JP5851408B2 - 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.
This application claims priority on October 1, 2010 based on Japanese Patent Application No. 2010-224125 for which it applied to Japan, and uses the content here.

In the granular detergent composition, fine particles are generated due to contact between the detergent composition particles during transportation and the like, and dust is easily generated. Since this dust generation is particularly problematic from the viewpoint of consumer usability, it is required to reduce the amount of fine powder generated (inhibition of dust generation) in the granular detergent composition.
In addition, the granular detergent composition is also required to have a high fluidity from the point of view of handling at the time of use.
In order to satisfy these dust generation suppression and fluidity, a granular detergent composition in which the surface of a granular detergent containing 20 to 50% by weight of an anionic surfactant is coated with a nonionic surfactant has been proposed ( Patent Document 1).

Moreover, in order to improve the fluidity | liquidity of a granular detergent composition, the technique of (1) and (2) shown below is proposed.
(1) Into the mixer, the inorganic salt in an amount corresponding to 0.5 to 20 times the amount of the specific chelating agent, which is part or all of the specific inorganic salt, is added in advance, and then A powder detergent composition in which a chelating agent and the remaining portion of the inorganic salt are added, and the remaining portion is added, while mixing or mixing the inorganic salt and the chelating agent, and then adding and mixing a nonionic surfactant Manufacturing method (refer patent document 2).
(2) From particles (I) containing a surfactant, (a) a specific chelating agent, and (b) a carboxylic acid or polycarboxylic acid or a salt thereof and an alkyl sulfate or polyoxyalkylene alkyl sulfate or a salt thereof A detergent composition containing partially neutralized organic chelating agent particles (II) containing one or more selected (see Patent Document 3).

JP-A-9-302383 JP 2008-174724 A JP 2002-20792 A

By the way, in recent years, detergent compositions having a low surfactant concentration have become mainstream due to changes in the laundry situation and increased awareness of environmental loads, and the blending ratio of inorganic builder or alkali agent in the detergent composition has increased. It is coming. Along with this, the granular detergent composition tends to increase the amount of fine powder generated than before, and it is becoming easier to generate dust.
The technique described in Patent Document 1 relates to a conventional granular detergent composition having a high surfactant concentration. When producing a detergent composition having a low surfactant concentration, the technique of Patent Document 1 (only coating with a nonionic surfactant) cannot suppress dust generation. On the other hand, although the method of increasing the usage-amount of nonionic surfactant can be considered, in that case, there exists a problem which a detergent composition particle | grain adheres and it is easy to generate | occur | produce lumps.
Since the technique described in Patent Document 2 only mixes detergent raw materials sequentially, when producing a detergent composition having a low surfactant concentration, dust generation is not sufficiently suppressed, and fluidity is also reduced. It is not satisfactory.
Since the technique described in Patent Document 3 simply mixes the particles (I) and (II), it tends to generate dust as the surfactant concentration decreases.

  The present invention has been made in view of the above circumstances, and provides a granular detergent composition that is difficult to generate dust and excellent in fluidity even when the surfactant is in a low concentration, and a method for producing the same. Let it be an issue.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the granular detergent composition of the present invention is characterized in that detergent particles containing a surfactant and an alkali agent are coated with a water-insoluble inorganic compound, an organic chelating agent, and a binder.
In the granular detergent composition of the present invention, the organic chelating agent is preferably at least one organic chelating agent selected from methylglycine diacetic acid and salts thereof.
In the granular detergent composition of the present invention, the water-insoluble inorganic compound is preferably zeolite.

Moreover, in the granular detergent composition of this invention, it is preferable that the said surfactant is at least 1 type of surfactant selected from the group which consists of an anionic surfactant and a nonionic surfactant.

In the granular detergent composition of the present invention, the alkaline agent is preferably at least one alkaline agent selected from the group consisting of sodium carbonate, potassium carbonate, and sodium bicarbonate.

In the granular detergent composition of the present invention, the binder is preferably a polyoxyalkylene alkyl ether.

  The method for producing the granular detergent composition of the present invention is the method for producing the granular detergent composition of the present invention, wherein the detergent particles containing a surfactant and an alkali agent are mixed with a water-insoluble inorganic compound and an organic chelate. It is characterized by coating with an agent and a binder.

  ADVANTAGE OF THE INVENTION According to this invention, even if surfactant is a low density | concentration, it can provide the granular detergent composition which is hard to generate dust, and is excellent in fluidity | liquidity, and its manufacturing method.

(Granular detergent composition)
In the granular detergent composition of the present invention, the detergent particles containing a surfactant and an alkali agent are composed of a water-insoluble inorganic compound, an organic chelating agent, and a binder (hereinafter, these three components are collectively referred to as “coating components”). It is covered with.
The term “coating” as used herein includes not only a state where the entire surface of the detergent particles is covered with the coating component (coverage rate 100%) but also a state where 50% or more of the surface area of the detergent particles is covered.
The coverage rate refers to the ratio of the area where the coating component adheres to the surface area of the detergent particles when the particles of the granular detergent composition are observed with an electron microscope or the like.
In the granular detergent composition of the present invention, for example, the detergent particles may be coated with a three-component mixture of a water-insoluble inorganic compound, an organic chelating agent, and a binder, and the three components may be mixed on the surface of the detergent particles. An inorganic compound, an organic chelating agent, and a binder may be coated independently and sequentially, and the coating component may be laminated on the surface of the detergent particles. An arbitrary two-component mixture of a water-insoluble inorganic compound, an organic chelating agent, and a binder. And the remaining one component, and a two-component mixture and the remaining one component laminated on the surface of the detergent particles. Of these, a mixture of three components on the surface of the detergent particles and a mixture of the two components and the remaining one component (the remaining one component is preferably an organic chelating agent) are preferably laminated on the surface of the detergent particles.

  The average particle size of the granular detergent composition is preferably 200-1500 μm, more preferably 300-1000 μm. Generation | occurrence | production of a fine powder is suppressed as an average particle diameter is more than a lower limit, and the solubility to water improves that it is below an upper limit on the other hand.

In the present invention, the “average particle size” is a value obtained by performing a classification operation 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. .
In the classification operation, the 9-stage sieve is stacked on a tray in the order of a sieve having a small mesh size and a sieve having a large mesh size, and a measurement sample of 100 g / time is put on the top sieve having a mesh size of 1680 μm. , Attached to a low-tap type sieve shaker (manufactured by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), shaken for 10 minutes, and then left on each sieve and tray Is collected for each mesh and the mass of the sample is measured.
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 set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle diameter (mass 50% diameter) can be determined from the following formula, where c is the total mass frequency from the screen to the aμm sieve and d% is the mass frequency on the aμm sieve.

The bulk density of the granular detergent composition can be determined in consideration of the bulk density of the detergent particles. For example, 500 to 1200 g / L is preferable, and 600 to 1100 g / L is more preferable. If the bulk density is equal to or higher than the lower limit value, the space (storage location) required for storing the granular detergent composition can be reduced, which is advantageous. On the other hand, if it is below an upper limit, the solubility in water of a granular detergent composition will become favorable.
In the present invention, the bulk density indicates a value measured by a method according to JIS K3362-1998 (hereinafter the same).

<Detergent particles>
The detergent particles contain a surfactant and an alkali agent.
The average particle size of the detergent particles is preferably 200 to 1000 μm, more preferably 300 to 500 μm. If the average particle size is at least the lower limit, the generation of fine powder is suppressed, while if it is at most the upper limit, the solubility in water is improved.
Here, the average particle diameter is a value determined by performing the classification operation described above.

  The bulk density of the detergent particles is preferably 500 to 1200 g / L, and more preferably 800 to 1000 g / L. If the bulk density of the detergent particles is equal to or higher than the lower limit value, the space (storage location) required for storing the granular detergent composition can be reduced, which is advantageous. On the other hand, if it is below an upper limit, the solubility in water of a granular detergent composition will become favorable.

≪Surfactant≫
The surfactant is not particularly limited as long as it is conventionally used in a detergent composition for clothing and the like, and various types of surfactants can be used.
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

Anionic surfactant Examples of the anionic surfactant include those shown below.
Α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
A linear or branched alkylbenzene sulfonate (LAS, ABS) having an alkyl group having 8 to 18 carbon atoms.
Alkane sulfonate (SAS) having 10 to 20 carbon atoms.
An alkyl ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 moles or less added ethylene oxide, propylene oxide, butylene oxide or a mixture thereof Sulfate or alkenyl ether sulfate (AES).
An alkyl ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 moles or less added ethylene oxide, propylene oxide, butylene oxide or a mixture thereof Carboxylate or alkenyl ether carboxylate.
Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms;
A higher fatty acid salt (soap) having 10 to 20 carbon atoms.
α-sulfo fatty acid salt or ester salt thereof. Preferably, it is a saturated or unsaturated α-sulfo fatty acid salt having 8 to 20 carbon atoms (more preferably 12 to 18) or an ester salt thereof (more preferably a methyl ester salt (MES), an ethyl ester salt or a propyl ester salt). ).

Nonionic surfactant Nonionic surfactants include, for example, those shown below.
A polyoxyalkylene alkyl ether obtained by adding an average of 3 to 30 mol, preferably an average of 5 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, or polyoxy Alkylene alkenyl ether (alcohol alkoxylate). Among these, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether are preferable.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group of the aliphatic alcohol may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.

  Polyoxyethylene alkyl phenyl ether, polyoxyethylene alkenyl phenyl ether.

A fatty acid alkyl ester alkoxylate represented by the following general formula (VI), for example, having an alkylene oxide added between ester bonds of a long-chain fatty acid alkyl ester.
_{^{R 1 CO- [OR 2] n}} '-OR 3 ··· (VI)
[In the formula (VI), R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OR ² represents an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms (for example, , Ethylene oxide, propylene oxide, etc.); n ′ represents the average number of moles of alkylene oxide added, preferably 3-30, more preferably 5-20. R ³ represents a lower (1 to 4 carbon) alkyl group which may have a substituent having 1 to ³ carbon atoms. ]

  Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, glycerin fatty acid ester.

Among the above, the nonionic surfactant preferably has a melting point of 5 ° C. to 50 ° C., more preferably 10 ° C. to 40 ° C., and preferably HLB of 7 to 16, Preferably it is 8-14.
The melting point here is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical product”.
HLB is a value determined by the Griffin method (see Yoshida, Shindo, Ogaki, Yamanaka, edited by "New Edition Surfactant Handbook", Kogyoshosho Co., Ltd., 1991, page 234).
Specific examples of such nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers having a melting point of 50 ° C. or lower and an HLB of 7 to 16. Examples include polyoxyethylene polyoxypropylene alkenyl ether, fatty acid methyl ester ethoxylate in which ethylene oxide is added to fatty acid methyl ester, and fatty acid methyl ester ethoxypropoxylate in which ethylene oxide and propylene oxide are added to fatty acid methyl ester.

-Cationic surfactant As the cationic surfactant, for example, a mono, di, or trialkyl cation having 1 to 3 long chain (preferably 8 or more carbon atoms) hydrocarbon groups can be used. In particular, a cationic surfactant containing 1 to 2 ester groups and 1 to 2 long-chain hydrocarbon groups in the molecule is preferable.
Specific examples of the cationic surfactant include mono long-chain alkyltrimethylammonium chloride containing one long-chain alkyl group or alkenyl group having 8 to 22 carbon atoms, two long-chain alkyl groups or alkenyl groups having 8 to 22 carbon atoms. Di-long-chain alkyldimethylammonium chloride containing three, tri-long-chain alkylmethylammonium chloride containing three long-chain alkyl groups or alkenyl groups having 8 to 22 carbon atoms, 1 long-chain alkyl group or alkenyl group having 8 to 22 carbon atoms N-acyloxyethyl-N, N-dimethyl-N-hydroxyethylammonium chloride, N, N-diacyloxyethyl-N, N-dimethyl containing two long-chain alkyl or alkenyl groups having 8 to 22 carbon atoms Ammonium chloride and the like can be used.

-Amphoteric surfactant As the amphoteric surfactant, sulfobetaine or carboxybetaine having one or two long chain (preferably having 8 or more carbon atoms) hydrocarbon groups can be used.
The long chain hydrocarbon group may include an ester group, an amide group, or an ether group. Further, the long chain hydrocarbon group may be a single chain type or a two chain type. Further, the ratio of the saturated / unsaturated type in the long chain hydrocarbon group, the distribution of the carbon chain length, the ratio of the cis isomer / trans isomer of the unsaturated group, etc. are not particularly limited. Further, the long chain hydrocarbon group may be derived from a fatty acid or a fatty acid methyl ester which is a raw material for producing the above-mentioned cationic surfactant.
Specific examples of amphoteric surfactants include betaines such as N, N-diacyloxyethyl-N-methylammonioethyl sulfate and N, N-diacyloxyethyl-N-methylammonioethylcarboxylate; N-acyloxy Ethyl-N-hydroxyethyl-N-methylammoniobetaines, N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxy And propylammoniobetaine.
The amphoteric surfactant may contain an aminobetaine such as a compound whose nitrogen atom is not quaternized, a raw material alkanolamine, a neutralized product thereof, or a quaternized product thereof.

  The salt forms in the surfactant include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts These may be mixed. Of these, alkali metal salts are preferred.

Surfactant can be used individually by 1 type or in combination of 2 or more types.
Among the above, the surfactant is preferably an anionic surfactant or a nonionic surfactant, and more preferably used in combination with an anionic surfactant and a nonionic surfactant, since the cleaning performance is improved.
The content of the surfactant in the detergent particles is preferably less than 30% by mass, more preferably 5 to 28% by mass, and particularly preferably 10 to 25% by mass.
If the content of the surfactant in the detergent particles is less than 30% by mass, the surfactant concentration with respect to the whole granular detergent composition becomes low, and the technical significance of the present invention becomes high. On the other hand, when the content of the surfactant is not less than the lower limit value, a good cleaning effect is easily obtained.

≪Alkaline agent≫
The alkali agent is not particularly limited as long as it is conventionally used in a detergent composition for clothing and the like; carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate; sodium bicarbonate, potassium bicarbonate Bicarbonates such as potassium carbonate; silicates such as sodium silicate and potassium silicate; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
An alkali agent can be used individually by 1 type or in combination of 2 or more types.
Among the above, it is preferable to use carbonate as the alkali agent.
The content of the alkali agent in the detergent particles is preferably 15 to 60% by mass, and more preferably 25 to 50% by mass.
A cleaning effect improves that content of an alkaline agent is more than a lower limit. On the other hand, the solubility with respect to water of a granular detergent composition improves that it is below an upper limit.

≪Other ingredients≫
The detergent particles may contain other components other than the surfactant and alkali agent as necessary.
Examples of other components include those usually used in detergent compositions for clothing, and examples include organic builders and inorganic builders.

・ Organic builder The organic builder is not particularly limited as long as it is conventionally used in a cleaning composition for clothing, for example, nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, asparagine Aminocarboxylates such as acid diacetate, methylglycine diacetate, and iminodisuccinate; and hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, and dihydroxyethylglycine salt Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate and gluconate; cyclocarboxylates such as pyromellitic acid salt, benzopolycarboxylate and cyclopentanetetracarboxylate; carboxymethyltartro Carboxymethyloxysuccine Ether carboxylates such as oxydisuccinate, tartaric acid mono- or disuccinate; polyacrylate, acrylic acid-allyl alcohol copolymer salt, acrylic acid-maleic acid copolymer salt, polyglyoxylic acid, etc. Salt of polyacetal carboxylic acid; salt of acrylic acid polymer or copolymer such as hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer; maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid And salts of polymers or copolymers such as succinic acid and aspartic acid; polysaccharide oxides such as starch, cellulose, amylose, and pectin; and polysaccharide derivatives such as carboxymethyl cellulose.
The organic builder can be used alone or in combination of two or more.
The content of the organic builder in the detergent particles is preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass.
A cleaning effect improves that content of an organic builder is more than a lower limit. On the other hand, when it is not more than the upper limit value, it becomes easy to prevent the detergent particles from solidifying.

-Inorganic builder The inorganic builder is not particularly limited as long as it is conventionally used in cleaning compositions for clothing, etc., and is a crystalline aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, etc. ), Amorphous aluminosilicates; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; crystalline silicate, carbonate and amorphous alkali Examples include composites with metal silicates.
An inorganic builder can be used alone or in combination of two or more.
Among the above, it is preferable to use crystalline aluminosilicate as the inorganic builder.
The content of the inorganic builder in the detergent particles is preferably 10 to 45% by mass, and more preferably 10 to 30% by mass.
A cleaning effect improves that content of an inorganic builder is more than a lower limit. Moreover, the fluidity | liquidity at the time of mixing a detergent raw material becomes good. On the other hand, when it is at most the upper limit value, it becomes easy to prevent the detergent particles from solidifying, and the bulk density of the granular detergent composition can be controlled to be high.

-Zinc sulfate In the granular detergent composition of the present invention, when using a bleaching agent such as percarbonate (for example, sodium percarbonate), an organic peracid precursor such as the bleaching agent and dodecanoyloxybenzenesulfonate From the viewpoint of sterilization performance, it is preferable that the detergent particles contain zinc sulfate. Among these, zinc sulfate hydrate is particularly preferable because gelation and aggregation of the detergent particles hardly occur when the granular detergent composition is dissolved in water.
As for the number of water molecules in zinc sulfate hydrate, gelation / aggregation of the detergent particles is less likely to occur when the granular detergent composition is dissolved in water, and it is also easy to obtain. 1 is particularly preferable because it is easy to handle as a raw material.
Zinc sulfate can be used alone or in combination of two or more.
The content of zinc sulfate in the detergent particles is preferably 0.01 to 3% by mass, more preferably 0.02 to 0.8% by mass, and 0.2 to 0.6% by mass. More preferably it is.
When the content of zinc sulfate is at least the lower limit, when the granular detergent composition is dissolved in water, gelation and aggregation of the detergent particles are less likely to occur, and the solubility of the granular detergent composition in water is improved. . On the other hand, if it is below the upper limit value, the blending effect is sufficiently obtained.

  In addition to the components described above, the detergent particles include, as other components, reducing agents, particle strength retention agents (sulfates such as sodium sulfate, silicates, etc.), optical brighteners, ultraviolet absorbers, enzyme agents, bleaching agents, Contains bleach activators (such as organic peracid precursors), bleach activation catalysts, softeners, recontamination (deposition) inhibitors, foam control agents, perfumes, surface modifiers, oil absorbers, grinding aids, etc. May be.

  The content of the detergent particles in the granular detergent composition is preferably 80% by mass to 99% by mass, more preferably 85% by mass to 98% by mass, and particularly preferably 90 to 98% by mass. If it is in the said range, a balance with the component for coating | cover will be taken and sufficient detergency can be exhibited.

<Coating ingredients>
In the granular detergent composition of the present invention, the detergent particles are coated with a water-insoluble inorganic compound, an organic chelating agent, and a binder (coating component).

≪Water-insoluble inorganic compound≫
In the present invention, “water-soluble” and “water-insoluble” are classified as water-insoluble in the chemical handbook basic edition II (Revised 2nd edition, pages 777 to 791, Maruzen, 1975). To do. Moreover, as a simple discrimination method, when 5 g of an inorganic compound is added to 100 mL of hot water (85 ° C. or higher), a part or all of which remains as a residue is defined as a water-insoluble inorganic compound.

Examples of water-insoluble inorganic compounds 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, zeolites of A type, X type, Y type, P type 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 .; 4A ZEOLITE (trade name) manufactured by ALUMINUM CORPORATION OF CHINA., LTD .; 4A Zeolite manufactured by Huying Chemical Products Co., LTD. Zeolite 4A Type (trade name) manufactured by Toi Chemical 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.

A water-insoluble inorganic compound can be used alone or in combination of two or more.
Among these, as the water-insoluble inorganic compound, aluminosilicate is preferable and zeolite is particularly preferable because the fluidity of the granular detergent composition is good.
In the granular detergent composition, the content of the water-insoluble inorganic compound as a coating component is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and particularly preferably 1 to 3% by mass.
If the content of the water-insoluble inorganic compound is not less than the lower limit, the fluidity of the granular detergent composition is improved. On the other hand, if the content is not more than the upper limit, it is balanced with other coating components, and dust generation is suppressed. Both the effects of improving fluidity can be easily obtained.

≪Organic chelating agent≫
The organic chelating agent is not particularly limited, and examples thereof include aminocarboxylic acid or a salt thereof, hydroxyaminocarboxylic acid or a salt thereof, and a polycarboxylic acid polymer compound.

Aminocarboxylic acid or hydroxyaminocarboxylic acid or a salt thereof Specific examples of aminocarboxylic acid or hydroxyaminocarboxylic acid or a salt thereof include ethylenediaminetetraacetic acid or a salt thereof, β-alanine diacetic acid or a salt thereof, Examples include compounds represented by formulas (I) to (III).

［式（Ｉ）中、Ｘは水素原子、アルカリ金属原子又はアルカリ土類金属原子を表す。ｐは１又は２の整数を表す。式（ＩＩ）中、Ｘ^１〜Ｘ^４は同一であっても異なっていてもよく、それぞれ水素原子、アルカリ金属原子、アルカリ土類金属原子又はカチオン性アンモニウム基を表す。Ｒは水素原子又は水酸基を表し、Ｑは水素原子又はアルキル基を表し、ｎ_１は０又は１の整数を表す。式（ＩＩＩ）中、Ｙはアルキル基、水酸基又は水素原子を表す。Ｘ^５〜Ｘ^７は同一であっても異なっていてもよく、それぞれ水素原子、アルカリ金属原子、アルカリ土類金属原子又はカチオン性アンモニウム基を表す。ｎ_２は０〜５の整数を表す。］

[In the formula (I), X represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom. p represents an integer of 1 or 2. In formula (II), X ^{1 to} X ⁴ may be the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cationic ammonium group. R represents a hydrogen atom or a hydroxyl group, Q represents a hydrogen atom or an alkyl group, and n ₁ represents an integer of 0 or 1. In formula (III), Y represents an alkyl group, a hydroxyl group or a hydrogen atom. X ^{5 to} X ⁷ may be the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cationic ammonium group. n ₂ represents an integer of 0 to 5. ]

-Compound represented by the general formula (I) In the formula (I), examples of the alkali metal atom in X include sodium and potassium.
Examples of the alkaline earth metal in X include calcium and magnesium. For example, in the case of calcium (Ca), “-(COOX) _p ” in formula (I) is represented as “-(COOCa _1/2 ) _p ”.
Of these, X is preferably a hydrogen atom.

In the formula (I), p represents an integer of 1 or 2, and is preferably 1.
When p is 2, the plurality of X may be the same or different from each other.
When p is 1, the bonding position of the “—COOX” group to the pyridine ring is preferably α-position with respect to the nitrogen atom. When p is 2, at least one “—COOX” group is preferably bonded to the α-position. The remaining “—COOX” groups may be bonded to either the β-position or the γ-position.

  Among the compounds represented by the general formula (I), a compound (2-pyridinecarboxylic acid) represented by the following chemical formula (1) or a salt thereof is preferable because it has a high dust suppressing effect. Or a compound represented by the following chemical formula (2) (2,6-pyridinedicarboxylic acid (dipicolinic acid)) or a salt thereof.

..Compound represented by the general formula (II) In the formula (II), as an alkali metal atom or an alkaline earth metal atom in X ^{1 to} X ^4, an alkali metal atom in X in the formula (I) And the same as the alkaline earth metal atom.
When any of X ^{1 to} X ⁴ is an alkaline earth metal atom, for example, when X ¹ is calcium (Ca), “—COOX ¹ ” in formula (II) is “—COOCa _1/2 ”. It is expressed.
As the cationic ammonium group, for example, “(R ¹¹ ) (R ¹² ) (R ¹³ ) (R ¹⁴ ) N ⁺ ” (wherein R ^{11 to} R ¹⁴ may be the same or different, Each of which is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group).
Among the above, X ^{1 to} X ⁴ are each preferably an alkali metal atom, and more preferably sodium or potassium.
X ^{1 to} X ⁴ may be the same as or different from each other.

In the formula (II), R represents a hydrogen atom or a hydroxyl group, and is preferably a hydroxyl group.
As an alkyl group in Q, it is preferable that it is C1-C4, and it is more preferable that it is C1-C3. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
n ₁ represents an integer of 0 or 1, and is preferably 1.

  Among the compounds represented by the general formula (II), a compound (2,2′-iminodisuccinic acid) represented by the following chemical formula (3) or Examples thereof include a salt thereof, a compound represented by the following chemical formula (4) (3-hydroxy-2,2′-iminodisuccinic acid) or a salt thereof.

-Compound represented by the general formula (III) In the formula (III), the alkyl group in Y preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

In the formula (III), examples of the alkali metal atom, alkaline earth metal atom and cationic ammonium group in X ^{5 to} X ⁷ include the alkali metal atom and alkaline earth in X ^{1 to} X ⁴ in the formula (II). The same thing as a metal atom and a cationic ammonium group is mentioned.
When any of X ^{5 to} X ⁷ is an alkaline earth metal atom, for example, when X ⁵ is calcium (Ca), “—COOX ⁵ ” in formula (III) is “—COOCa _1/2 ”. It is expressed.
Among the above, X ^{5 to} X ⁷ are all preferably alkali metal atoms, and more preferably sodium or potassium.
X ^{5 to} X ⁷ may be the same as or different from each other.

n ₂ represents an integer of 0 to 5, is preferably 0-2.

  Among the compounds represented by the general formula (III), the compound represented by the following chemical formula (5) (nitrilotriacetic acid) and the following chemical formula (6) are preferable because they have a high dusting suppression effect. Or a compound represented by the following chemical formula (7) (serine diacetate) or a salt thereof. Of these, methylglycine diacetic acid or a salt thereof (MGDA) is more preferable.

When the detergent particles are coated with the compounds represented by the general formulas (I) to (III), a part or all of the terminal group “—COOX” becomes “—COO ⁻ ”, and the detergent particles are formed on the surface of the detergent particles. Adsorbed.

Polycarboxylic acid polymer compound Here, “polycarboxylic acid polymer compound” means a polymer having a structural unit (repeating unit) containing a carboxy group, preferably a polymer having a weight average molecular weight of 1000 or more. Say things.
The polycarboxylic acid polymer compound preferably has a weight average molecular weight of 1000 or more, more preferably in the range of 1500 to 200000, and still more preferably in the range of 2000 to 60000. When the weight average molecular weight of the polycarboxylic acid polymer compound is 1000 or more, particularly 1500 or more, it can be sufficiently adsorbed on the surface of the detergent particles, and in particular, the effect of suppressing dust generation is improved. Improves the adsorptive properties.
In the present specification, “weight average molecular weight” indicates a value obtained by analysis by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

Preferred examples of the polycarboxylic acid polymer compound include those obtained by introducing a carboxy group or a side chain containing a carboxy group into a main chain having a hydrocarbon group.
For example, what has a structural unit represented by the following general formula (IV) is mentioned preferably.

［式（ＩＶ）中、Ｚは水素原子、直鎖状もしくは分岐鎖状のアルキル基、又は下記一般式（Ｖ）で表される基を表す。複数のＺは同一であってもよく、異なっていてもよい。ただし、複数のＺのうち、少なくとも一つは下記一般式（Ｖ）で表される基であって、ＷがＣＯＯＭ’である。］

[In formula (IV), Z represents a hydrogen atom, a linear or branched alkyl group, or a group represented by the following general formula (V). A plurality of Z may be the same or different. However, at least one of the plurality of Z is a group represented by the following general formula (V), and W is COOM ′. ]

［式（Ｖ）中、Ｗはアミノ基又はＣＯＯＭ’（Ｍ’は水素原子、アルカリ金属原子、アルカリ土類金属原子、アルカノールアミン、又はＮＨ_４である）を表す。ｑは０〜２の整数を表す。］

[In formula (V), W represents an amino group or COOM ′ (M ′ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an alkanolamine, or NH ₄ ). q represents the integer of 0-2. ]

In said formula (IV), as an alkyl group in Z, it is preferable that it is C1-C4, and it is more preferable that it is C1-C3. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
In the formula (V), the amino group in W is preferably —NR ¹ R ² (wherein R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). It is done.
The alkali metal atom in M ′ is preferably sodium or potassium. As the alkaline earth metal atom, calcium and magnesium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable.
Among these, as M ′, an alkali metal atom is preferable, and sodium is particularly preferable.
When there are two or more M ′, the plurality of M ′ may be the same or different from each other.
q represents an integer of 0 to 2, and 0 is preferable.

The polycarboxylic acid polymer compound may be a polymer composed of repetitions of the same structural unit, or may be a copolymer composed of repetitions of plural types of structural units. In the case of a copolymer composed of repeating plural kinds of structural units, the copolymer may be a random copolymer or a block copolymer.
Specific examples of the polycarboxylic acid polymer compound include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyhydroxyacrylic acid, polyfumaric acid, polyacetal carboxylic acid, and a copolymer of acrylic acid and maleic acid (acrylic acid). -Maleic acid copolymer), a copolymer of acrylic acid and acrylic acid amide (acrylic acid-acrylic acid amide copolymer), or a salt thereof.
Among them, the polycarboxylic acid polymer compound preferably has a structural unit derived from an acrylic acid monomer because of its high dust suppression effect, and is preferably an acrylic acid homopolymer, an acrylic acid copolymer, or these A salt is more preferable, and an acrylic acid-maleic acid copolymer or a salt thereof is particularly preferable.

The organic chelating agent can be used alone or in combination of two or more.
Among these, as the organic chelating agent, an aminocarboxylic acid or hydroxyaminocarboxylic acid or a salt thereof is preferable because the effect of suppressing dust generation is particularly high, and the compound represented by the general formula (III) is more preferable. Preferably, methylglycine diacetic acid or a salt thereof (MGDA) is particularly preferable.
In the granular detergent composition, the content of the organic chelating agent as a coating component is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and particularly preferably 0.3 to 1% by mass. .
If the content of the organic chelating agent is equal to or higher than the lower limit, the effect of suppressing the dust generation of the granular detergent composition is improved. On the other hand, if the content is lower than the upper limit, the balance with other coating components is improved, and the dust is generated. Both suppression and fluidity improvement effects are likely to be obtained.

≪Binder≫
As the binder, an alkylene oxide addition polymer having a melting point of 10 ° C. or higher is preferable, and an alkylene oxide addition polymer having a melting point of 10 to 40 ° C. is more preferable. When the melting point of the binder is equal to or higher than the lower limit, it can be easily used as a stock solution or a solution, and the detergent particles are easily coated by a method such as spraying.
Specific examples of the binder include glycols such as polyethylene glycol (PEG) and polypropylene polyethylene glycol (PPEG); nonionic surfactants such as polyoxyalkylene alkyl ethers; saturated fatty acids or salts thereof, and higher alcohols.

As polyethylene glycol (PEG) and polypropylene polyethylene glycol (PPEG), those having an average molecular weight of 100 to 100,000 are preferred, those having an average molecular weight of 500 to 10,000 are more preferred, and those having an average molecular weight of 600 to 6000 are even more preferred.
The average molecular weight of PEG or PPEG here refers to the average molecular weight described in the cosmetic raw material standard (the second edition comment).

As a polyoxyalkylene alkyl ether, C12-20 of an alkyl group is preferable, and C12-16 is more preferable.
As the added alkylene oxide, ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO) are preferable.
As addition mole number of the alkylene oxide added, 3-30 are preferable and 5-20 are more preferable.

The saturated fatty acid or salt thereof preferably has 8 to 24 carbon atoms, more preferably 12 to 20 carbon atoms, still more preferably 14 to 20 carbon atoms, and particularly preferably 14 to 18 carbon atoms. Manufacturability is good when the carbon number is 8 or more, while solubility in water in the granular detergent composition is improved when the carbon number is 24 or less.
Specific examples of the saturated fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and lauric acid, myristic acid, palmitic acid, stearic acid. preferable.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt; ammonium salt Alkaline earth metal salts are preferable, and calcium salts are particularly preferable.

As the higher alcohol, a higher alcohol having 8 to 24 carbon atoms is preferable, a higher alcohol having 12 to 20 carbon atoms is more preferable, a higher alcohol having 14 to 20 carbon atoms is further preferable, and a higher alcohol having 14 to 18 carbon atoms is particularly preferable. preferable. Manufacturability is good when the carbon number is 8 or more, while solubility in water in the granular detergent composition is improved when the carbon number is 24 or less.
Of the higher alcohols, primary higher alcohols are preferred. Specifically, lauryl alcohol, myristyl alcohol, and stearyl alcohol are preferable, and myristyl alcohol and stearyl alcohol are more preferable.

A binder can be used individually by 1 type or in combination of 2 or more types as appropriate.
Among these, as the binder, a nonionic surfactant is preferable, and polyoxyalkylene alkyl ether is particularly preferable because it is excellent in the effect of suppressing dust generation of the granular detergent composition.
In the granular detergent composition, the content of the binder as a coating component is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and particularly preferably 0.3 to 1% by mass.
If the content of the binder is not less than the lower limit, the effect of suppressing the dust generation of the granular detergent composition is improved. On the other hand, if the content is not more than the upper limit, it is balanced with other coating components, and the dust generation is suppressed. Both the effects of improving fluidity can be easily obtained.

In the granular detergent composition, the mixing ratio of the water-insoluble inorganic compound as the coating component and the organic chelating agent is preferably a mass ratio of water-insoluble inorganic compound / organic chelating agent = 0.4-20. 10 to 10 is more preferable. When the mass ratio is less than or equal to the upper limit value, the effect of suppressing dust generation is easily obtained. On the other hand, fluidity improves that it is more than the lower limit of this mass ratio.
In the granular detergent composition, the mixing ratio of the water-insoluble inorganic compound as the coating component and the binder is preferably a mass ratio of water-insoluble inorganic compound / binder = 1-10, and preferably 4-7. More preferred. When the mass ratio is less than or equal to the upper limit value, the effect of suppressing dust generation is easily obtained. On the other hand, when the mass ratio is equal to or more than the lower limit value, it is difficult to generate lumps caused by the detergent composition particles sticking to each other.
In the granular detergent composition, the mixing ratio of the organic chelating agent as the coating component and the binder is, by mass ratio, preferably organic chelating agent / binder = 0.2-10, and is 0.5-2. It is more preferable. Solidification of the detergent composition accompanying a long-term storage is suppressed as it is below the upper limit of this mass ratio. On the other hand, when the mass ratio is not less than the lower limit value, the raw material mixture hardly adheres to the mixing device.

The detergent particles may be further coated with other coating components in addition to the water-insoluble inorganic compound, the organic chelating agent and the binder.
As other coating components, fatty acid divalent metal salts such as calcium stearate may be used.

(Method for producing granular detergent composition)
As a method for producing the granular detergent composition of the present invention described above, specifically, a step of preparing detergent particles containing a surfactant and an alkaline agent (hereinafter referred to as “detergent particle preparation step”), And a method including a step of coating the detergent particles with a water-insoluble inorganic compound, an organic chelating agent, and a binder (hereinafter referred to as “coating step”).

[Detergent particle preparation process]
In the detergent particle preparation step, detergent particles are prepared by granulation using a conventionally known kneading pulverization method (kneading / extrusion / pulverization), stirring granulation method, rolling granulation method, or the like.
Especially, since the shearing force applied to the detergent raw material is large and the detergent raw material is easily mixed uniformly, the kneading pulverization method (kneading, extrusion, pulverization) and the stirring granulation method are preferable, and the kneading pulverization method is more preferable. .
Specifically, for example, detergent particles can be prepared as follows.

First, a surfactant and an alkali agent are mixed to prepare a detergent raw material mixture.
As a method for mixing the detergent raw material, a conventionally known method is used. For example, a surfactant, an alkaline agent and other components are uniformly mixed with water to prepare a detergent slurry, and the detergent slurry is spray-dried; A method of simply mixing an activator, an alkali agent and other components can be mentioned.
The usage amount of the surfactant and the alkali agent is a part or all of the predetermined blending amount, and the usage amount when blending a part of the predetermined blending amount may be appropriately determined throughout the entire process.

Next, granulation is performed on the mixture obtained above.
When the kneading pulverization method (kneading, extrusion, pulverization) is used as the granulation method, the granulation is performed as follows.
For example, using a kneading and kneading machine such as a continuous or batch kneader, the kneading and kneading are carried out by blending predetermined components into the mixture obtained above.
Examples of the predetermined component include a part of a surfactant such as a nonionic surfactant (such as polyoxyethylene alkyl ether) and an anionic surfactant (such as MES), a small amount of water, or a mixture thereof.
Since this surfactant can perform kneading and kneading more favorably, it is preferable to mix one containing 0.1 to 30% by weight of water, and one containing 1 to 20% by weight. It is more preferable to blend, and it is even more preferable that 5 to 15% by mass is included.
Since a small amount of water can perform kneading and kneading more favorably, it is preferable to blend 0.01 to 10 parts by mass of water with respect to 100 parts by mass of the mixture obtained above. It is more preferable to mix part by weight of water, and it is more preferable to add 0.5 to 2 parts by weight of water.
When the kneading treatment is performed, the treatment temperature is preferably controlled to 30 to 80 ° C, more preferably 40 to 70 ° C, and the treatment time is preferably 20 to 90 seconds, 30 More preferably, it is set to ˜60 seconds.
Next, the kneaded material obtained by the kneading kneading is extruded through small holes using an extruder to obtain pellets.
Thereafter, the obtained pellet-like material is pulverized using a hammer such as a Fitzmill or a speed mill, or a cutter mill type pulverizer, and the particles are sized to produce detergent particles.
During the pulverization, it is preferable to use a pulverization aid because adhesion between the pulverized particles of the pellet-like material is suppressed. Examples of the grinding aid include zeolite, sodium carbonate, silica derivatives, and clay minerals.

When the stirring granulation method is used as the granulation method, the mixture obtained above and the predetermined components are introduced into a conventionally known batch type or continuous stirring granulator and stirred. To produce detergent particles.
As suitable granulation conditions in the stirring granulation method, the following formula Froude number (Fr) = V / (r × g) ^0.5
It is preferable to control the fluid number (Fr) defined by 1 to 1 to 4, and more preferably to 1.2 to 3.
If the fluid number is equal to or greater than the lower limit, consolidation is promoted. On the other hand, when the Froude number is less than or equal to the upper limit value, the particle size distribution does not become too wide, which is preferable.
In the above formula, V represents the peripheral speed [m / s] of the tip of the stirring blade, r represents the rotation radius of the stirring blade [m], and g represents the acceleration of gravity [m / s ² ].

[Coating process]
In the coating step, a granular detergent composition is produced by coating the detergent particles obtained in the detergent particle preparation step with a water-insoluble inorganic compound, an organic chelating agent, and a binder (coating component).
As a method of coating the detergent particles with the coating component, a conventionally known method can be used, for example, a method of mixing the detergent particles and the coating component while rolling them in a container rotating cylindrical mixer, or a detergent. Examples thereof include a method of mixing while spraying a part of the coating component (preferably a binder) while rolling the particles and the coating component.

The temperature in the container rotating cylindrical mixer is preferably 10 to 50 ° C, more preferably 15 to 40 ° C.
The relative humidity in the container rotating cylindrical mixer is preferably 50 to 100%, and more preferably 70 to 90%.
The rotation speed of the container rotating cylindrical mixer is preferably 10 to 50 rpm, more preferably 15 to 30 rpm.
The filling rate of the container rotating cylindrical mixer is preferably 10 to 50% by volume, more preferably 20 to 40% by volume. The “filling rate” here refers to the ratio of the volume occupied by the detergent raw materials (detergent particles, coating components and other components) to the total volume of the rotating container.
The rotation time (coating time) of the container-rotating cylindrical mixer is preferably 0.5 to 3 minutes, and more preferably 1 to 2 minutes.
When a part of the coating component is sprayed, the droplet diameter of the coating component is preferably 20 to 200 μm, and more preferably 40 to 150 μm.
As a suitable mixing condition in the container rotating type cylindrical mixer, the following formula Froude number (Fr ′) = V _C ² / (R × g)
Is preferably controlled to 0.01 to 0.8, more preferably 0.05 to 0.6.
It is preferable that the fluid number is within the above-mentioned preferable range because the particles are mixed well and the coating component is sufficiently coated with the detergent particles.
In the above formula, the peripheral speed of the outermost periphery in V _C is the container rotating cylindrical mixer [m / s], R is the radius from the rotational center of the outermost periphery of the container rotating cylindrical mixer (m), g is The gravitational acceleration [m / s ² ] is shown respectively.

About the component for coating | cover, since the effect of dust generation suppression increases more and it is suitable also for spraying, it is preferable to use a binder in a liquid form (stock solution, solution).
In addition, since it is easy to handle at the time of blending, it is preferable to use a water-insoluble inorganic compound and an organic chelating agent as they are, respectively, as they are, and the effect of suppressing dust generation is further increased. It is particularly preferable to use one having an average particle size.
The average particle size of the water-insoluble inorganic compound is preferably 1 to 50 μm, and more preferably 2 to 30 μm. When the average particle size of the water-insoluble inorganic compound is not less than the lower limit value, it is difficult to produce fine powder of the water-insoluble inorganic compound itself, whereas when it is not more than the upper limit value, the covering property to the detergent particles becomes good, The effect of suppressing dust generation of the granular detergent composition is further increased.
The average particle size of the water-insoluble inorganic compound is a value determined by performing the classification operation described above.
The average particle size of the organic chelating agent is preferably 50 to 1500 μm, and more preferably 60 to 1400 μm. When the average particle size of the organic chelating agent is not less than the lower limit, fine powder of the organic chelating agent itself is less likely to be generated, while when it is not more than the upper limit, the coverage with the detergent particles becomes good, and the granular detergent The effect of suppressing dust generation of the composition is further enhanced.
The average particle diameter of the organic chelating agent is a value measured as a volume-based median diameter by a laser light scattering method using a particle size distribution analyzer (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.). is there.

When coating the detergent particles, the method of blending the coating component is not particularly limited. For example, it may be blended as a three-component mixture of a water-insoluble inorganic compound, an organic chelating agent, and a binder. A chelating agent and a binder may be blended arbitrarily and sequentially, respectively, or a water-insoluble inorganic compound, an organic chelating agent, and a binder may be blended separately into a two-component mixture and the remaining one component.
In particular, since the effect of suppressing dust generation is further increased, the method of blending as the above three-component mixture is preferable, and the method of blending separately into the two-component mixture and the remaining one component, and among them, the effect of suppressing dust generation is preferable. Since it increases further, the method of mix | blending as a 3 component mixture is more preferable.

  Specifically, as a method of blending as a three-component mixture, a method of mixing detergent particles with a mixture in which a water-insoluble inorganic compound (powder), an organic chelating agent (powder) and a binder (powder) are mixed in advance. A method in which a mixture in which a water-insoluble inorganic compound (powder) and an organic chelating agent (powder) are mixed in advance is added to the detergent particles, and mixing is performed while spraying a binder (liquid).

  Specifically, as a method of mixing separately into the two-component mixture and the remaining one component, a mixture in which a water-insoluble inorganic compound (powder) and a binder (powder) are mixed in advance is added to the detergent particles and mixed. Thereafter, a method in which an organic chelating agent (powder) is added and mixed separately; a water-insoluble inorganic compound (powder) is added to the detergent particles, and the binder (liquid) is mixed while sprayed, and then separately. For example, an organic chelating agent (in powder form) may be added and mixed.

The granular detergent composition of the present invention is difficult to generate dust and excellent in fluidity even when the surfactant is at a low concentration. The reason why such an effect is obtained is not clear, but the organic chelating agent that absorbs moisture at the time of production of detergent particles having a low surfactant concentration and a high blending ratio such as an alkaline agent is synergistic with the water-insoluble inorganic compound and the binder. This is thought to be due to the fact that they act and coat each other.
The granular detergent composition and the method for producing the same of the present invention are techniques suitable for obtaining a detergent composition having a low surfactant concentration and a high blending ratio of an alkali agent or the like.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

<Measuring method of average particle diameter>.
-Average particle diameter of MGDA In this Example, the average particle diameter of MGDA is based on volume by laser light scattering method using a particle size distribution analyzer (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.). The median diameter was measured.

-Average particle diameter other than MGDA The average particle diameter other than MGDA was subjected to the classification operation described above, and the average particle diameter (mass 50%) was determined from the above formula.

<Method for measuring bulk density>
In this example, the bulk density was measured by a method according to JIS K3362-1998.

<Method for measuring water content>
In this example, the moisture content was measured using an infrared moisture meter (manufactured by Kett Scientific Laboratory) under the conditions of a sample 5 g, a sample surface temperature of 130 ° C., and a measurement time of 20 minutes.

The composition of the granular detergent composition manufactured by the manufacturing method of each example is shown in Tables 1 and 2.
The raw materials used in this example are as follows.

<Detergent particles>
Surfactant MES paste: α-sulfo fatty acid alkyl ester salt-containing paste [paste composition: α-sulfo fatty acid methyl ester salt (MES-Na) 63% by mass, nonionic surfactant (polyoxyethylene alkyl ether described later) 16 Mass%, impurities such as di-salt and methyl sulfate 8 mass%, water content 13 mass%], fatty acid chain length of α-sulfo fatty acid alkyl ester salt is 16 and 18, carbon number is 16 and carbon number 18 mixing ratio with C16 / C18 = 8/2 (mass ratio).
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Co., Ltd., Rypon LH-200 (LAS-H pure content 96 mass%)], and detergent particles (A) will be described later. [Preparation Example of Detergent Particles (A)-Kneading Crushing] Compound Neutralized with 48% by Mass of Aqueous Sodium Hydroxide at Preparation of Aqueous Slurry; Detergent Particles (B) Compound neutralized with powdered sodium carbonate in the spray-dried particles during stirring with the spray-dried particles in Preparation Example-Agitation Granulation].
LAS-H: linear alkyl (C10-C14) benzenesulfonic acid [manufactured by Lion Corporation, Rypon LH-200 (96% by mass pure)].
Polyoxyethylene alkyl ether: ECOROL 26 (trade name, manufactured by ECOGREN; alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (melting point: 40 ° C.). Pure content 90% by mass, moisture content 10% by mass.
Soap: Fatty acid sodium having 12 to 18 carbon atoms (C) [manufactured by Lion Corporation, pure content 67% by mass, titer 40 to 45 ° C .; fatty acid composition C12 0.7% by mass, C14 11.4% by mass, C16 29 2% by weight, C18F0 (stearic acid) 0.7% by weight, C18F1 (oleic acid) 56.8% by weight, C18F2 (linoleic acid) 1.2% by weight; molecular weight 289].
MES-Na powder (α-sulfo fatty acid alkyl ester salt powder): fatty acid chain length carbon number; C16 / C18 = 8/2 (mass ratio), active ingredient = 75 mass%, zeolite 12 mass%, moisture 5 .5%, average particle size 500 μm, [manufactured by Lion Eco Chemicals, trade name: MIZULAN]
AOS-K: α-olefin potassium sulfonate having an alkyl group having 14 to 18 carbon atoms, pure 53%, manufactured by Lion Corporation. Sodium silicate: sodium silicate 2 (pure 40%, SiO 2 / Na 2 O ratio ( Molar ratio) = 2.5). Made by Fuji Chemical Co., Ltd.
LAS-K: linear alkylbenzene sulfonic acid, Raipon LH-200 (AV value (mg number of potassium hydroxide required to neutralize 1 g of LAS-H) = 180.0) in slurry for preparing spray-dried particles Neutralized with 48% by mass potassium hydroxide solution, manufactured by Lion Co., Ltd. (the amount in the table indicates the mass% as LAS-K)

-Alkaline agent Potassium carbonate: Potassium carbonate (powder) (manufactured by Asahi Glass Co., Ltd.) average particle size 490 μm, bulk density 1.30 g / cm ³ ).
Sodium carbonate: granular ash (manufactured by Asahi Glass Co., Ltd.) average particle size 320 μm, bulk density 1.07 g / cm ³ ).
Sodium hydrogen carbonate: manufactured by Penrice Co., Ltd., average particle size of 300 μm.
Inorganic builder Zeolite: Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 μm.

Other components MA agent: Acrylic acid-maleic acid copolymer salt, manufactured by Nippon Shokubai Co., Ltd., trade name “AQUALIC TL-400”, pure content 40% by mass.

Zinc sulfate: Sulfate monohydrate, manufactured by Shinyo Co., Ltd., trade name “Dry Zinc Sulfate (K)”.
Sodium sulfate: sodium sulfate, manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”.
Sodium percarbonate granulated product: manufactured by Zhejiang JINKE CHEMICALS, trade name “SPCC”, effective oxygen amount 13.8% by mass, average particle size 870 μm.

<Coating ingredients>
-Water-insoluble inorganic compound Zeolite: Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 μm.

-Binder Polyoxyethylene alkyl ether: ECOROL 26 (trade name, manufactured by ECOGREN; alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (melting point: 40 ° C). Pure content 90% by mass, moisture content 10% by mass.

Organic chelating agent MGDA (average particle diameter 80 μm): trisodium methylglycine diacetate, manufactured by BASF, trade name “Trilon M Powder”, coordination position 4.
MGDA (average particle diameter 1300 μm): trisodium methylglycine diacetate, manufactured by BASF, trade name “Trilon M Compactate”.

<Production example of granular detergent composition>
According to the composition components and contents (mass%) of the compositions shown in Tables 1 and 2, granular detergent compositions were produced by the following production methods.
In the table, the content of the compounding component indicates a pure equivalent amount.
In the table, “detergent particles” means the following detergent particles (A), detergent particles (B), detergent particles (C), detergent particles (D) or detergent particles (E). "Mass%" here shows content in detergent particle | grains (A), detergent particle | grains (B), detergent particle | grains (C), detergent particle | grains (D), or detergent particle | grains (E).

Detergent particles (A):
MES-Na 11.0% by mass, LAS-Na 2.0% by mass, soap 6.0% by mass, polyoxyethylene alkyl ether 4.0% by mass, zeolite 15.0% by mass, MA agent 2.0% by mass , Potassium carbonate 5.5% by mass, sodium carbonate 30.6% by mass, zinc sulfate 0.5% by mass, mirabilite 15.0% by mass, impurities (from MES paste) 1.4% by mass, water 7.0% by mass

Detergent particles (B):
LAS-Na 13.0% by mass, soap 5.0% by mass, polyoxyethylene alkyl ether 5.0% by mass, zeolite 15.0% by mass, MA agent 2.0% by mass, potassium carbonate 5.5% by mass, Sodium carbonate 32.0 mass%, zinc sulfate 0.5 mass%, mirabilite 15.0 mass%, water 7.0 mass%

Detergent particles (C):
MES-Na 10.0% by mass, LAS-Na 1.8% by mass, soap 5.5% by mass, polyoxyethylene alkyl ether 4.0% by mass, zeolite 15.0% by mass, MA agent 2.0% by mass , Potassium carbonate 5.0% by mass, sodium carbonate 28.4% by mass, zinc sulfate 0.5% by mass, mirabilite 14.5% by mass, sodium percarbonate 5.0% by mass, impurities (from MES paste) 1.3 Mass%, water 7.0 mass%

Detergent particles (D):
MES-Na 8.0 mass%, LAS-Na 1.5 mass%, soap 5.0 mass%, polyoxyethylene alkyl ether 3.0 mass%, zeolite 12.0 mass%, MA agent 2.0 mass% , Potassium carbonate 4.0% by mass, sodium carbonate 22.0% by mass, zinc sulfate 0.5% by mass, mirabilite 10.0% by mass, sodium percarbonate 5.0% by mass, sodium bicarbonate 20.0% by mass, Impurities (derived from MES paste) 1.0% by mass, water 6.0% by mass

Detergent particles (E):
MES-Na powder (trade name: MIZULAN, manufactured by Lion Eco Chemicals) 5.0% by mass, LAS-K 8.0% by mass, AOS-K 6.4% by mass, soap 4.2% by mass, polyoxyethylene Alkyl ether 3.5% by mass, zeolite 12.0% by mass, sodium silicate 3.4% by mass, sodium carbonate 12.5% by mass, zinc sulfate 0.5% by mass, mirabilite 14.5% by mass, sodium percarbonate 10 0.0% by mass, sodium bicarbonate 15.0% by mass, water 5.0% by mass

[Preparation Example of Detergent Particles (A)-Kneading]
Among the compositions shown in the detergent particles (A), all the ingredients except polyoxyethylene alkyl ether, MES paste, a part of zeolite (for grinding aid), and zinc sulfate are prepared at a preparation temperature of 80 ° C. By stirring for 17 minutes, an aqueous slurry having a solid content of 62% by mass was obtained.
Subsequently, the aqueous slurry was spray-dried to prepare spray-dried particles having a water content of 5% by mass.
Along with 75.4 parts by mass of these spray-dried particles, 1.3 parts by mass of polyoxyethylene alkyl ether (water content 10% by mass), 17.5 parts by mass of MES paste (water content 13% by mass), and zinc sulfate 0.5 parts by mass and a small amount (0.8 parts by mass) of tap water (Edogawa-ku, Tokyo) are introduced into a continuous kneader (Kurimoto Iron Works, KRC-S4 type) at a temperature of 55 to 65 ° C. Kneading was continued for 40 seconds.
Next, the kneaded product obtained by the kneading was continuously supplied to a pelleter (made by Fuji powder, die hole diameter 10 mmφ) and extruded to form a pellet-shaped solid detergent.
Thereafter, Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKASO-6 type) was arranged in three stages in series, and the obtained solid detergent and a part of the zeolite (4.5 parts by mass, for grinding aid) Were introduced together with cold air at 15 ° C., and crushed and granulated so that the average particle size was 300 to 500 μm.
The detergent particles (A) thus obtained had a bulk density in the range of 800 to 1000 g / L.

[Preparation example of detergent particles (B)-stirring granulation]
Of the composition shown in the detergent particles (B), all the ingredients except polyoxyethylene alkyl ether and LAS-H are stirred at a preparation temperature of 80 ° C. for 17 minutes, whereby an aqueous solution having a solid content of 62% by mass. A slurry was obtained.
Subsequently, the aqueous slurry was spray-dried to prepare spray-dried particles having a water content of 5% by mass.
Along with 78.4 parts by mass of the spray-dried particles, 5.5 parts by mass of polyoxyethylene alkyl ether (water content 10% by mass), 12.2 parts by mass of LAS-H, 0.5 parts by mass of zinc sulfate, and a small amount (3.4 parts by mass) of tap water (Edogawa-ku, Tokyo) is put into a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.) with a shovel-wall clearance of 5 mm (filling rate 30% by volume) Then, stirring was started at a main shaft of 200 rpm, a chopper of 2000 rpm, and jacket water flow of 20 ° C. At that time, the granulation was carried out while controlling the fluid number (Fr) to 1.2.
Stirring was stopped after 5 minutes from the start of stirring, and the obtained powder was classified using a sieve or the like, and a granulated product having a particle size of 300 to 500 μm was obtained. In addition, when the lump was produced | generated, it classified and used after crushing.
The detergent particles (B) thus obtained had a bulk density in the range of 800 to 850 g / L.

[Production Example of Detergent Particles (C)-Kneading]
After adjusting the components excluding sodium percarbonate in the same manner as the detergent particles (A), the obtained particles and sodium percarbonate were mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, volume 131.7 L). The inner wall surface of the drum has two baffle plates with a clearance of 20 mm and a height of 45 mm. The filling ratio of the horizontal cylindrical rolling mixer is 30% by volume, the rotation speed is 22 rpm, and the temperature is 25 ° C. The mixture was mixed for 1 minute under conditions of 80% relative humidity to obtain detergent particles (C).
The detergent particles (C) thus obtained had a bulk density in the range of 800 to 1000 g / L.

[Production Example of Detergent Particles (D)-Kneading]
After adjusting the components excluding sodium percarbonate and sodium bicarbonate in the same manner as the detergent particles (A), the obtained particles, sodium percarbonate and sodium bicarbonate were mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length). 490 mm in length and 131.7 L in the inner wall of the drum having a clearance between the inner wall of 20 mm and a height of 45 mm, and a filling ratio of the horizontal cylindrical rolling mixer of 30% by volume The mixture was mixed for 1 minute under the conditions of a rotational speed of 22 rpm, a temperature of 25 ° C., and a relative humidity of 80% to obtain detergent particles (D).
The detergent particles (D) thus obtained had a bulk density in the range of 800 to 1000 g / L.

[Production Example of Detergent Particles (E)-Kneading]
After the components except MES-Na powder, sodium percarbonate and sodium hydrogen carbonate were prepared in the same manner as the detergent particles (A), the obtained particles, MES-Na powder, sodium percarbonate and sodium hydrogen carbonate were placed in a horizontal cylinder. Put in a type rolling mixer (having two baffle plates with a clearance of 20 mm and a height of 45 mm on the inner wall of the drum with a cylinder diameter of 585 mm, a cylinder length of 490 mm, and a volume of 131.7 L). Detergent particles (E) were obtained by mixing for 1 minute under the conditions of a filling rate of 30% by volume of a cylindrical rolling mixer, a rotation speed of 22 rpm, a temperature of 25 ° C., and a relative humidity of 80%.
The detergent particles (E) thus obtained had a bulk density in the range of 800 to 1000 g / L.

Example 1
Detergent particles (A) have two horizontal cylindrical rolling mixers (cylinder diameter 585 mm, cylinder length 490 mm, volume 131.7 L on the drum inner wall surface with two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm. Stuff).
Then, according to the composition shown in Table 1, zeolite (powder) and MGDA (powder) are added, the horizontal cylindrical rolling mixer has a filling rate of 30% by volume, a rotational speed of 22 rpm, a temperature of 25 ° C., a relative humidity of 80 Mixing is started while spraying polyoxyethylene alkyl ether (solution) using a pressure nozzle so that the droplet diameter is 40 to 150 μm, and mixing for 1 minute to obtain a granular detergent composition. Obtained. At that time, the fluid number (Fr ′) was controlled to 0.2.
A blending method in which polyoxyethylene alkyl ether (solution) is mixed while spraying the above detergent particles with zeolite (powder) and MGDA (powder) added and mixed is referred to as “detergent particle coating method 1”. "

(Examples 2 and 3)
A granular detergent composition was obtained in the same manner as in Example 1 except that the blending amount was changed according to the composition shown in Table 1.

(Examples 4 and 7 to 9)
A granular detergent composition was obtained in the same manner as in Example 1 except that the detergent particles (A) were changed to the detergent particles (B), (C), (D), or (E).

(Example 5)
Detergent particles (A) have two horizontal cylindrical rolling mixers (cylinder diameter 585 mm, cylinder length 490 mm, volume 131.7 L on the drum inner wall surface with two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm. Stuff).
Next, according to the composition shown in Table 1, zeolite (powder) is added, and mixing is started under the conditions of a filling ratio of 30% by volume of the horizontal cylindrical rolling mixer, a rotation speed of 22 rpm, a temperature of 25 ° C., and a relative humidity of 80%. Then, using a pressure nozzle, polyoxyethylene alkyl ether (solution) was added while spraying so that the droplet diameter was 40 to 150 μm, and mixed for 1 minute. At that time, the fluid number (Fr ′) was controlled to 0.2.
Thereafter, MGDA (powder) was added separately, and mixed for 1 minute under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, a temperature of 25 ° C., and a relative humidity of 80% to obtain a granular detergent composition.
A blending method in which zeolite (powder) is added to the detergent particles and mixed while spraying polyoxyethylene alkyl ether (solution) and then MGDA (powder) is added separately and mixed is referred to as “detergent particles”. Coating method 2).

(Example 6)
A granular detergent composition was obtained in the same manner as in Example 1 except that MGDA (average particle size 80 μm) was changed to MGDA (average particle size 1300 μm).

(Comparative Examples 1-3, 5)
A granular detergent composition was obtained in the same manner as in Example 1 except that the blending components and blending amounts were changed according to the composition shown in Table 2.

(Comparative Example 4)
The detergent particles (B) were used as they were as the granular detergent composition.

(Comparative Example 6)
In the preparation example of the detergent particles (A) described above, when spray-dried particles, polyoxyethylene alkyl ether, MES paste, zinc sulfate, and tap water are put into a continuous kneader (Kurimoto Iron Works, KRC-S4 type), Detergent particles (hereinafter referred to as “detergent particles (A ′)”) were prepared in the same manner except that the coating components (three components having the same blending ratio as in Example 1) were also added at the same time. (A ′) was used as is.

(Comparative Example 7)
The detergent particles (C) were used as they were as the granular detergent composition.

(Comparative Example 8)
As the granular detergent composition, the detergent particles (D) were used as they were.

(Comparative Example 9)
The detergent particles (E) were used as they were as the granular detergent composition.

<Evaluation of granular detergent composition>
About the granular detergent composition of each example, evaluation of "dust generation" and "fluidity" was performed by the evaluation method shown below, respectively. The results are shown in Tables 1 and 2.

[Evaluation of dust generation]
LD-3 type digital dust meter (trade name, Shibata) capable of measuring the amount of fine powder (dust) generated in the granular detergent composition in the upper part of a container 40 cm high x 30 cm wide x 30 cm deep Scientific Instruments Industry Co., Ltd.) was installed.
Then, the atmosphere in the container is maintained at a temperature of 25 ° C. and a relative humidity of 60%, and 50 g of the granular detergent composition is dropped into the container from the sample inlet provided in the upper part of the container. At the same time, the digital dust meter The switch was turned on and the dust count after 5 minutes of standing was read.
Dust generation was evaluated based on the following evaluation criteria using the dust count as an index. Considering the feeling of use at home in particular, A, B, and C are preferable, and A and B are particularly preferable.
Evaluation criteria A: The dust count number was 500 or less.
B: The dust count was more than 500 and 800 or less.
C: The dust count was more than 800 and 1500 or less.
D: The dust count was over 1500.

[Evaluation of fluidity]
The fluidity was evaluated by measuring the angle of repose (°) by the following method.
Place an acrylic measuring instrument with a horizontal cover (height 10 cm x depth 10 cm x width 3 cm) with an angle scale on a flat surface, and the horizontal cover (height 10 cm x width 3 cm side of the measuring instrument) ) Was closed, and the granular detergent composition of each example was poured into the measuring device from the position where the height from the upper surface of the measuring device was 1 to 2 cm.
When the granular detergent composition was in a heaped state with a height from the upper surface of the measuring device exceeding about 0 to 1 cm, the lateral lid was gently opened, and the granular detergent composition was naturally discharged by gravity.
After discharging, the angle (tilt angle) formed by the surface (inclined surface) of the granular detergent composition remaining in the measuring instrument and the horizontal surface was read from the scale. The angle of repose measured in this way was obtained by performing the above operation three times and using the average value. And fluidity | liquidity was evaluated based on the following evaluation criteria. In particular, from the viewpoint of manufacturability, A and B are preferable.
In addition, the said measuring instrument made from acrylic used the thing which the horizontal cover was provided in one of the side surfaces which height and width make, and the scale of the angle was written in the side surface which height and depth made.
Evaluation criteria A: The angle of repose was 60 ° or less.
B: The angle of repose was more than 60 ° and 70 ° or less.
C: The angle of repose was more than 70 ° and 80 ° or less.
D: The angle of repose was more than 80 °.

  From the results shown in Tables 1 and 2, it can be seen that all of the granular detergent compositions of Examples 1 to 9 are less likely to generate dust and have excellent fluidity even when the surfactant is at a low concentration.

  ADVANTAGE OF THE INVENTION According to this invention, even if surfactant is a low density | concentration, it can provide the granular detergent composition which is hard to generate dust, and is excellent in fluidity | liquidity, and its manufacturing method.

Claims (8)

Detergent particles containing a surfactant and an alkali agent are coated with at least one organic chelating agent selected from methylglycine diacetate and salts thereof, a water-insoluble inorganic compound, and a binder. Granular detergent composition. Granular detergent composition according to claim 1, wherein the water-insoluble inorganic compound is a zeolite. The granular detergent composition according to claim 1 or 2 , wherein the surfactant is at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant. The granular detergent composition according to any one of claims 1 to 3 , wherein the alkaline agent is at least one alkaline agent selected from the group consisting of sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. The granular detergent composition according to any one of claims 1 to 4 , wherein the binder is a polyoxyalkylene alkyl ether. The granular detergent composition as described in any one of Claims 1-5 whose mixing ratio of the said water-insoluble inorganic compound and the said binder is a water-insoluble inorganic compound / binder = 1-10 by mass ratio. The mixing ratio of the water-insoluble inorganic compound and the organic chelating agent is, as a mass ratio, water-insoluble inorganic compound / organic chelating agent = 0.4 to 20, according to any one of claims 1 to 6. Granular detergent composition. A method of manufacturing a granular detergent composition according to any one of claims 1 to 7
A granular detergent characterized by coating detergent particles containing a surfactant and an alkali agent with at least one organic chelating agent selected from methyl glycine diacetic acid and salts thereof, a water-insoluble inorganic compound, and a binder. A method for producing the composition.