JP5560166B2 - Granular detergent composition and method for producing the same - Google Patents

Description

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

A granular detergent composition, particularly a granular detergent composition used as a detergent for clothing, is produced by spray drying from an aqueous slurry containing a surfactant, an inorganic builder and the like, and is composed of spray-dried particles having voids inside the particles. Detergents have been used.
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. For this reason, in recent years, granular detergent compositions with increased bulk density, so-called compact detergents, have become mainstream in place of the above-mentioned spray-dried particles.
Conventionally, as a method for producing a granular detergent composition having a high bulk density, a slurry containing a surfactant and an inorganic builder is prepared, and spray-dried particles obtained by spray-drying the slurry and other components are mixed. There is known a pulverization granulation method in which a kneaded product is kneaded after being kneaded with a kneader or the like (for example, Patent Document 1). The detergent composition thus obtained is solid inside the particles and has a high bulk density.

In recent years, detergents having a low surfactant concentration (less than 30% by mass) have become mainstream due to changes in washing circumstances and increased awareness of environmental burdens. In reducing the surfactant concentration, the cleaning power is maintained and improved by increasing the amount of inorganic builder or the like. As the inorganic builder, from the viewpoint of cost and detergency, alkali metal carbonates (sodium carbonate, potassium carbonate, etc.), hydrogen carbonates (sodium bicarbonate, potassium bicarbonate, etc.) and the like are preferably used.
However, when the amount of the inorganic builder is increased, there is a problem that the granular detergent composition obtained is easily solidified during storage.
In order to solve these problems, a detergent composition comprising nonionic surfactant-containing particles in which nonionic surfactant-containing particles are treated with an alkaline agent and the treated surface is treated with an anionic surfactant acid precursor has been proposed. (For example, Patent Document 2).

JP-A 64-6095 JP 2005-239786 A

However, there is a need for further weight loss of surfactants in granular detergent compositions. In the invention of Patent Document 1, when the amount of sodium carbonate or potassium carbonate is simply increased, the detergent composition is easily solidified. In addition, when sodium hydrogen carbonate or potassium hydrogen carbonate was used as the inorganic builder, solidification tended to progress over time, although solidification was not observed in the detergent composition immediately after production.
Moreover, the technique of patent document 2 has not yet been satisfactory in the effect of solidification suppression.
Then, this invention aims at the granular detergent composition which is hard to solidify even if it increases sodium hydrogencarbonate or potassium hydrogencarbonate.

The granular detergent composition of the present invention comprises (A) component: sodium hydrogen carbonate particles or potassium hydrogen carbonate particles, (B) component: surfactant-containing particles having a bulk density of 600 g / dm ³ or more, and (C) component. : It is characterized by containing coated particles coated with a binder.
In the component (A), particles having a particle size of 1000 μm or more are 5% by mass or more in the component (A), and in the component (B), particles having a particle size of 149 μm or less are 5 in the component (B). It is preferable that the average particle diameter of {(B)} / {average particle diameter of (A)} is 0.1 to 0.75, and (C) / {(A) + ( B)} is preferably 0.001 to 0.02.

  The manufacturing method of the granular detergent composition of this invention is a manufacturing method of the said granular detergent composition of this invention, Comprising: The said (C) component is added, making the said (A) component and the said (B) component flow. And the step of obtaining the coated particles.

  According to the present invention, solidification can be prevented even when the amount of sodium hydrogen carbonate or potassium hydrogen carbonate is increased.

(Granular detergent composition)
The granular detergent composition of the present invention contains coated particles.
Although the average particle diameter of a granular detergent composition is not specifically limited, It is preferable that it is 200-1500 micrometers, and it is more preferable that it is 250-1000 micrometers. If the average particle diameter is 200 μm or more, powdering during use is suppressed. On the other hand, if it is 1500 micrometers or less, the solubility to water will improve. The average particle size in this article is a value calculated from the particle size distribution by sieving according to the particle size test described in the Japanese Pharmacopoeia.

  The average particle diameter can be measured by a classification operation using a 9-stage sieve having openings of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm, and a tray. In the classification operation, a small sieve sieve is stacked on a tray in the order of a large sieve sieve, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, the lid is capped, and a low-tap sieve shaker (stock) (Made by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute) After shaking for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve, Measure the mass. Then, when the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is “a μm”, and the opening of the sieve that is one step larger than a μm is “ bμm ”, the integrated value of the mass frequency from the tray to the aμm sieve is“ c% ”, and the mass frequency on the aμm sieve is“ d% ”. %) To obtain the average particle diameter of the sample.

The granular detergent composition is a so-called high bulk density granular detergent composition, and the bulk density is preferably 500 to 1200 g / dm ³ , more preferably 600 to 1100 g / dm ³ . When the bulk density is 500 g / dm ³ or more, the space (storage location) required for storing the granular detergent composition can be reduced. On the other hand, if it is 1200 g / dm ³ or less, the solubility in water will be good.
In addition, the bulk density in this paper shows the value measured according to JISK3362-1998.

Although the moisture content of a granular detergent composition is not specifically limited, 4-10 mass% is preferable from a viewpoint of solubility and storage stability, 5-9 mass% is more preferable, and 6-8 mass% is further more preferable. In the present specification, the moisture content is a value measured at a sample surface temperature of 140 ° C. for 20 minutes using a Kett moisture meter (trade name, infrared moisture meter, manufactured by Kett Scientific Laboratory).
However, when the component (A) is contained in the granular detergent composition, it is a value obtained by subtracting carbon dioxide and moisture from which the component (A) is volatilized by thermal decomposition.
When sodium hydrogen carbonate is contained as the component (A), the bimolecular sodium hydrogen carbonate generates and vaporizes one molecule of carbon dioxide and one molecule of water by heating in the measurement of the water content (granular detergent composition). 37% by mass of the mass of sodium hydrogen carbonate contained in the product is volatilized). For example, when 10% by mass of sodium hydrogen carbonate is contained in the granular detergent composition, the content obtained by subtracting 3.7% by mass that volatilizes by decomposition from the above measured value is the moisture in the granular detergent composition. .

<Coated particles>
The coated particles of the present invention comprise (A) component: sodium hydrogen carbonate particles or potassium hydrogen carbonate particles, (B) component: surfactant-containing particles having a bulk density of 600 g / dm ³ or more, and (C) component: binder. It is covered with. That is, it is a particle having the component (A) as a core material and the components (B) and (C) as a coating material.

The coating state of the coated particles is, for example, a mixture of the component (B) and the component (C) on the surface of the component (A), a first coating layer in which the component (A) is coated with the component (B), A first coating layer formed by coating the first coating layer with the component (C), a first coating layer coated with the component (A) with the component (C), and the first coating layer. Any of those formed with a second coating layer coated with the component (B). The coated particles are preferably coated with 70% or more of the surface area by the component (B) and the component (C), more preferably 90% or more, and 100% may be coated. .
The ratio (coverage) of the coated area to the surface area of the component (A) is, for example, that the coated particle is a microscope (manufactured by Asahi Optical Co., Ltd., Handi Scope TM) or a scanning electron microscope (for example, Hitachi, Ltd.). The surface can be observed with an energy dispersive X-ray analyzer (for example, EMAX-7000, manufactured by Horiba, Ltd.) and an image processing or surface elemental analysis.

The average particle diameter of the coated particles is not particularly limited, but is, for example, 200 to 1500 μm. The average particle size of the coated particles can be determined in the same manner as the average particle size of the granular detergent composition described above.
The bulk density of the coated particles can be determined according to the bulk density required for the granular detergent composition, and is preferably in the range of 500 to 1200 g / dm ³ , for example.

≪ (A) component≫
The component (A) is sodium hydrogen carbonate particles or potassium hydrogen carbonate particles. Among them, sodium hydrogen carbonate particles are inexpensive and excellent in solubility, but tend to promote solidification of the granular detergent composition over time. Therefore, the effect of the present invention is remarkable in the granular detergent composition in which the component (A) is sodium hydrogen carbonate particles.

  (A) The effect of this invention is so high that the purity of sodium hydrogencarbonate or potassium hydrogencarbonate is high, for example, the purity of 98 mass% or more is preferable, and the purity of 100 mass% is more preferable.

Although the particle diameter of (A) component is not specifically limited, For example, 10-1000 micrometers of average particle diameters are preferable, and 50-500 micrometers is more preferable. If it is 10 micrometers or more, while the powdering in the manufacturing process of a granular detergent composition will be suppressed, granulation of the granulation process mentioned later is easy. If it is 1000 micrometers or less, the solubility to water will be favorable at the time of use. In addition, the average particle diameter of (A) component can be measured by the method similar to the average particle diameter of a granular detergent composition.
The particle size distribution of the component (A) is not particularly limited, but preferably contains particles having a particle size of 1000 μm or more. By including such particles, it becomes easy to produce coated particles.
Furthermore, as for (A) component, it is preferable that 5 mass% or more of particles with a particle diameter of 1000 micrometers or more are contained in (A) component, and it is more preferable that 10 mass% or more is contained. By containing 5% by mass or more of particles having a particle size of 1000 μm or more, it is easy to produce coated particles.
In addition, the particle diameter of (A) component can be adjusted by sieving.

  Although the compounding quantity of (A) component in a granular detergent composition is not specifically limited, 1-40 mass% is preferable, 5-30 mass% is more preferable, 10-30 mass% is further more preferable. If it is 1 mass% or more, the function as an inorganic builder is fully exhibited, and if it is 40 mass% or less, the detergency is hardly reduced. In addition, the granular detergent composition tends to solidify as the blending amount of the component (A) increases. For this reason, the effect of this invention is remarkable in the granular detergent composition with many compounding quantities of (A) component.

≪ (B) component≫
The component (B) is a surfactant-containing particle, and the surfactant-containing particle is a granular material containing a surfactant. By blending the component (B), it is possible to improve the cleaning effect of the granular detergent composition.

(B) the bulk density of the component is 600 g / dm ³ or more, preferably 600~1200g / dm ^3, more preferably from 700~1200g / dm ^3, more preferably from 800~1200g / dm ^3. By setting the bulk density to 600 g / dm ³ or more, the granular detergent composition can be made to have a ^high bulk density, and the space required for storage (storage location) can be reduced. On the other hand, if it is 1200 g / dm ³ or less, the solubility in water will be good.

The average particle size of the component (B) is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and particularly preferably 300 to 700 μm. This is because when the average particle size is in the above range, the solubility is excellent. In addition, the average particle diameter of (B) component can be measured by the method similar to the average particle diameter of a granular detergent composition.
In addition, the particle size distribution of the component (B) is not particularly limited, but preferably includes particles having a particle size of 149 μm or less. By including such particles, it becomes easy to produce coated particles.
Furthermore, 5 mass% or more is preferable and, as for content in (B) component of particle diameter 149 micrometers or less, 10 mass% or more is more preferable. By containing 5% by mass or more of particles having a particle size of 149 μm or less, it is easy to produce coated particles.
The particle size of the component (B) can be adjusted by sieving.

  The water content of the component (B) is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and further preferably 5.5 to 8.5% by mass from the viewpoint of achieving both solubility and storage stability. preferable.

  60 mass% or more is preferable, as for the compounding quantity of (B) component in a granular detergent composition, 70 mass% or more is more preferable, and 80 mass% or more is further more preferable. This is because if it is less than 60% by mass, the cleaning effect may not be improved.

  As the surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant may be blended, and one or two or more of them may be used in combination. When (B) component contains the following surfactant, 10-30 mass% is preferable and, as for the total amount of surfactant in (B) component, 15-30 mass% is more preferable.

[Anionic surfactant]
The following are mentioned as an anionic surfactant mix | blended with (B) component.
(1) Methyl, ethyl or propyl ester salt (α-sulfo fatty acid alkyl ester salt) of a saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms.
(2) Alkali metal salts or alkaline earth metal salts (soaps) of higher fatty acids having a fatty acid average carbon number of 10 to 20.
(3) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(4) Alkane sulfonate having 10 to 20 carbon atoms.
(5) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(6) C10-20 alkyl sulfate or alkenyl sulfate (AS).
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(9) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(10) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(11) Long chain monoalkyl, dialkyl or sesquialkyl phosphate.
(12) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate. These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants can be used alone or in combination of two or more.

  When an anionic surfactant is used as the surfactant, the blending amount of the anionic surfactant in the component (B) is preferably 10 to 25% by mass, more preferably 12 to 22% by mass, and further 14 to 20% by mass. preferable. If it is less than 10% by mass, the detergency may be deteriorated, and the adhesive force to the component (A) is weakened and the coating tends to be fragile. If it exceeds 25% by mass, the coated particles tend to adhere to each other and tend to solidify.

[Nonionic surfactant]
The following are mentioned as nonionic surfactant mix | blended with (B) component.
(1) An average of 3 to 30 mol, preferably 5 to 20 mol, more preferably 10 to 18 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. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Fatty acid alkyl ester alkoxylates represented by, for example, the following general formula (I) in which an alkylene oxide is added between the ester bonds of a long-chain fatty acid alkyl ester.

R ¹ CO (OA) _m OR ² (I)

[In Formula (I), R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 represents an alkylene oxide addition unit, and m represents the average number of added moles of alkylene oxide, generally 3 to 30, preferably 5 to 20. R ² represents an optionally substituted lower (1-4 carbon atoms) alkyl group which may have a substituent having 1 to 3 carbon atoms. ]

(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.

[Cationic surfactant]
(B) As a cationic surfactant mix | blended with a component, the following can be mentioned, for example.
(1) Dilong chain alkyl dishort chain alkyl type quaternary ammonium salt.
(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.
However, the above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms. The “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyoxy having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms An alkylene group is mentioned as a suitable thing.

[Amphoteric surfactant]
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.

  Among the above surfactants, an anionic surfactant is preferably used, and an α-sulfo fatty acid alkyl ester salt is more preferable. The α-sulfo fatty acid alkyl ester salt is excellent in the coverage of the component (A) and can further suppress the solidification of the component (B) itself.

[Optional component in component (B)]
In the component (B), a detergency builder, a fluorescent brightening agent, polymers, an enzyme stabilizer, an anti-caking agent, a reducing agent, a metal ion scavenger, a pH adjuster and the like can be blended as necessary.

Examples of the detergency builder include inorganic builder and organic builder other than the component (A).
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite; crystalline layered sodium silicate (for example, trade name “Na-SKS manufactured by Clariant Japan Ltd.) -6 "(crystalline alkali metal silicates such as δ-Na ₂ O · 2SiO ₂ ), amorphous alkali metal silicates; sulfates such as sodium sulfate and potassium sulfate; alkali metals such as sodium chloride and potassium chloride Chloride: orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, etc .; crystalline aluminosilicate, amorphous aluminosilicate, sodium carbonate and amorphous Alkali metal silicate composites (for example, NABION15 (trade name) manufactured by Rhodia) It is. Among these, alkali metal carbonates and sulfates are preferable, sodium carbonate and sodium sulfate are more preferable, and it is more preferable to use sodium carbonate and sodium sulfate in combination. By using sodium carbonate and sodium sulfate in combination, the strength of the component (B) can be improved, and the fluidity of the component (B) can be increased.
When sodium carbonate and sodium sulfate are used in combination, the mass ratio represented by sodium carbonate / sodium sulfate in component (B) is preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 to 10. If the mass ratio of sodium carbonate / sodium sulfate is less than 1, the detergency of the component (B) tends to decrease, and if it exceeds 10, the strength of the component (B) becomes insufficient, ) The fluidity of the component is reduced, and the production efficiency of the coated particles may be reduced.

  Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyimino Hydroxyaminocarboxylates such as disuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, Cyclocarboxylates such as benzopolycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; Acrylate, salt of acrylic acid-allyl alcohol copolymer, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid 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 above detergency builders, the detergency and stain dispersibility in the washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid It is preferable to use an organic builder such as a polymer salt or a polyacetal carboxylic acid salt in combination with an inorganic builder such as zeolite.

The blending amount of the detergency builder in the component (B) can be determined in consideration of the type and blending amount of the surfactant, the detergency of the detergency builder, and the like, preferably 10 to 80% by mass, and 20 to 75% by mass. More preferred.
In addition, when blending an inorganic builder as a detergency builder, the blending amount of the inorganic builder in the component (B) is preferably 30 to 50% by mass, and more preferably 35 to 45% by mass.

≪ (C) component≫
Component (C) is a binder. The binder can be determined in consideration of the type of component (A) and component (B), production conditions, and the like. For example, an anionic surfactant or an acid precursor thereof, a nonionic surfactant, a water-soluble polymer, or these An aqueous solution etc. are mentioned, Among these, a nonionic surfactant or its aqueous solution is preferable.

  Examples of the anionic surfactant used for the component (C) or an acid precursor thereof include linear alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms and higher fatty acid having an alkyl group having 8 to 20 carbon atoms. A linear or branched alkyl having 10 to 20 carbon atoms (or an average of 0.5 to 10 moles of one or more selected from a salt, ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO) (or And alkyl (or alkenyl) ether sulfate having an alkenyl) group.

  Examples of the nonionic surfactant used as the component (C) include polyoxyalkylene alkyl (or alkenyl) ether, polyoxyalkylene alkyl (or alkenyl) phenyl ether, and fatty acid methyl ester alkoxy obtained by adding EO or PO to fatty acid methyl ester. Rate and the like.

As the polyoxyalkylene alkyl (or alkenyl) ether used as the component (C), one obtained by adding one or more selected from EO, PO and BO to a saturated or unsaturated alcohol having 8 to 40 carbon atoms is preferable. Of these, EO or PO added alone or in combination is more preferable. In addition, the average added mole number of alkylene oxide is preferably 3 to 35 mol, and more preferably 5 to 30 mol.
The polyoxyalkylene alkyl (or alkenyl) phenyl ether is preferably an alkylphenol having 8 to 12 carbon atoms or an alkenylphenol to which one or more selected from EO, PO and BO are added. Those added by mixing are more preferred. In addition, the average added mole number of alkylene oxide is preferably 5 to 25 mol, more preferably 8 to 20 mol.
As fatty acid methyl ester alkoxylate having EO or PO added to fatty acid methyl ester, EO or PO is added to saturated or unsaturated fatty acid methyl ester having an average carbon number of 8 to 40 alone or as a mixture thereof. preferable. In addition, the average added mole number of alkylene oxide is preferably 5 to 30 moles.

The nonionic surfactant used as component (C) is preferably HLB 10-16, more preferably HLB 12-16, and particularly preferably HLB 15. If the HLB is less than 10, the bonding strength is lowered and the coating may be insufficient. If the HLB exceeds 16, the crystal structure of the component (A) tends to be broken, and the components (A) may be united.
Here, “HLB” refers to the relative strength between hydrophilicity and lipophilicity of the surfactant molecule, and represents the hydrophilic / lipophilic balance in a quantitative manner, which is determined by the Griffin method. This is the required value (see Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho, 1991, page 234).

  Examples of the water-soluble polymer used as the component (C) include polyethylene glycol (weight average molecular weight 200 to 20000), polyethylene glycol fatty acid ester (fatty acid group having 8 to 22 carbon atoms, degree of polymerization of ethylene glycol (average addition of EO). Number of moles) 5 to 25), decaglycerin fatty acid ester (fatty acid group having 8 to 22 carbon atoms), sorbitan fatty acid ester (fatty acid residue having 8 to 22 carbon atoms), acrylic acid maleic acid copolymer (weight average molecular weight 1000) ˜100,000) and the like.

  The blending amount of the component (C) in the granular detergent composition can be determined in consideration of the types and blending ratios of the component (A) and the component (B), and for example, 0.1 to 10% by mass is preferable. 2-5 mass% is more preferable, and 0.3-3 mass% is further more preferable. If it is less than 0.1% by mass, the coating tends to be insufficient, and if it exceeds 10% by mass, there is a possibility that a lumpy material is generated and adhered in the coating apparatus.

  The particle diameter ratio represented by {(B) average particle diameter} / {(A) average particle diameter} in the coated particles is preferably 0.1 to 0.75, more preferably 0.1 to 0.50. preferable. If it is less than 0.1, the coverage may be insufficient. If it exceeds 0.75, the component (B) is a core material, and the component (A) and the component (C) are coated. May be formed.

  The mass ratio represented by (C) / {(A) + (B)} in the coated particles can be determined in consideration of the type of the component (C), for example, 0.001 to 0.02 is preferable. 0.003-0.01 is more preferable and 0.003-0.0075 is still more preferable. If it is less than 0.001, the binding force of the component (C) is not sufficiently exhibited, and the coating may be insufficient. If it exceeds 0.02, the coated particles tend to adhere to each other and tend to solidify.

  The mass ratio represented by (B) / (A) in the coated particles can be determined in consideration of the average particle diameter of the component (A) and the component (B), and is preferably 1 or more, and more preferably 2 or more. Preferably, 5 or more is more preferable. If (B) / (A) is less than 1, the coverage may be insufficient. On the other hand, (B) / (A) is preferably 20 or less, and more preferably 10 or less. When (B) / (A) exceeds 20, the blending amount of the component (A) becomes insufficient.

<Optional components in granular detergent composition>
In addition to the above-mentioned coated particles, the granular detergent composition of the present invention may contain a bleaching agent, a bleaching activator, a bleaching activation catalyst, an enzyme, an antifoaming agent, a fragrance, a pigment, and the like as necessary. .

(Production method)
The method for producing a granular detergent composition of the present invention includes a step of obtaining coated particles. For example, the first step of obtaining the component (B), the obtained component (B) and the component (A) And (3) a component having a second step of obtaining coated particles and a third step of regulating the size of the coated particles.

<First step>
The first step is a step of obtaining the component (B), and a conventionally known method can be used. For example, it is possible to prepare a spray-drying slurry by dispersing and dissolving a surfactant or an optional component in water (slurry preparation operation), and drying the spray-drying slurry with a spray dryer to obtain spray-dried particles. (Spraying operation). Furthermore, (B) component can be obtained by granulating the spray-dried particles obtained by the spraying operation together with the surfactant and optional components (granulating operation). If necessary, the obtained component (B) may be sieved and adjusted to the desired average particle size and particle size distribution (first sieving operation).

In the spraying operation, a high temperature gas is supplied into the spray drying tower at the time of spray drying of the slurry for spray drying. 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. The temperature of the high-temperature gas is preferably 170 to 300 ° C, and more preferably 200 to 280 ° C. If it is this range, the slurry for spray-drying can fully be dried, and the spray-drying particle | grains of the desired water content can be obtained easily.
Moreover, it is preferable that the temperature of the gas discharged | emitted from a spray-drying tower is 70-125 degreeC normally, and it is more preferable that it is 70-115 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, etc.) are introduced from the lower part of the spray drying tower and brought into contact with the spray drying particles, thereby preventing the spray drying particles from adhering to the inner walls of the spray drying tower. The fluidity of spray-dried particles can be improved. The spray drying tower may be a countercurrent type or a cocurrent type, and among them, the countercurrent 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 them, it is preferable to use a pressure spray nozzle that can easily obtain a desired average particle diameter. Here, the “pressure spray nozzle” includes all nozzles used when spraying and atomizing the slurry for spray-drying from the spray port of the nozzle by applying pressure. Among these, a nozzle having a structure in which the slurry for spray drying is guided from one or a plurality of inlets of the nozzle to the spiral chamber in the nozzle and sprayed from the spray port as a swirling flow in the spiral chamber is particularly preferable. As a pressure at the time of spraying, 2-4 MPa (gauge pressure) is preferable, More preferably, it is 2.5-3 MPa (gauge pressure).

For the granulation operation, a conventionally known method can be used. For example, pulverization granulation for kneading and pulverizing spray-dried particles and other optional components, stirring granulation, rolling granulation, fluidized bed granulation Etc.
In the first sieving operation, for example, a plurality of types of sieves are prepared and stacked in the order of a sieve having a small mesh size and a sieve having a large mesh size to form a sieve unit. And shake the sieve unit. The component (B) remaining on the sieve is recovered for each sieve, and the recovered component (B) can be mixed to obtain the component (B) having a desired average particle size or particle size distribution.

<Second step>
The second step is a step of coating the component (A) with the component (B) and the component (C), and a conventionally known method can be used. For example, the component (C) is added while the component (A) and the component (B) are fluidized in a stirring granulator, a tumbling granulator, and a fluidized bed granulator, and the coated particles are further dispersed by flowing. What is obtained (coating operation) is mentioned. Prior to the second step, the average particle size and particle size distribution of the component (A) can be adjusted in advance (second sieving operation). The second sieving operation is the same as the first sieving operation.

  For the coating operation, for example, using a container rotating cylindrical mixer equipped with a stirring blade in a bottomed cylindrical container, the component (C) is added while the component (A) and the component (B) are fluidized. The method of doing is mentioned. In the coating operation using the container rotating cylindrical mixer, the fluid number (Fr) represented by the following formula (2) is preferably set to 0.01 to 0.8. By setting Fr within the above range, the component (A) can be satisfactorily covered with the component (B) and the component (C).

Fr = V ² / (R × g) (2)
[However, in the formula (2), V represents the peripheral speed (m / s) of the outermost periphery of the stirring blade of the container-rotating cylindrical mixer. R represents a radius (m) from the outermost rotation center in the container rotating cylindrical mixer. g represents a gravitational acceleration (m / s ² ). ]

The addition method of (C) component can be determined according to the kind etc. of (C) component, for example, the addition method by dripping or spraying is mentioned. (C) When spraying a component, it is preferable that the droplet diameter shall be 100-200 micrometers.
In order to add the component (C) by spraying, it is preferable to adjust the viscosity so that it can be atomized by heating or an aqueous solution. When the component (C) is heated, the component (C) is preferably room temperature (20 ° C.) to 95 ° C., more preferably 70 to 85 ° C. If the temperature is lower than room temperature, the component (C) is not sufficiently refined, and if it exceeds 95 ° C., the viscosity may decrease too much and the spray pressure may increase.
Moreover, when adding (C) component as aqueous solution, Preferably content of (C) component in this aqueous solution is 70 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 85 mass% or more. To do. If the content of the component (C) in the aqueous solution is small, the amount of the aqueous solution to be added will be increased. With this increase, the amount of moisture adhering to the granulated product will increase, and the solidification preventing effect of the granular detergent composition will be impaired. There is a risk of being.

<Third step>
The third step is a step of adjusting the particle size of the coated particles obtained in the second step to a desired average particle size and particle size distribution. In the third step, for example, the coated particles obtained in the second step are dried as necessary to obtain an arbitrary amount of water (drying operation), and the dried coated particles are sieved (third sieving operation) ).
The drying operation is not particularly limited, and for example, the coated particles can be dried using a fluidized bed dryer. The third sieving operation is the same as the first sieving operation.
The coated particles thus obtained may be used directly as a granular detergent composition, or may be further mixed with other optional components to form a granular detergent composition.

As for (A) component, it is known that the trace amount anhydrous carbonate (sodium carbonate, potassium carbonate) which exists on the surface will form double salt with (A) component. When this double salt is formed, the granular detergent composition is solidified due to cross-linking between particles. In addition, in a hot and humid environment, sodium sesquiate or sodium carbonate is produced from sodium hydrogen carbonate, and potassium carbonate is produced from potassium hydrogen carbonate. This sodium sesquiate, sodium carbonate or potassium carbonate tends to cause interparticle cross-linking, and when these substances occur, the granular detergent composition tends to solidify during storage.
According to the present invention, by covering the component (A) with the component (B) and the component (C), the exposed area of the component (A) is reduced to suppress the formation of the double salt, and (A ) The formation of sodium sesquiate, sodium carbonate or potassium carbonate from the component can be suppressed. In addition, since the bulk density of the component (B) is 600 g / dm ³ or more, the component (B) coated with the component (A) can be prevented from being disintegrated in a hot and humid environment or by transportation. ) The effect of the component coating can be maintained. As a result, solidification suppression of the granular detergent composition can be achieved.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Unless otherwise specified, the compounding amounts of the components used in each example are pure conversion values.

(Raw material)
The raw materials used in each example and each comparative example are shown below.
<(A) component)>
A-1 to A-5: Sodium hydrogen carbonate particles (produced in Production Example 1 described later)

<(B) component)>
Α-sulfo fatty acid alkyl ester salt (MES): MES mixed concentrate (produced in Production Example 2 described later)
-Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure; 67% by mass, titer; 40 to 45 ° C., fatty acid composition; C12 = 11.7% by mass, C14 = 0.4% by mass, C16 = 29.2 mass%, C18F0 (stearic acid) = 0.7 mass%, C18F1 (oleic acid) = 56.8 mass%, C18F2 (linoleic acid) = 1.2 mass%, molecular weight; 289)
Sodium carbonate: granular ash, average particle size 320 μm, bulk density 1.07 g / cm ³ , manufactured by Asahi Glass Co., Ltd. Sodium sulfate: neutral anhydrous sodium sulfate A0, manufactured by Shikoku Kasei Co., Ltd. Zeolite: A-type zeolite, product name; Shilton B, 80% by mass pure, manufactured by Mizusawa Chemical Co., Ltd. Potassium carbonate: potassium carbonate (powder), average particle size 490 μm, bulk density 1.30 g / cm ³ , manufactured by Asahi Glass Co., Ltd. Na hydroxide: flaky caustic soda , Manufactured by Tsurumi Soda Co., Ltd. ・ LAS salt: LAS-H (linear alkyl (carbon number: 10-14) benzenesulfonic acid (manufactured by Lion Corporation, product name: Lipon LH-200 (pure content: 96 mass%)), Neutralized with a 48% strength by weight aqueous potassium hydroxide solution (the amount in the table indicates the weight% as LAS-K (potassium))
MA agent: acrylic acid / maleic anhydride copolymer sodium salt, trade name: AQUALIC TL-400, pure 40% by weight aqueous solution, manufactured by Nippon Shokubai Co., Ltd.

<(C) component>
-AE-5 (ECOROL26 (product name, manufactured by ECOGREEN, an alcohol having an alkyl group having 12 to 16 carbon atoms) ethylene oxide average 5 mol adduct), 100% pure, HLB: 11, manufactured by Lion Corporation AE-9 (ECOROL 26 (product name, manufactured by ECOGRENE, alcohol having an alkyl group having 12 to 16 carbon atoms), an average of 9 mol of ethylene oxide), 100% pure, HLB: 13, manufactured by Lion Corporation -15 (ECOROL 26 (product name, manufactured by ECOGREEN, alcohol having an alkyl group having 12 to 16 carbon atoms) ethylene oxide average 15 mol adduct), 100% pure, HLB: 15, manufactured by Lion Corporation ・ AE- 25 (ECOROL 26 (product name, manufactured by ECOGREEN, an alcohol having an alkyl group having 12 to 16 carbon atoms) (L)) Ethylene oxide average 25 mol adduct), 100% pure, HLB: 17, manufactured by Lion Co., Ltd. AE-15W (ECOROL26 (product name, manufactured by ECOGREEN, alcohol having an alkyl group having 12 to 16 carbon atoms) ) Ethylene oxide average 15 mol adduct), pure content 90%, HLB: 15, moisture 10%, manufactured by Lion Corporation

(Production Example 1) Adjusting the particle size of sodium hydrogen carbonate 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 149 μm were stacked in the order of a sieve having a small opening to a sieve having a large opening to obtain a sieve unit. With this sieve unit, Ecoblast EB-20 (average particle size 1 mm product, manufactured by Asahi Glass Co., Ltd.) and Ecoblast EB-60 (average particle size 0.3 mm product, manufactured by Asahi Glass Co., Ltd.) are each sieved, An operation of collecting the sample remaining on the saucer for each sieve was performed, and a predetermined average particle diameter and a particle size of 1000 μm or more were adjusted to a predetermined ratio to obtain A-1 to A-5. Table 1 shows the particle diameters of A-1 to A-5.

(Production Example 2) Production of MES mixed concentrate <Sulfonation step>
First, methyl palmitate (trade name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (trade name: Pastel M-180, manufactured by Lion Corporation) were methyl palmitate: methyl stearate = 80: It mixed so that it might become 20 (mass ratio), and also the hydrogenation process by the conventional method reduced the iodine number to 0.2, refine | purified, and purified fatty acid methyl ester was obtained. This purified fatty acid methyl ester was subjected to a reaction molar ratio (SO ₃ / saturated fatty acid ester) = 1.18 with a SO ₃ gas diluted to 7% by mass with dehumidified air using a falling-type thin film reactor, and a reaction temperature of 80 ° C. The sulfonation product was obtained by sulfonation under the following conditions.

<Aging process>
The resulting sulfonated product was then introduced into a loop ripening tube with a double tube jacket having an average residence time of 20 minutes. Three loop type ripening tubes were connected in succession, and the average residence time was 60 minutes. In order to maintain sufficient agitation and constant temperature, the sulfonation product is allowed to flow through a loop-type aging tube at a linear speed of 0.16 m / s, and the aging reaction is controlled at 78 to 82 ° C. to complete the sulfonation. As a result, α-sulfo fatty acid methyl ester was obtained.

<Esterification and bleaching process>
After introducing 20 parts by mass of methanol (industrial grade, moisture of 500 mass ppm or less, manufactured by Sumitomo Chemical Co., Ltd.) with respect to 100 parts by mass of the obtained α-sulfo fatty acid methyl ester, this mixture and 35% by mass hydrogen peroxide 5.7 parts by mass (35% industrial hydrogen peroxide, industrial grade, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was introduced into a continuous loop reactor equipped with a mixing mixer and a heat exchanger, and bleached. A sulfo fatty acid methyl ester bleached product was obtained.

<Neutralization process>
48 mass% NaOH aqueous solution (manufactured caustic soda, industrial grade, manufactured by Daiso Co., Ltd.) 28 mass parts, nonionic surfactant (AE-15) 25 with respect to 125 mass parts of the obtained α-sulfo fatty acid methyl ester bleached product Mass parts, 69 parts by mass of water and 24 parts by mass of methanol were continuously supplied to obtain a neutralized product.

<Concentration process>
Using the above neutralized product as a raw material surfactant aqueous solution, recycling flash evaporation described in JP-A-2004-210807 is performed, lower alcohol is removed and concentrated, and MES mixed concentrate (MES 63 mass%, nonion) Surfactant (AE-15) 16 mass% water-containing slurry) was obtained.

Production Example 3 Production of Component (B) According to the composition shown in Table 2, spray-dried particles K-1 to K-4 were obtained by the following production method.
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 75 ° C. LAS salt and soap were added to this, and after stirring for 10 minutes, MA agent was added. After further stirring for 10 minutes, A-type zeolite, sodium carbonate, potassium carbonate, and sodium sulfate were added. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a solid content of 60% by mass (slurry preparation operation).

The slurry for spray-drying was spray-dried under the following conditions using a counter-current spray-drying tower (moisture content of 40% by mass was dried to 5% by mass). Further, a predetermined amount of A-type zeolite (for coating) was introduced as a spray-dried particle coat coating agent from the lower part of the spray-drying tower to obtain spray-dried particles (spraying operation). Table 2 shows the properties of the obtained spray-dried particles.
[Spraying conditions]
・ Spray dryer: counter-current type, tower diameter 2.0m, effective length 5.0m
・ Atomization method: Pressurized nozzle method ・ Spraying pressure: 30 kg / cm ²
・ Hot air inlet temperature: 250 ℃
-Hot air outlet temperature: 100 ° C

In accordance with the composition of Table 3, MES mixed concentrate, spray-dried particles, LAS-K, nonionic surfactant (AE-15W) and water were put into a continuous kneader (KRC-S4 type, manufactured by Kurimoto Steel Corporation). And kneading (kneader rotational speed 135 rpm, jacket temperature: jacket inlet 5 ° C., outlet 25 ° C. (cooled by passing water through the jacket)) to obtain a dough-like product. The temperature of the resulting dough was 55 ± 15 ° C.
The obtained dough-like material was put into a pelleter double (product name: EXD-100 type, manufactured by Fuji Powder Co., Ltd.), extruded from a die having a hole diameter of 10 mm and a thickness of 10 mm, and cut at the same time, to form a pellet-shaped product (To be ground) (diameter of about 10 mm, length of 70 mm or less (substantially 5 mm or more)) was obtained (the cutter peripheral speed of the pelleter (cutter) was 5 m / s).

Next, 6.4 parts by mass of zeolite as a grinding aid was added to 93.6 parts by mass of the pellet-shaped molded body, and Fitzmill (DKA-6 type, Hosokawa Micron Co., Ltd.) arranged in three stages in the presence of air blowing. And surfactant-containing particles B-1 to B-8 were obtained by pulverization under the following pulverization conditions. The temperature of the surfactant-containing particles was 30 ± 10 ° C. (granulation operation).
[Crushing conditions]
・ Blower temperature: 15 ± 3 ℃
・ Blowing rate (gas / solid ratio): 2.8 ± 0.25 m ³ / kg
・ Screen diameter: 6mm, 4mm, 2mm from 3 steps
・ Crusher rotation speed: 100% = 4700 rpm (circumferential speed about 60 m / s)
・ Processing speed: 230kg / hr

The following operations were performed on the obtained surfactant-containing particles.
A sieve unit was prepared by stacking 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm in the order of a sieve having a small opening to a sieve having a large opening. Surfactant-containing particles are sieved by this sieving unit, and the operation of collecting the samples remaining on the respective sieving plates and trays for each sieving is performed. A predetermined average particle diameter and particles having a size of 149 μm or less have a predetermined mass. It adjusted so that it might become a ratio (1st sieving operation).

(Examples 1 to 21, Comparative Example 1)
According to the composition of Tables 4-6, the granular detergent composition was obtained with the following method. A container rotating cylindrical mixer was used for the production of the granular detergent composition. This container rotating cylindrical mixer has a diameter of 0.7 m, a length of 1.4 m, an inclination angle of 3.0 °, an outlet weir height of 0.15 m, an internal mixing blade of height 0.1 m, and a length. It has a specification in which four 1.4 m flat blades are attached every 90 °. Moreover, the rotation speed of the internal mixing blade was adjusted so that the Froude number was Fr = 0.2.

  Component (A), Component (B), and A-type zeolite for coating (Silton B, pure 80% by mass, manufactured by Mizusawa Chemical Co., Ltd.) are charged into the container-rotating cylindrical mixer having the above specifications at a rate of 15 kg / min. did. The component (C) previously adjusted to 75 ° C. was sprayed on the particle group fluidized by rotating the container. The component (C) was sprayed using an empty conical nozzle (K008, manufactured by Ikeuchi Co., Ltd.) at a spraying pressure of 0.30 to 0.50 MPa and a predetermined flow rate and droplet diameter (150 μm). The spraying of component (C) was performed within a range of 2/3 from the upper end in the region where the particle group spread along the rotation direction. When spraying the component (C), the average temperature of the particle group was set to 35 ° C. Thus, coated particles obtained by coating the component (A) with the components (B) and (C) were obtained, and the obtained coated particles were used as a granular detergent composition. About the obtained granular detergent composition, solidification property and coverage are evaluated, and the results are shown in Table 6.

(Comparative Example 2)
A granular detergent composition was obtained in the same manner as in Example 1 except that the component (B) was spray-dried particles K-4 obtained by the spraying operation of Production Example 3. About the obtained granular detergent composition, solidification property and coverage are evaluated, and the results are shown in Table 6.

(Comparative Example 3)
A granular detergent composition was obtained in the same manner as in Example except that B-1 was changed to B-8. About the obtained granular detergent composition, solidification property and coverage are evaluated, and the results are shown in Table 6.

(Comparative Example 4)
(C) A granular detergent composition was obtained in the same manner as in Example except that the component was not blended. In this granular detergent composition, the component (A) and the component (B) are present independently. About the obtained granular detergent composition, solidification property and coverage are evaluated, and the results are shown in Table 6.

(Evaluation method)
<Evaluation of solidification>
Using paper consisting of three layers of coated cardboard (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ) from the outside, A box having a length of 15 cm, a width of 9.3 cm, and a height of 18.5 cm was produced. The granular detergent composition 1.1kg of each example was put into this box, and operation which increases the contact point of particle | grains by dropping 10 times from the height of 10 cm was performed. Then, the box containing the granular detergent composition was stored for 14 days in a constant temperature and humidity chamber of 45 ° C., 85% RH for 8 hours and 25 ° C., 65% RH for 16 hours. After leaving the box taken out of the thermostatic chamber at 20 ° C. and 60% RH for 6 hours, the granular detergent composition in the box was gently transferred onto a sieve having an opening of 5 mm. After gently shaking the sieve left and right 10 times, the residue on the sieve and the mass passed through the sieve were determined, and the solidification rate was calculated from the following formula (3). The obtained solidification rate was classified into the following criteria, and the solidification property was evaluated.

Solidification ratio (%) = (weight of granular detergent compositions on the sieve) ÷ {(mass of the granular detergent composition which has passed through the sieve) + (mass of the granular detergent composition on sieve)} × 100 · · · ( 3)

◎: Less than 6% ○: 6% or more and less than 11% △: 11% or more and less than 20% ×: 20% or more

<Coverage>
Each example using an energy dispersive X-ray analyzer (EDS, HORIBA EMAX-7000, manufactured by Horiba, Ltd.), which is an accessory function of a scanning electron microscope (SEM, HITACHI S-2380N, manufactured by Hitachi, Ltd.) Elemental analysis of the particle surfaces of the coated (A) component particles and (B) component particles in the granular detergent composition was performed, and the coverage was calculated by the following equation (4).
For the detection intensity of S (sulfur) and Na (sodium) in the granular detergent composition of each example, an average value of measured values of arbitrary five particles was used.
In addition, S of a detection element is S in S containing compounds, such as (alpha) -sulfo fatty-acid alkylester salt (MES) which is surfactant in (B) component, Na is (A) component and ( B) Na of sodium carbonate or sodium sulfate contained in the component is a detection target.
For example, since the component (A) before coating does not contain S, the S / Na detection intensity ratio of the component (A) before coating is 0.
The surface of the component (A) approaches the S / Na detection intensity ratio of the component (B) as the coverage of the component (B) increases. For this reason, the S / Na detection intensity ratio of the granular detergent composition is the S / Na detection intensity ratio of the component (A), and the coverage is defined as 100%.

  Coverage (%) = [{S / Na detected intensity ratio of granular detergent composition} / {(S) Na / S detected intensity ratio of component (B)}] × 100 (4)

≪EDS measurement conditions≫
・ Acceleration voltage: 20KV
Probe current: 0.2nA
・ Working distance: 25mm
-Detection element: S and Na detection intensity

As shown in Tables 4 to 6, all of Examples 1 to 21 to which the present invention was applied had a coverage of 26% or more and good solidification properties.
On the other hand, Comparative Example 1 having a coverage of 23% has a solidification evaluation of “x”, and is Comparative Example 2 in which spray-dried particles having a bulk density of less than 600 g / dm ³ are blended in place of the component (B). The solidification property was “x”. Further, Comparative Example 3 in which the core material is the component (B) and the film is the component (A) and the component (C), and the component (A) and the component (B) are simply mixed without containing the component (C). In Comparative Example 4, which is a product, the solidification property was “x”.

Claims (4)

(A) Component: Sodium bicarbonate particles or potassium bicarbonate particles coated with (B) component: surfactant-containing particles having a bulk density of 600 g / dm ³ or more and (C) component: binder A granular detergent composition comprising 1 to 40% by mass of the component (A) in the granular detergent composition.   In the component (A), particles having a particle size of 1000 μm or more are 5% by mass or more in the component (A), and in the component (B), particles having a particle size of 149 μm or less are 5 in the component (B). The granular detergent according to claim 1, wherein the granular detergent has a mass% or more and {average particle diameter of (B)} / {average particle diameter of (A)} is 0.1 to 0.75. Composition.   The granular detergent composition according to claim 1 or 2, wherein a mass ratio represented by (C) / {(A) + (B)} is 0.001 to 0.02. It is a manufacturing method of the granular detergent constituent given in any 1 paragraph of Claims 1-3,
A method for producing a granular detergent composition, comprising the step of adding the component (C) while flowing the component (A) and the component (B) to obtain the coated particles.