20 20 20 Sodium percarbonate 5 5 Bleach Activator Assembly One One Enzyme particles One One One One One One A / B mixing rate 10/69 20/59 10/69 10/63 70/29 10/63 Average particle diameter [㎛] 460 480 330 440 530 440 Bulk Density [g / L] 890 910 860 860 880 860 Amount of surfactant in granular detergent composition [%] 24 24 22 19 25 19 Solubility A A A A B A High Mars ◎ ◎ ◎ ◎ ○ ◎ Smear ◎ ◎ ◎ ◎ ○ ◎ liquidity ○ ◎ ◎ ◎ ◎ ◎

Claims (20)

(A) Nonionic surfactant containing particle | grains which contain 10-50% of nonionic surfactants and less than 45% of water-soluble inorganic compounds, and have an average particle diameter of 200-1000 micrometers and a bulk density of 650 g / L or more; And (B) Anionic surfactant-containing particles containing 10 to 40% of anionic surfactant, having an average particle diameter of 200 to 1000 µm and a bulk density of 650 g / L or more. Containing a particle mixture comprising: (C) Detergent composition. The method of claim 1, (D) (i) fatty acids, salts of fatty acids, or salts of fatty acids and fatty acids,     (ii) a water soluble polymer, or     (iii) (i) and (ii) above    A water-soluble inorganic salt particle further coated with a composition, characterized in that it further comprises. The method of claim 1, The amount of the water-soluble inorganic compound contained in (A) nonionic surfactant containing particle | grains is 1 to 20% with respect to the total amount of the said particle | grains, The composition characterized by the above-mentioned. The method of claim 1, The bulk density of (A) nonionic surfactant containing particle | grains is 700-1000g / L, The composition characterized by the above-mentioned. The method of claim 1, The bulk density of the (B) anionic surfactant containing particle | grains is 700-1000g / L, The composition characterized by the above-mentioned. The method of claim 1, The composition containing (A) nonionic surfactant containing particle | grains and (B) anionic surfactant containing particle | grains by the ratio of (A) / (B) = 5 / 95-80 / 20 by mass ratio. The method of claim 1, The composition containing (A) nonionic surfactant containing particle | grains and (B) anionic surfactant containing particle | grains by the ratio of (A) / (B) = 10 / 90-50 / 50 by mass ratio. The method of claim 1, (A) A composition wherein the nonionic surfactant-containing particles contain more than 20% and less than 85% of aluminosilicate relative to the total amount of the particles. The method of claim 1, (A) A composition wherein the nonionic surfactant-containing particles contain 30% to 60% of aluminosilicate relative to the total amount of the particles. The method of claim 1, (A) Polyoxyalkylene alkyl ether which the nonionic surfactant contained in a nonionic surfactant containing particle added an average of 3-30 mol of alkylene oxides of 2-4 carbon atoms to a C6-C22 aliphatic alcohol, and A composition characterized in that it is selected from the group consisting of fatty acid alkyl ester alkoxylates represented by the following formula (1): R ¹ CO (OA) _n OR ² (1) In the formula ^(1), R 1 CO represents a fatty acid residue having a carbon number of 6 ~ 22, OA represents the addition unit of alkylene oxide having a carbon number of 2 ~ 4, n represents an average addition mole number of the alkylene oxide from 3 to It is a number of 30, R <^2> represents a lower (C1-C4) alkyl group. The method of claim 1, (A) The composition characterized in that the water-soluble inorganic compound contained in the nonionic surfactant-containing particles is selected from the group consisting of sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate and sodium tripolyphosphate. The method of claim 8, (A) The composition characterized in that the aluminosilicate contained in the nonionic surfactant-containing particles is crystalline aluminosilicate represented by the following formula (I): x ¹ (M ₂ O)? Al ₂ O ₃ ? y ¹ (SiO ₂ )? w ¹ (H ₂ O) (I) In the formula (I), M represents an alkali metal atom, x ¹ , y ¹ and w ¹ represent the moles of each component, x ¹ represents 0.7 to 1.5, y ¹ represents a number of 0.8 to 6, w ¹ represents any Represents an integer. The method of claim 1, (B) Anionic surfactant contained in anionic surfactant containing particle | grains, Alkali metal salts of linear or branched alkylbenzene sulfonic acids having an alkyl group having 8 to 18 carbon atoms (LAS); Alkali metal salts of α-olefinsulfonic acids having 10 to 20 carbon atoms (AOS); Alkali metal salts of alkyl ether sulfates having straight or branched chain alkyl groups or alkenyl groups having 10 to 20 carbon atoms and added with ethylene oxide, propylene oxide, butylene oxide or a mixture thereof of 10 moles or less (AES) ; Alkali metal salts of higher fatty acids having 10 to 20 carbon atoms; And Alkali metal salts of saturated or unsaturated α-sulfofatty acids (α-SF) having 8 to 20 carbon atoms Compositions selected from the group consisting of. 3. The method of claim 2, (D) In the coated water-soluble inorganic salt particles, the fatty acid is lauric acid, The water-soluble polymer is a vinyl polymer having a carboxyl group or a sulfo group, The water-soluble inorganic salt particles are selected from the group consisting of sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate and sodium tripolyphosphate. The method according to any one of claims 1 to 14, The composition characterized in that the low temperature coagulation rate obtained by the following [formula 1] at 5 degreeC is less than 20%, and the solidification rate obtained by the following [formula 2] is less than 20%: [Equation 1] Low temperature coagulation rate (%) = dry mass of the detergent composition remaining on the sieve / granular detergent composition mass x 100 put in a sieve [Equation 2] Solidification rate (%) = Mass of the detergent composition remaining on the sieve / mass of granular detergent composition x100 put in the box. (A) Polyoxyalkylene alkyl ether which averaged 3-30 mol of C2-C4 alkylene oxides to a C6-C22 aliphatic alcohol, and following formula (1): R ¹ CO (OA) _n OR ² (1) (In the formula (1), R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, OA represents an additional unit of alkylene oxide having 2 to 4 carbon atoms, n represents an average added mole number of alkylene oxide 3 Is a number of ～ 30, and R ² represents a lower alkyl group) 10-50% of nonionic surfactants selected from the group consisting of fatty acid alkyl ester alkoxylates, Nonionic with less than 1-20% of water-soluble inorganic compounds selected from the group consisting of sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate and sodium tripolyphosphate, with an average particle diameter of 200-1000 μm and a bulk density of 700-1000 g / L Surfactant-containing particles, (B) the following groups: Alkali metal salts of linear or branched alkylbenzene sulfonic acids having an alkyl group having 8 to 18 carbon atoms (LAS); Alkali metal salts of alpha -olefin sulfonic acids having 10 to 20 carbon atoms (AOS); Alkali metal salts of alkyl ether sulfuric acid (AES) having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, and an ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having an average added mole number of 10 mol or less. ; Alkali metal salts of higher fatty acids having 10 to 20 carbon atoms; And Alkali metal salts of saturated or unsaturated α-sulfofatty acids (α-SF) having 8 to 20 carbon atoms Anionic surfactant-containing particles having an anionic surfactant selected from the group consisting of 10 to 40%, an average particle diameter of 200 to 1000 µm and a bulk density of 700 to 1000 g / L. (C) detergent composition comprising a. The method of claim 16, (D) A composition characterized by further comprising sodium carbonate and enzyme particles coated with lauric acid and maleic / acrylic acid copolymer sodium salt. The method of claim 16 or 17, The composition characterized in that the low temperature coagulation rate obtained by the following [formula 3] at 5 degreeC is less than 20%, and the solidification rate obtained by the following [formula 4] is less than 20%: [Equation 3] Low temperature coagulation rate (%) = dry mass of the detergent composition remaining on the sieve / granular detergent composition mass x 100 put in a sieve [Equation 4] Solidification rate (%) = mass x 100 of the granular detergent composition put into the mass / box of the detergent composition remaining on the sieve. (A) Nonionic surfactant containing particle | grains with 10-50% of nonionic surfactant and less than 45% of water-soluble inorganic compounds, whose average particle diameter is 200-1000 micrometers, and bulk density is 650g / L or more, (B) Anionic Mixing the anionic surfactant-containing particles containing a surfactant and having an average particle diameter of 200 to 1000 µm and a bulk density of 650 g / L or more Including, (C) The manufacturing method of the granular detergent composition which improved low temperature solubility. The method of claim 19, (D) (i) fatty acids, salts of fatty acids, or salts of fatty acids and fatty acids,     (ii) a water soluble polymer, or     (iii) (i) and (ii) above     The water-soluble inorganic salt particles coated with a furnace Manufacturing method characterized in that it further comprises.