JP2010254768A - Method for producing granular detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method by which a granular detergent composition having excellent solubility can be produced with good granulability even if the concentration of a surfactant is low. <P>SOLUTION: The method for producing a granular detergent composition containing 5-28 mass% of a surfactant, 15-60 mass% of a water-soluble inorganic salt, and 10-45 mass% of a water-insoluble inorganic salt includes: a process 1 for obtaining a kneaded material of a detergent raw material containing the surfactant, the water-soluble inorganic salt, and the water-insoluble inorganic salt; a process 2 for obtaining an extruded product by supplying the kneaded material obtained in the process 1 and a water-soluble inorganic salt to an extruder, and a process 3 for granulating the extruded product obtained in the process 2. In the method, the ratio (mass ratio) of the water-soluble inorganic salt used in the process 1 to the water-soluble inorganic salt used in the process 2: [water-soluble inorganic salt used in the process 1]/[water-soluble inorganic salt used in the process 2] is in the range of 2-11. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a granular detergent composition.

In the granular detergent composition, organic components such as surfactants and organic polymer compounds are usually blended for the purpose of improving cleaning performance and imparting various other performances.
In recent years, due to environmental considerations, there has been a tendency to reduce the concentration of organic components in detergent compositions. For example, the surfactant concentration of a general garment detergent 15 years ago was approximately 30-40%. At present, about 20 to 30% is the mainstream, and there is a detergent for clothing having a surfactant concentration of 20% or less.

Conventionally, granular detergent compositions, in particular granular detergent compositions used as garment detergents, are produced by spray drying from aqueous slurries containing surfactants, alkali builders, etc., and spray-dried particles having voids inside the particles. A detergent consisting of has been used. However, since the spray-dried particles are bulky, the volume used for one washing is large, and the spray-drying method has a large energy loss and is not economical. Therefore, in recent years, granular detergent compositions with increased bulk density have become the mainstream in place of the above-mentioned spray-dried particles.
As a method for producing a granular detergent composition having a high bulk density, for example, a detergent raw material such as the spray-dried particles is kneaded with a kneader or the like, and then the kneaded product (kneaded product) is pulverized.・ The grinding method is known. For example, Patent Document 1 discloses that a neutralized product obtained by neutralizing an alkylarylsulfonic acid with a concentrated aqueous potassium hydroxide solution and other detergent components are kneaded, mixed, crushed, and then a specific particle size. A method of coating with a water-insoluble fine powder is described. Patent Document 2 discloses a method in which a detergent raw material is kneaded with a kneader, the kneaded detergent raw material is supplied to an extrusion granulator for detergent processing having a specific structure, molded, and then supplied to a crusher to crush and granulate. Is described. In addition, Patent Document 3 includes a crystallized anionic surfactant and a crystalline inorganic compound, and in the production of a detergent composition containing an anionic surfactant as a main surfactant, It describes that the production conditions are controlled or set so that the area ratio of the anisotropic substance in the inside is within a specific range.

JP-A 61-272300 JP 2000-006139 A JP 2003-105393 A

In the case of producing a granular detergent composition by the kneading and pulverizing method as described above, the surfactant functions as a binder. Therefore, when the surfactant concentration is high, this is not a problem. However, when the surfactant concentration is low, various problems arise in terms of production or quality. For example, as the amount of binder decreases, the concentration of inorganic components becomes relatively high, the kneaded product becomes brittle, and adhesion to the pulverizer due to poor kneading tends to occur. is there.
To cope with this problem, it is possible to increase the kneading strength by changing the paddle pattern in the kneading machine. However, increasing the kneading strength tends to degrade the solubility of the resulting detergent composition, and there is a limit to increasing the kneading strength.
This invention is made in view of the said situation, Comprising: Even if surfactant concentration is low, the manufacturing method which can manufacture the granular detergent composition which has favorable granulation property and excellent solubility is provided. For the purpose.

As a result of intensive studies, the present inventors have found that one of the causes of the deterioration in productivity in the prior art is an increase in the amount of water-soluble inorganic salt, particularly sodium salt, accompanying the decrease in the amount of surfactant. In particular, it has been found that when the amount of sodium carbonate exceeds 26% by mass in the kneaded product, the kneaded state deteriorates and the adhesion to the apparatus or the like increases rapidly. Moreover, it discovered that the particle size of the water-soluble inorganic salt disperse | distributed in a kneaded material became small as one of the causes which solubility deteriorates when kneading | mixing intensity | strength is raised. As a result of further investigation based on such knowledge, in the production of a granular detergent composition containing a surfactant, a water-soluble inorganic salt and a water-insoluble inorganic salt, after the kneading and before pulverization, an extrusion process is performed, It has been found that the above problem can be solved by adding a part of the water-soluble inorganic salt to the kneaded product in the extrusion step, and the present invention has been completed.
That is, this invention is a manufacturing method of the granular detergent composition containing 5-28 mass% of surfactant, 15-60 mass% of water-soluble inorganic salts, and 10-45 mass% of water-insoluble inorganic salts,
Step 1 for obtaining a kneaded product of a detergent raw material containing a surfactant, a water-soluble inorganic salt and a water-insoluble inorganic salt,
Step 2 for supplying the kneaded product and water-soluble inorganic salt obtained in Step 1 to an extruder to obtain an extrudate, and Step 3 for granulating the extrudate obtained in Step 2;
Have
The ratio (mass ratio) between the water-soluble inorganic salt used in the step 1 and the water-soluble inorganic salt used in the step 2 is [water-soluble inorganic salt used in step 1] / [water-soluble inorganic salt used in step 2]. It is in the range of 2-11, It is a manufacturing method of the granular detergent composition characterized by the above-mentioned.

  According to the present invention, even when the surfactant concentration is low, a granular detergent composition having excellent granulation properties and excellent solubility can be produced.

Hereinafter, the production method of the present invention will be described in more detail.
In the production method of the present invention, a granular detergent composition containing 5 to 28% by mass of a surfactant, 15 to 60% by mass of a water-soluble inorganic salt and 10 to 45% by mass of a water-insoluble inorganic salt is produced.
Here, in the present specification and claims, the content of each of these components is a ratio to the total mass of the granular detergent composition. Hereinafter, the content may be referred to as a concentration.
The concentration of the surfactant is measured according to a method for determining the amount corresponding to the surfactant described in JIS K3362-1998.
Regarding the classification of “water-soluble inorganic salt” and “water-insoluble inorganic salt”, the salt represented by the solubility product in the Basic Manual II (2nd revised edition, pages 777-791, Maruzen, 1975) is regarded as water-insoluble. To do. Further, as a simple discrimination method, a solution that completely dissolves when 5 g is added to 100 mL of hot water (85 ° C. or higher) is water-soluble, and a portion that remains as a residue is water-insoluble.

In the granular detergent composition, the concentration of the surfactant is preferably 5 to 25% by mass, and more preferably 8 to 20% by mass. If the concentration is less than the lower limit of the above range, sufficient cleaning performance as a detergent composition may not be obtained, and exceeding the upper limit is not preferable for environmental reasons.
In the granular detergent composition, the concentration of the water-soluble inorganic salt is preferably 15 to 50% by mass, and more preferably 18 to 45% by mass. If the concentration is less than the lower limit of the above range, the concentration of the surfactant or water-insoluble inorganic salt is relatively high, and the solubility of the granular detergent composition may be lowered. When the upper limit is exceeded, the total concentration of inorganic salts in the granular detergent composition is increased, and the solubility of the granular detergent composition may be reduced.
In the granular detergent composition, the concentration of the water-insoluble inorganic salt is preferably 12 to 40% by mass, more preferably 13 to 35% by mass. If the concentration is less than the lower limit of the above range, the concentration of the surfactant or water-soluble inorganic salt is relatively high, and the solubility of the granular detergent composition may be lowered. If the upper limit is exceeded, the cleaning performance of the granular detergent composition may be reduced.
In the granular detergent composition, the total concentration of the water-soluble inorganic salt and the water-insoluble inorganic salt is preferably 60 to 90% by mass, and more preferably 65 to 85% by mass. When the concentration is less than the lower limit of the above range, the surfactant in the granular detergent becomes relatively high, which is undesirable from the environmental viewpoint, and a problem arises in handling properties such as solidification of the product. On the other hand, if the upper limit is exceeded, the cleaning performance as a detergent composition may be reduced.

In this invention, while performing the following processes 1-3, the granular detergent composition of the said composition is used by the water-soluble inorganic salt (henceforth water-soluble inorganic salt (1)) used at the process 1, and the process 2. The ratio (mass ratio) with the water-soluble inorganic salt (hereinafter referred to as water-soluble inorganic salt (2)) is [water-soluble inorganic salt (1)] / [water-soluble inorganic salt (2)] = 2-11. Manufacture by making it within the range. The value of [water-soluble inorganic salt (1)] / [water-soluble inorganic salt (2)] is preferably 2.5 to 10, and more preferably 3 to 9.
Process 1: The process of obtaining the kneaded material of the detergent raw material containing surfactant, water-soluble inorganic salt (1), and water-insoluble inorganic salt.
Step 2: A step of supplying the kneaded product and water-soluble inorganic salt (2) obtained in Step 1 to an extruder to obtain an extrudate.
Step 3: A step of granulating the extrudate obtained in Step 2 above.
The granular detergent composition usually contains an inorganic salt as an alkali builder, neutral builder or the like. Conventionally, when producing such a composition, the entire amount of the inorganic salt is added all at once during the kneading, but in the present invention, a part of the water-soluble inorganic salt is divided from the inorganic salt, Add during extrusion. Thereby, productivity improves and the solubility to water also improves.
The reason why such an effect can be obtained is that, by first dividing a part of the water-soluble inorganic salt, an apparatus trouble due to kneading (kneading) failure due to an increase in the amount of the water-soluble inorganic salt can be suppressed. It is thought that it will be done. Furthermore, when quality is considered, the production | generation of the gel structure produced when the refined | miniaturized inorganic salt and surfactant contact with water can be reduced, and the solubility deterioration at low temperature of detergent particles can be suppressed. Further, by adding a part of the water-soluble inorganic salt at the time of extrusion, the water-soluble inorganic salt having a certain large particle diameter is dispersed in the finally obtained detergent composition, so that the granular detergent composition It is thought that the solubility in water is also improved.
Hereinafter, each process will be described in more detail.

<Step 1>
In step 1, a kneaded product of detergent raw materials containing a surfactant, a water-soluble inorganic salt (1) and a water-insoluble inorganic salt is obtained.

[Surfactant]
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Any one of these may be used alone, or two or more may be used in combination. Also good.
Examples of the anionic surfactant include a sulfonate type anionic surfactant, a sulfate ester type anionic surfactant, a carboxylate type anionic surfactant, and a phosphate ester type anionic surfactant.
“Salts” in these anionic surfactants include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; alkanolamine salts such as triethanolamine; and ammonium salts. Alkali metal salts are preferred.

Examples of the sulfonate type anionic surfactant include alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid dialkali metal salt, α-sulfo fatty acid alkyl ester salt and the like.
More specifically, examples of the alkyl benzene sulfonate include linear or branched alkyl benzene sulfonates having an alkyl group having 8 to 18 carbon atoms, and linear alkyl benzene sulfonates are particularly preferable. .
As the alkane sulfonate, the alkane sulfonate is also called paraffin sulfonate, and examples thereof include alkane sulfonate having 10 to 21 carbon atoms. The alkane sulfonate preferably contains a secondary alkane sulfonate. Preferred alkane sulfonates have, for example, 10 to 21 carbon atoms per molecule, preferably at least 80% by weight, more preferably at least 90% by weight have 10 to 14 carbon atoms per molecule. Mention may be made of mixtures of secondary alkyl sulfonates with small amounts of primary alkyl sulfonates, disulfonates or polysulfonates.
Examples of the α-olefin sulfonate include α-olefin sulfonate having 10 to 20 carbon atoms.
Examples of the α-sulfo fatty acid dialkali metal salt include saturated or unsaturated α-sulfo fatty acid dialkali metal salts having 8 to 20 carbon atoms.
Examples of the α-sulfo fatty acid alkyl ester salt include methyl, ethyl or propyl ester salts of the α-sulfo fatty acid salt.

Sulfate ester type anionic surfactants include alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates, polyoxyalkylene alkenyl phenyl ethers. Examples thereof include sulfates and alkyl polyhydric alcohol ether sulfates.
More specifically, examples of the alkyl sulfate or alkenyl sulfate include alkyl sulfates or alkenyl sulfates having 10 to 20 carbon atoms.
Polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl phenyl ether sulfate, and polyoxyalkylene alkenyl phenyl ether sulfate are alkyl ether sulfate, alkenyl ether sulfate, and alkyl phenyl ether, respectively. An alkylene oxide added to a sulfate or alkenyl phenyl ether sulfate.
As the alkylene oxide, one having 2 to 4 carbon atoms or a mixture of ethylene oxide (EO) and propylene oxide (PO) is preferable. When EO and PO coexist, the ratio is preferably in the range of EO / PO = 0.1 / 9.9 to 9.9 / 0.1 in terms of molar ratio. As the alkylene oxide, EO is particularly preferable.
In the case of polyoxyalkylene alkyl ether sulfate or polyoxyalkylene alkenyl ether sulfate, the number of moles of alkylene oxide added is preferably 0.5 to 10 moles on average. Moreover, in the case of polyoxyalkylene alkyl phenyl ether sulfate and polyoxyalkylene alkenyl phenyl ether sulfate, 3-30 mol is preferable on average.
The number of carbon atoms of the alkyl group or alkenyl group in the polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkylphenyl ether sulfate, and polyoxyalkylene alkenyl phenyl ether sulfate is preferably 8 to 20. The alkyl group or alkenyl group may be linear or branched.
Examples of the alkyl polyhydric alcohol ether sulfate include alkyl glyceryl ether sulfonate having 10 to 20 carbon atoms.

Examples of the carboxylate type anionic surfactant include polyoxyalkylene alkyl ether carboxylate, polyoxyalkylene alkenyl ether carboxylate, and higher fatty acid salt (soap) having 10 to 20 carbon atoms.
Examples of the alkylene oxide in the polyoxyalkylene alkyl ether carboxylate and polyoxyalkylene alkenyl ether carboxylate include the same as those described in the description of the sulfate ester type anionic surfactant.
As for carbon number of the alkyl group or alkenyl group in polyoxyalkylene alkyl ether carboxylate and polyoxyalkylene alkenyl ether carboxylate, 10-20 are preferred. The alkyl group or alkenyl group may be linear or branched.
Phosphate ester type anionic surfactants include long chain monoalkyl phosphate, long chain dialkyl phosphate, long chain sesquialkyl phosphate, polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate And polyoxyethylene sesquialkyl phosphate. The “long-chain” alkyl group has 8 or more carbon atoms, and preferably 10-20.

Examples of nonionic surfactants include the following.
(1) A polyoxyalkylene alkyl (or alkenyl) ether obtained by adding an alkylene oxide to an aliphatic alcohol.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

Among the above, in the polyoxyalkylene alkyl (or alkenyl) ether of (1), examples of the aliphatic alcohol include primary alcohols and secondary alcohols, with primary alcohols being preferred. Further, the alkyl group of the aliphatic alcohol may be linear or branched. 6-22 are preferable and, as for carbon number of this aliphatic alcohol, 8-18 are more preferable.
The alkylene oxide added to the aliphatic alcohol preferably has 2 to 4 carbon atoms, and the number of moles added is preferably 3 to 30 moles on average, more preferably 5 to 20 moles, and even more preferably 7 to 18 moles. .
The polyoxyalkylene alkyl (or alkenyl) ether of (1) is preferably polyoxyethylene alkyl (or alkenyl) ether or polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether.

Examples of the fatty acid alkyl ester alkoxylate (3) include those represented by the general formula: R ⁴ CO (OA) _m OR ⁵ .
In the formula, R ⁴ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.
OA represents an addition unit of an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide.
m shows the average addition mole number of alkylene oxide, 3-30 mol is preferable, 5-20 mol is more preferable, 7-18 mol is further more preferable.
R ⁵ represents a lower (carbon number 1 to 4) alkyl group which may have a substituent having 1 to 3 carbon atoms.

Examples of the cationic surfactant include dilong chain alkyl dishort chain alkyl type quaternary ammonium salt, mono long chain alkyl trishort chain alkyl type quaternary ammonium salt, tri long chain alkyl monoshort chain alkyl type quaternary ammonium salt, and the like. Is mentioned.
Here, the above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.
“Short chain alkyl” refers to an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms. The alkyl group may have a substituent such as an alkylphenyl group, a benzyl group, a hydroxy group, or a hydroxyalkyl group, and may have an ether bond between carbons. “Short chain alkyl” is an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; 2 to 4 carbon atoms, preferably A few polyoxyalkylene groups are preferred.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

Any one of these surfactants may be used alone, or two or more thereof may be used in combination.
In the present invention, considering the cleaning performance, it is preferable that the granular detergent composition contains at least an anionic surfactant as the surfactant.
In this case, the ratio of the anionic surfactant to the total of all the surfactants is preferably 60% by mass or more, more preferably 65 to 95% by mass, and further preferably 68 to 85% by mass.
As anionic surfactants, α-sulfo fatty acid alkyl ester salts, alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfates, polysulfates, detergency, solubility, and powder physical properties of the resulting granular detergent are considered. One or more selected from the group consisting of oxyalkylene alkyl ether sulfates and higher fatty acid salts (soaps) are preferred, and in particular the group consisting of α-sulfo fatty acid alkyl ester salts, alkylbenzene sulfonates and higher fatty acid salts (soaps). 1 or more types selected from are preferable.

The granular detergent composition preferably further contains a nonionic surfactant in addition to the anionic surfactant. Thereby, detergency, dust generation, and solubility are improved.
In this case, 1-40 mass% is preferable and, as for the ratio of the nonionic surfactant with respect to the sum total of all the surfactants, 5-30 mass% is more preferable.
The nonionic surfactant is preferably a polyoxyalkylene alkyl (or alkenyl) ether in which an alkylene oxide is added to the aliphatic alcohol of the above (1) in consideration of the solidification property and fluidity of the granular detergent to be obtained. A polyoxyalkylene alkyl (or alkenyl) ether obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having several 12 to 16 is preferable.

[Water-soluble inorganic salt (1), water-insoluble inorganic salt]
As the water-soluble inorganic salt (1) and the water-insoluble inorganic salt, the above-mentioned definitions of the water-soluble inorganic salt and the water-insoluble inorganic salt have been made from among the inorganic salts conventionally incorporated in the detergent composition as a detergent component. Applicable ones can be selected as appropriate.
As an inorganic salt mix | blended as a detergent component with a detergent composition, the inorganic salt (inorganic builder) used as an alkali builder and a neutral builder is mentioned, for example.
Examples of inorganic builders include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite; sodium silicate, crystalline alkali metal silicate (crystalline Layered sodium silicate, etc.), alkali metal silicates such as amorphous alkali metal silicates; composites of sodium carbonate and amorphous alkali metal silicates (for example, NABION 15 (trade name) manufactured by Rhodia); sodium sulfate, Alkali metal sulfates such as potassium sulfate; alkali metal chlorides such as sodium chloride and potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; Aluminum such as crystalline aluminosilicate and amorphous aluminosilicate Silicates; and the like.

Among these inorganic builders, those corresponding to the water-soluble inorganic salt (1) include alkali metal carbonates, alkali metal sulfites, alkali metal silicates, alkali metal sulfates, alkali metal chlorides, phosphates, etc. Is mentioned.
Examples of water-insoluble inorganic salts include calcium carbonate, white carbon, and aluminosilicate.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferred from the viewpoint of cation exchange ability.
As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like can be suitably blended. The average primary particle size of the crystalline aluminosilicate is preferably 0.1 to 10 μm.
Commercially available crystalline aluminosilicates include ZEOLITE 4A (trade name) manufactured by HAIXING CHEMICAL CO., LTD. OF DONGYING CITY; FUJIAN RISHENG C. 4A ZEOLITE (trade name) manufactured by L., LTD .; 4A-Zeolite (trade name) manufactured by Shanxi Yuchi Changi High-Tech Co., Ltd .; ▲ minutes ▼ 4A ZEOLITE (trade name) manufactured by ALUMINUM OF OF CHINA., LTD .; 4A Zeolite manufactured by Huying Chemical Products Co., LTD; Zeolite 4A Type (trade name) manufactured by Toi Silicate Chemicals Co., Ltd .; COLITE-P (trade name) manufactured by COSMO FINE CHEMICALS CO., LTD .; manufactured by PQ Chemical (PQ Chemicals) VALFOR 100 Zeolite NaA; Shiruton B (trade name) manufactured by Mizusawa Chemical Industry Co., Ltd. and the like are preferable.

In addition to the inorganic builder, examples of the inorganic salt blended in the detergent composition as a detergent component include alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate as a pH adjuster, surfactant acid precursors, and the like. Examples thereof include alkali metal hydroxide salts such as sodium hydroxide and potassium hydroxide blended as body neutralizing agents.
Among these, examples of the water-soluble inorganic salt (1) include alkali metal dihydrogen phosphate and alkali metal hydroxide.

You may mix | blend other components other than surfactant, water-soluble inorganic salt (1), and water-insoluble inorganic salt with a detergent raw material as needed.
The other is not particularly limited, and can be appropriately selected from the components conventionally blended in detergent compositions. For example, organic compounds (organic builder) used as detergent builders, fluorescent agents, ultraviolet absorption Agents, polymers, enzyme stabilizers, anti-caking agents, metal ion scavengers, pH adjusters, water and the like. Specific examples of these components are shown below.

[Organic Builder]
Examples of organic builders include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; poly Crylate, acrylic acid-allyl alcohol copolymer salt, acrylic acid-maleic acid copolymer salt, polyacetal carboxylic acid salt such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, Examples thereof include polysaccharide oxides such as cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethylcellulose.
Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000-80000, polyacrylate, acrylic acid-maleic anhydride copolymer having a weight average molecular weight of 1000-80000 And polyacetal carboxylates such as polyglyoxylic acid having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) (for example, those described in JP-A No. 54-52196) are suitable.
The said organic builder can be used individually by 1 type or in combination of 2 or more types as appropriate.

In the present invention, the organic builder is preferably used in combination with an inorganic builder because the cleaning power and stain dispersibility in the washing liquid are improved.
As the organic builder used at this time, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid and the like are preferable.

[Fluorescent agent]
Examples of the fluorescent agent (fluorescent brightening agent) include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, Examples include 2- (styrylphenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives. The said fluorescent brightening agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
Commercially available fluorescent agents include: Whitetex SA, Whitetex SKC (above, trade name) manufactured by Sumitomo Chemical Co., Ltd .; Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (manufactured by Ciba Japan Co., Ltd.) As mentioned above, Lemonite CBUS-3B (trade name) manufactured by Khyati Chemicals and the like are preferable. Of these, chinopearl CBS-X and chinopearl AMS-GX are more preferable.

[Ultraviolet absorber]
The ultraviolet absorber is not particularly limited as long as it is a substance that absorbs ultraviolet rays, converts them into infrared rays, visible rays, and the like and emits them. Specifically, aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, amyl p-dimethylaminobenzoate, ethylene glycol salicylate, dipropylene glycol salicylate, octyl salicylate Salicylic acid derivatives such as myristyl salicylate, methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, p-methoxycinnamate-2-ethylhexyl, butyl p-methoxycinnamate, etc. Cinnamic acid derivatives, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, benzophenone derivatives such as 2,2′-dihydroxy-4-methoxybenzophenone, urocanic acid, ethyl urocanate Etc. Examples thereof include azole compounds and 4-t-butyl-4′-methoxybenzoylmethane.

[Polymers]
As the polymers, for example, they are generally used as a binder or a powder physical property adjusting agent when preparing detergent particles, or as a recontamination preventing agent that imparts a recontamination preventing effect on hydrophobic fine particles (dirt). The thing that is. Examples of such a polymer include polyethylene glycol having an average molecular weight of 200 to 200,000, a salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, polyvinyl alcohol, hydroxypropylmethylcellulose (HPMC), carboxymethylcellulose salt (CMC). ) And the like.
Moreover, the copolymer of the repeating unit derived from terephthalic acid and the repeating unit derived from ethylene glycol and / or propylene glycol, which are used as a soil release agent, or a terpolymer is also included.
Moreover, polyvinyl pyrrolidone etc. which are used in order to give the color transfer prevention effect are also mentioned.
Among the above polymers, HPMC is preferable and HPMC having a weight average molecular weight of 20,000 or more is more preferable from the viewpoint of imparting flexibility to an object to be washed and preventing recontamination.
Such polymers can be used singly or in appropriate combination of two or more.

[Enzyme stabilizer]
As an enzyme stabilizer, calcium salt, magnesium salt, a polyol, formic acid, a boron compound etc. can be mix | blended, for example. Of these, sodium tetraborate, calcium chloride and the like are preferable.
An enzyme stabilizer can be used individually by 1 type or in combination of 2 or more types as appropriate.

[Anti-caking agent]
As the anti-caking agent, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.

[Metal ion scavenger]
The metal ion scavenger captures trace metal ions and the like in tap water and has an effect of suppressing the adsorption of metal ions to the fiber (object to be washed).
As metal ion scavengers, in addition to those included in the alkali builder, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycolethylenediaminehexaacetic acid; 1-hydroxyethane-1,1-diphosphonic acid (HEDP- H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid , Hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) Organic phosphones such as Derivative or a salt thereof; diglycolic acid, citric acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.

[PH adjuster]
The granular detergent composition of the present invention is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by weight aqueous solution (25 ° C.) of the granular detergent composition is preferably 8 or more. It is more preferable that pH in a mass% aqueous solution is 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
The pH of the granular detergent composition can be usually adjusted by blending an alkaline agent. Examples of the alkaline agent include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, sodium hydroxide, potassium hydroxide and the like in addition to the inorganic builder and organic builder. Specifically, sodium carbonate is preferably used from the viewpoint of solubility in water and alkalinity.
In order to prevent the pH of the granular detergent composition from becoming too high, the pH can be adjusted to the above pH range using an acid or the like. Examples of such acids include the metal ion scavengers, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or their polycarboxylic acids, citric acid, sulfuric acid, hydrochloric acid. Etc. can be used.
In addition, it is also possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.
The said pH adjuster can be used individually by 1 type or in combination of 2 or more types as appropriate.

These detergent raw materials are prepared by, for example, preparing spray-dried particles containing a part of the detergent raw material, adding liquid components (remaining detergent raw materials, moisture, etc.) to the spray-dried particles, and kneading them. it can. Further, each detergent raw material may be directly kneaded without being spray-dried particles.
When preparing spray-dried particles, if a component that is not suitable for spray-drying as a detergent component (for example, nonionic surfactants, alcohols, fragrances, esters, etc. that are unstable to heat) is included, It is preferable not to add to the spray-dried particles but to add them separately.
For example, when α-sulfo fatty acid alkyl ester salt, alkylbenzene sulfonate, higher fatty acid salt and nonionic surfactant are used as the surfactant, among these, α-sulfo fatty acid alkyl ester salt and nonionic surfactant are liquids. It is preferable to contain the alkylbenzene sulfonate, higher fatty acid salt and other components in the spray-dried particles.

The spray-dried particles can be produced by a conventionally known production method.
Specifically, a part of detergent raw material (part of surfactant, water-soluble inorganic salt (1), water-insoluble inorganic salt, etc.) is dissolved and dispersed in water to prepare a slurry for spray drying, and the spray It can be produced by spray drying the slurry for drying.
The solid content concentration of the slurry for spray drying is preferably about 50 to 70% by mass. The pH of the slurry is preferably about 7-11. The temperature of the slurry is preferably about 50 to 85 ° C.
Spray drying can be performed by a known method. For example, the spray-drying slurry is transferred to a spray-drying tower, and spray-dried particles are produced by spraying at a predetermined spray pressure from a spray-drying slurry atomizer installed in the spray-drying tower. it can.
The spray-drying tower may be a counter-current type or a co-current type. Among them, the counter-current type is preferable because thermal efficiency and dry powder (spray-dried particles) can be sufficiently dried.
Examples of the atomizer for the slurry for spray drying include a pressure spray nozzle, a two-fluid spray nozzle, and a rotary disk type. Among these, it is preferable to use a pressure spray nozzle that makes it easy to obtain a desired average particle diameter, and the spray pressure is preferably in the range of 15 to 40 kg / cm ² .

During spray drying of the slurry for spray drying, high temperature gas is supplied into the spray drying tower. This hot gas is supplied from, for example, the lower part of the spray drying tower and discharged from the top of the spray drying tower.
100-500 degreeC is preferable and, as for the inlet temperature of this hot gas, 200-300 degreeC is more preferable. Moreover, 70-150 degreeC is preferable and the temperature of the gas discharged | emitted from a spray-drying tower has more preferable 72-120 degreeC.
In addition, when high temperature gas is supplied from the lower part of a spray-drying tower and discharged | emitted from the tower top of a spray-drying tower (countercurrent type), in order to suppress that the temperature of the spray-dried particle obtained becomes too high, it sprays. Cold air can be supplied from the bottom of the drying tower. At the same time, for example, inorganic fine particles (zeolite or the like) may be introduced as a coating agent from the lower part of the spray drying tower, and contacted with the spray dried particles to adhere to the surface of the spray dried particles. Thereby, adhesion of the spray-dried particles to the inner wall of the spray-drying tower can be prevented, and the fluidity of the obtained spray-dried particles can be improved.

The bulk density of the spray-dried particles is preferably 0.25 to 0.50 g / L, more preferably 0.3 to 0.46 g / L in consideration of handling properties, prevention of breakage, and the like. The bulk density of the spray-dried particles can be measured according to JIS K 3362-1998.
The water content of the spray-dried particles is preferably 3 to 9% by mass and more preferably 4 to 8% by mass in consideration of solidification, adhesion, productivity, and the like. The moisture content is measured using an infrared moisture meter (manufactured by Kett Co., Ltd.) under measurement conditions of a sample surface temperature of 165 ° C. for 20 minutes.
The average particle diameter of the spray-dried particles is not particularly limited, but is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and particularly preferably 300 to 700 μm in consideration of dust generation suppression, particle breakage, and the like. The average particle size is determined by performing classification using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm, and from the mass frequency of each particle size to 50% by mass It is obtained by calculating (median diameter).
These physical properties of the spray-dried particles are adjusted by adjusting the production conditions of the spray-dried particles, such as the constituents of the slurry for spray drying, the solid content concentration, and the atomization conditions (nozzle type, spray pressure) of the spray drying device. it can.

A kneaded product can be obtained by charging the spray-dried particles together with a liquid component into a kneading (kneading) apparatus. When spray-dried particles are not prepared, a kneaded product can be obtained by putting each detergent raw material directly or by adding a premixed mixture to a kneading (kneading) apparatus.
In the kneading apparatus, the introduced detergent raw material is mixed in stages through transportation, compaction, and kneading (kneading) while applying a shearing force to form a kneaded product (kneaded product).
As a kneading (kneading) apparatus, a known apparatus can be used as appropriate. For example, a hermetic consolidation apparatus, preferably a horizontal continuous kneader is preferably used. In addition to the kneader, a single screw or twin screw extruder may be used. These apparatuses may be either a batch type or a continuous type.
The temperature of the material to be kneaded or the contents in the kneading (kneading) apparatus is generally 30 to 80 ° C, preferably 35 to 75 ° C, more preferably 40 to 70 ° C. When the temperature is lower than 30 ° C., the viscosity and hardness of the kneading (kneading) are increased, so that the load on the apparatus becomes excessive or the kneading failure due to the shortage of the binder tends to occur, which is not preferable. On the other hand, when the temperature is higher than 80 ° C., the adherence of the kneaded product (the kneaded product) is increased, and it tends to adhere to an apparatus used in a subsequent process such as a pulverizer, which is not preferable.
In order to suppress the temperature rise due to the kneading (kneading) of the material to be kneaded (detergent raw material), it is desirable to perform kneading (kneading) while passing the refrigerant through the jacket of the kneading (kneading) device. As the refrigerant, an aqueous solution of ethylene glycol is suitable, and its concentration is 15 to 30% by mass, preferably 20 to 25% by mass.

<Step 2>
In step 2, the kneaded product and the water-soluble inorganic salt (2) obtained in step 1 are supplied to an extruder to obtain an extrudate (molded product).
Examples of the water-soluble inorganic salt (2) are the same as those mentioned as the water-soluble inorganic salt (1). In particular, when the granular detergent composition contains a sodium salt such as sodium carbonate or sodium sulfate as the water-soluble inorganic salt, it is preferable to blend a part or all of the sodium salt as the water-soluble inorganic salt (2). . The smaller the amount of sodium salt used during kneading, the better the kneading state. Moreover, solubility is also improved by adding a sodium salt at the time of extrusion.

In the present invention, the water-soluble inorganic salt (2) has an average particle diameter of 50 to 300 μm and the average particle diameter of the water-soluble inorganic salt (1) present in the kneaded product obtained in step 1. It is preferable to use one that is 2 to 30 times the dispersed particle size. Thereby, the effect of the present invention is further improved.
Methods for measuring the average particle size of the water-soluble inorganic salt (2) and the dispersed particle size of the water-soluble inorganic salt (1) in the kneaded product are shown in the examples described later.
60-250 micrometers is preferable and, as for the average particle diameter of water-soluble inorganic salt (2), 60-200 micrometers is more preferable.
The average particle size is preferably 2 to 30 times the dispersion particle size, and more preferably 5 to 10 times. This value can be adjusted by adjusting the average particle size of the water-soluble inorganic salt (2) used and the value of the dispersed particle size of the water-soluble inorganic salt (1) in the kneaded product. The dispersed particle size of the water-soluble inorganic salt (1) in the kneaded product is the average particle size of the water-soluble inorganic salt (1) used in step 1, kneading conditions (shearing force to be applied, kneading temperature, kneading time, etc.), etc. It can be adjusted by adjusting.

As the extrusion apparatus, those generally used for the production of granular detergent compositions can be used, and examples thereof include a uniaxial or biaxial screw type extruder, a disk type extruder, and a roll type extruder. Among these, a screw type is preferable and a biaxial type is more preferable.
The conditions of the die thickness, die opening ratio, die hole diameter, die shape, etc. in the extruder are in consideration of the physical properties of the kneaded product to be processed, the shape of the extruded product (molded product), and the ease of pulverization in the next step. It is preferable to set appropriately.

45-95 degreeC is preferable and the temperature of the kneaded material supplied to an extrusion apparatus has more preferable 48-65 degreeC. When it is 45 ° C. or higher, it is easy to handle, and when it is 95 ° C. or lower, the stability of the components is good.
The temperature of the water-soluble inorganic salt (2) is not particularly limited, and may be about room temperature.
The temperature in the extrusion apparatus (extrusion temperature) is generally 20 to 80 ° C, preferably 30 to 70 ° C, more preferably 40 to 60 ° C. When the temperature is lower than 20 ° C., the load on the extruder tends to be excessive, which is not preferable. On the other hand, if the temperature is higher than 80 ° C., the kneaded material tends to adhere to the inside of the apparatus, which is not preferable.
In an extruder, when a kneaded material adheres to a screw etc. and extrusion capability falls, it is preferable to cool or heat with a jacket. In particular, when steam is introduced into the screw surface, the effect of suppressing adhesion is great.

The shape of the extrudate (molded product) is not particularly limited, and examples thereof include pellets and noodles. A pellet shape is particularly preferable.
For example, in the case of a pellet form, the diameter of the pellet is generally preferably 1 to 20 mmφ, preferably 3 to 15 mmφ, and more preferably 5 to 12 mmφ. If the diameter of the pellet is too small, it causes troubles such as deformation of a die attached to the extruder due to an increase in extrusion pressure. On the other hand, if the diameter of the pellet is too large, the load on the pulverizer increases in the next step. Further, the length of the pellet is appropriately 5 to 30 mm, preferably 5 to 15 mm in consideration of the adhesion to the pellet cutting knife and the load on the pulverizer in the next step.

<Step 3>
In step 3, the extrudate obtained in step 2 is granulated.
The granulation of the extrudate can be carried out by a known method, for example, a method of pulverization using a pulverizer.
Examples of the pulverizer include a pulverizer and granulator equipped with a rotating body and a classification screen inside, preferably an impact pulverizer such as a hammer mill, an atomizer, and a pulverizer, and a cutting / shear type such as a cutter mill and a feather mill. A pulverizer is used.
The pore size of the classification screen is generally set by the pulverizability of the material to be crushed and the desired particle size. Usually, in the production of a granular detergent, a screen having a pore size 3.0 to 30.0 times, preferably 4.0 to 25.0 times the desired average particle size can be used. For example, when particles (powder) having an average particle diameter of 500 μm are to be obtained, a screen having a pore diameter of 1.5 to 15 mm may be selected and used depending on the size of the object to be crushed. In addition, more effective pulverization can be performed by setting two or more hole diameters in one stage.
As the pulverizer, it is preferable to use a hammer mill or cutter mill type pulverizer equipped with a blade and a screen. Moreover, it is preferable to arrange a plurality of pulverizers in series and perform pulverization in multiple stages because the particle size distribution becomes sharp. In the case of multistage pulverization, it is preferable to reduce the screen diameter toward the lower stage.

The pulverization is preferably performed while blowing into the pulverizer for temperature control of the object to be pulverized. Preferably, the temperature-controlled cold air or hot air is supplied so that the temperature of the powder (granular detergent) immediately after pulverization is in the range of 30 to 40 ° C. It is preferable that the powder temperature is within the above range in that the adhesion of the apparatus can be further suppressed.
The blowing temperature is preferably 10 to 40 ° C, more preferably 10 to 20 ° C. Further, the blown amount is preferably 0.1 to ⁵ m ³ / kg (per unit mass of the pulverized product).

In pulverization, it is preferable to add a pulverization aid together with the extrudate into the pulverizer. By adding the grinding aid, the grinding aid adheres to the surface of the pulverized product (powder) and reduces the surface activity of the pulverized product, thereby preventing adhesion to the pulverizer and the accompanying pulverization power. Reduction and improvement of fluidity of the pulverized product can be achieved. In the present invention, when a grinding aid is used, the grinding aid is also one of the components constituting the granular detergent composition.
Examples of the grinding aid include stearates, aluminosilicates such as A-type zeolite, calcium carbonate, magnesium carbonate, alkaline earth metal carbonates, amorphous silica, calcium silicate, magnesium silicate and the like. Desirable are clay minerals such as silicate, talc and bentonite, silicon dioxide, titanium dioxide, finely divided sodium carbonate and sodium sulfate.
The average particle size of the grinding aid is preferably 50 μm or less, and preferably 20 μm or less.
0.5-10 mass% is suitable for the addition amount of a grinding | pulverization adjuvant with respect to the whole quantity of a to-be-ground material.
As a method for adding the grinding aid, there are a method of mixing in advance before grinding, a method of adding all of the necessary amount at the first stage of multistage grinding, and a method of adding each part separately. Any of these may be selected, but batch addition is desirable in terms of the effect of the auxiliary agent and economy. Furthermore, by using a system in which the pulverizers are directly connected and each stage is hermetically sealed (sealed direct connection type), the loss of the pulverization aid is reduced, and it can be effectively operated with a small amount of auxiliary agent added. .

The granular detergent composition produced as described above preferably has a bulk density of 600 to 990 g / L, more preferably 750 to 970 g / L, and more preferably 820 to 960 g / L in consideration of solubility, appearance, and the like. L is more preferable.
The water content of the granular detergent composition is preferably 4 to 12% by mass, more preferably 5 to 9% by mass in consideration of solubility, handling properties, stability and manufacturability.
Although the average particle diameter of a granular detergent composition is not specifically limited, When solubility, fluidity | liquidity, an external appearance, etc. are considered, 200-1500 micrometers is preferable, 250-1000 micrometers is more preferable, 300-700 micrometers is especially preferable.
The bulk density, water content, and average particle diameter of the granular detergent composition can be measured by the same measurement methods as the bulk density, water content, and average particle diameter of the spray-dried particles, respectively.
These physical properties of the granular detergent composition depend on the manufacturing conditions of the granular detergent composition, for example, the composition of the extrudate to be used in Step 3, the type and amount of the grinding aid, the structure of the grinding apparatus, and the grinding conditions (rotation speed, treatment). Volume, temperature, cold air temperature and air volume).

  The granular detergent composition obtained as described above may be used as it is as a granular detergent, or may be mixed with other components as detergent particles. The other components can be appropriately selected from those generally blended into granular detergents, such as bleaching agents, bleach activators, bleach activation catalysts, enzymes, antifoaming agents, perfumes, dyes, alkaline agents. Etc.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.
The raw materials used in the following examples and comparative examples are shown below.
(Surfactant)
MES-Na: α-sulfo fatty acid methyl ester sodium salt having an alkyl group having 14 to 18 carbon atoms (Lion Corporation, 63% pure).
LAS-Na: linear alkylbenzene sulfonic acid (Lypon LH-200, manufactured by Lion Corporation) (AV value (mg number of potassium hydroxide required to neutralize 1 g of LAS-H) = 180.0) Neutralized with 48 mass% sodium hydroxide solution in slurry for preparing spray-dried particles. ). In addition, the compounding quantity of Table 1 shows the compounding quantity (mass% with respect to the granular detergent composition whole quantity) as a pure part of LAS-Na.
LAS-K: linear alkylbenzene sulfonic acid (Lypon LH-200, manufactured by Lion Corporation) (AV value (mg number of potassium hydroxide required to neutralize 1 g of LAS-H) = 180.0) Neutralized with 48 mass% potassium hydroxide solution in slurry for preparing spray-dried particles. ). In addition, the compounding quantity of Table 1 shows the compounding quantity (mass% with respect to the granular detergent composition whole quantity) as a pure part of LAS-K.
Nonionic surfactant 1: Ethylene oxide average 15 mol adduct of alcohol having an alkyl group having 12 to 14 carbon atoms (manufactured by Lion Corporation, pure content 90%).
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12: 11.7%, C14: 0.4%, C16: 29 2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid): 1.2%, molecular weight: 289).

(Water-soluble inorganic salt (1), (2))
Sodium carbonate (a): grain ash (manufactured by Soda Ash Japan Co., Ltd., average particle size 500 μm)
-Sodium carbonate (b): The thing which grind | pulverized the grain ash (The soda ash Japan company make, average particle diameter of 500 micrometers) and made the average particle diameter of 70 micrometers.
-Sodium carbonate (c): The thing which grind | pulverized the grain ash (The soda ash Japan company make, average particle diameter of 500 micrometers) and made the average particle diameter of 160 micrometers.
-Sodium carbonate (d): The thing which grind | pulverized the grain ash (The soda ash Japan company make, average particle diameter of 500 micrometers) and was made into the average particle diameter of 5 micrometers.
Sodium carbonate (e): granular ash (manufactured by Soda Ash Japan Co., Ltd., average particle size 500 μm).
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.).
Sodium sulfate: neutral anhydrous sodium sulfate A0 (manufactured by Shikoku Kasei Co., Ltd.).
-Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).

(Water-insoluble inorganic salt)
Zeolite (A type): Shilton B (manufactured by Mizusawa Chemical Co., Ltd., 80% pure), A type slurry zeolite (manufactured by Nippon Chemical Co., Ltd.). Among these, what was mix | blended in the detergent slurry is A-type slurry zeolite, and what was used for the other processes is Shilton B.
Zeolite (P-type): DOUCIL A24 P-type zeolite (manufactured by Crossfield).
・ Calcium carbonate: Heavy calcium carbonate (manufactured by Nitto Flour Industries).

(Organic builder)
Acrylic acid / maleic acid copolymer salt: Aqualic TL-400 (weight average molecular weight by GPC method: 50000, manufactured by Nippon Shokubai Co., Ltd., pure 40 mass% aqueous solution).

(Other)
-Fluorescent agent + ultraviolet absorber: Tinopearl CBS-X (manufactured by Ciba Japan Co., Ltd.) which is a fluorescent agent and Chinosorb FD (manufactured by Ciba Japan Co., Ltd.) which is an ultraviolet absorber are used at a mass ratio of 10/1.

(Crushing aid)
・ Zeolite (A type): Shilton B (manufactured by Mizusawa Chemical Co., Ltd., pure content 80%)
・ Calcium stearate: Calcium stearate (manufactured by Kawamura Kasei Kogyo Co., Ltd.)

<Examples 1-3, Comparative Examples 1-4>
(Process 1)
Among the compositions shown in Table 1, a solid content containing components other than MES-Na, nonionic surfactant 1, water-soluble inorganic salt (2) (water-soluble inorganic salt added separately during extrusion described later) and a grinding aid. A 62% aqueous slurry was prepared at a preparation temperature of 80 ° C. and a stirring time of 17 minutes. This aqueous slurry was spray-dried to prepare spray-dried particles having a moisture content of 5.5% by mass.
A continuous kneader (Azuma Kurimoto Co., Ltd.) containing the spray-dried particles, nonionic surfactant 1 (water content 10%) and MES-Na (water content 12%) shown in Table 1 and a small amount of tap water (Edogawa-ku, Tokyo). KRC-S4 type manufactured by Kosho, and kneaded continuously at a temperature of 49-60 ° C.
(Process 2)
Next, the obtained kneaded product and the water-soluble inorganic salt (2) are continuously supplied to a pelleter (made by Fuji Powder, die hole diameter 10 mmφ) using a quantitative feeder, and extruded to form a pellet-like extrudate. Formed.
(Process 3)
Thereafter, Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKASO-6 type) was arranged in series, and the extrudate obtained above and the grinding aid shown in Table 1 were introduced together with cold air at 15 ° C. A granular detergent composition was obtained by crushing and granulating so as to have a diameter of 350 to 700 μm.
About the obtained granular cleaning composition, the water | moisture content and bulk density were measured with the following measuring method. The moisture measurement results are shown in Table 1 as “water”. The bulk density was in the range of 820 to 950 g / L.
(Method of measuring moisture)
The water content was measured using an infrared moisture meter (Kett Co., Ltd.) under the measurement conditions of a sample surface temperature of 130 ° C. for 20 minutes.
(Measurement method of bulk density)
The bulk density of the granular detergent composition was measured according to JIS K 3362-1998.

In Examples 1 to 3 and Comparative Examples 1 to 3, the average particle diameter of the water-soluble inorganic salt (2) supplied to the pelleter in Step 2 by the following measurement method, the hardness and moisture of the kneaded material, and the kneaded material The dispersed particle size of the water-soluble inorganic salt (1) therein was determined. The results are shown in Table 1.
[Average particle diameter of water-soluble inorganic salt (2)]
The average particle size of the water-soluble inorganic salt (2) is measured by a dry particle size distribution using a laser light scattering particle size distribution analyzer LDSA-1400A (manufactured by Tohnichi Computer Applications Co., Ltd.) equipped with a powder measurement unit PD-10S. And obtained from the particle size distribution.

[Moisture of kneaded material]
The water content was measured using an infrared moisture meter (Kett Co., Ltd.) under the measurement conditions of a sample surface temperature of 130 ° C. for 20 minutes.
[Measurement of hardness of kneaded material]
The hardness of the kneaded product (kneaded product) was measured with a load-type hardness meter (manufactured by Kyoden Co., Ltd.) under the temperature conditions of the obtained kneaded product.

[Measurement of dispersed particle size of water-soluble inorganic salt (1) in kneaded product]
A granular detergent composition (pulverized product) was produced in the same manner except that the water-soluble inorganic salt (2) was not blended, and 30 g of the pulverized product was dissolved in 1 L of a non-aqueous solvent (methanol) at 25 ° C. At this time, the residue that remained undissolved was collected by filtration using filter paper corresponding to three types described in JIS P 3801, and dried in vacuum. This was designated as Sample 1.
Next, 30 g of the same pulverized product was dissolved in 25 ° C. hot water. At this time, the residue that remained undissolved was collected in the same manner as described above, and was vacuum-dried. This was designated as Sample 2.
The particle size distributions of Samples 1 and 2 were measured under dry conditions using a laser light scattering particle size distribution analyzer LDSA-1400A (manufactured by Tohnichi Computer Applications Co., Ltd.). The amount obtained by subtracting the frequency of sample 2 from the frequency of sample 1 was used as the particle size distribution of the water-soluble inorganic salt (1) in the kneaded product. The average particle size obtained from the particle size distribution was taken as the dispersed particle size.

Moreover, productivity of the granular detergent composition in Examples 1 to 3 and Comparative Examples 1 to 4 was evaluated by the following evaluation methods, respectively. The results are shown in Table 1.
[Productivity evaluation method]
In step 1, the state of the kneaded material after 10 minutes from the start of kneading (kneaded state) and the degree of adhesion of the kneaded material to the continuous kneader (apparatus adhesion) were visually observed. Using these as indicators, Productivity was evaluated based on the criteria.
(Criteria)
◎ (No production problems): There is no problem in the kneading state, and no device adhesion is observed.
○ (Good production): There is no problem in the kneading state, and the device is slightly adhered.
Δ (Possible to produce): The kneaded material is hard or soft, and a little adhering to the device is recognized.
X (Unsuitable for production): The kneaded material is loose or sticky, and the device is found to be attached.

Further, the solubility of these granular detergent compositions was evaluated by the following evaluation method. The results are shown in Table 1.
[Method for evaluating solubility]
Using each granular detergent composition obtained above as a sample, the following evaluation using tap water adjusted to 5 ° C. with a two-tub washing machine CW-225 (W) type (manufactured by Mitsubishi Electric Corporation) Went.
The total mass of the cloth to be washed was three kinds of cloth for evaluation, including two acrylic shirts, two nylon slips, two cotton shirts, and five skin shirts for weight balance. Was 1.5 kg.
The washing cloth was charged into a two-tank washing machine so that all three kinds of washing cloths for evaluation could be seen when viewed from above. The cloth to be washed was soaked under conditions of 30 L of water and a bath ratio of 1:20, and washing was performed for 5 minutes with 30 g of the sample.
After washing, after the washing cloth is dehydrated for 1 minute, the degree of adhesion of the sample to the washing cloth is visually observed, and the solubility of the granular detergent composition is evaluated according to the following criteria. ◎ and ○ were taken as passing grades.
(Criteria)
◎ (No unresolved residue): No or almost no deposits are observed.
○ (very little undissolved): Very little adhering material is observed.
Δ (Some remaining undissolved): Slightly adhering matter.
X (large remaining undissolved): Many adhering substances are recognized.

As shown to the said result, in Examples 1-3, the granular detergent composition could be manufactured with the outstanding productivity, and the solubility of the obtained granular detergent composition was also high.
On the other hand, Comparative Example 1 in which the ratio (mass ratio) of the water-soluble inorganic salt (1) / water-soluble inorganic salt (2) was more than 11 had poor solubility and poor productivity. Further, Comparative Examples 2 to 3 having this ratio of less than 2 had poor solubility although productivity was relatively good. Moreover, the comparative example 4 which did not perform the process 2 was bad in both productivity and solubility.

Claims (2)

A method for producing a granular detergent composition comprising 5 to 28% by weight of a surfactant, 15 to 60% by weight of a water-soluble inorganic salt and 10 to 45% by weight of a water-insoluble inorganic salt,
Step 1 for obtaining a kneaded product of a detergent raw material containing a surfactant, a water-soluble inorganic salt and a water-insoluble inorganic salt,
Step 2 for supplying the kneaded product and water-soluble inorganic salt obtained in Step 1 to an extruder to obtain an extrudate, and Step 3 for granulating the extrudate obtained in Step 2;
Have
The ratio (mass ratio) between the water-soluble inorganic salt used in the step 1 and the water-soluble inorganic salt used in the step 2 is [water-soluble inorganic salt used in step 1] / [water-soluble inorganic salt used in step 2]. = The method of manufacturing the granular detergent composition characterized by being in the range of 2-11.   The water-soluble inorganic salt used in the step 2 has an average particle size of 50 to 300 μm, and the average particle size is 2 to 2 of the dispersed particle size of the water-soluble inorganic salt present in the kneaded product obtained in the step 1. The manufacturing method of the granular detergent composition of Claim 1 which is 30 times.