JP2011219739A - Method of manufacturing granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a granular detergent composition excellent in solubility to water even when the content of a surfactant is in a low concentration less than 30 mass%.SOLUTION: The method of manufacturing the granular detergent composition containing less than 30 mass% of the surfactant, an inorganic builder, and an alkali agent includes: a pretreatment process for mixing the surfactant, the inorganic builder, and the alkali agent to prepare the mixture having a water content below 15 mass%; and a granulation process for blending a sulfate hydrate and an organic chelator containing a nitrogen atom in a molecular into the mixture and granulating the resultant mixture.

Description

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

In general, a granular detergent composition is prepared by spray-drying an aqueous slurry in which raw materials such as a surfactant and a builder are mixed in advance to prepare spray-dried particles. (Extruding and pulverizing) or granulating with stirring.
Conventionally, as a method for producing a granular detergent composition, for example, a detergent slurry is prepared using an anionic surfactant, a part of a nonionic surfactant and other raw materials, and the obtained slurry is used as a countercurrent spray drying tower. The dried product and the remaining nonionic surfactant and water are introduced into a continuous kneader and kneaded to obtain a kneaded product. A manufacturing method is disclosed in which a Japanese product is extruded, formed into a cylindrical pellet, introduced into a speed mill, and pulverized (for example, see Patent Documents 1 and 2).

JP 2003-105378 A JP 2000-006139 A

By the way, 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 connection with this, the compounding ratio of the inorganic builder or alkali agent in detergent is increasing.
However, in the conventional method for producing a granular detergent composition as described in Patent Documents 1 and 2, when the surfactant concentration is low, the detergent particles are dissolved when the produced granular detergent composition is dissolved in water. Causes gelation / aggregation, resulting in poor water solubility, and the granular detergent composition remains undissolved in the laundry tub or on the article to be washed.

  This invention is made | formed in view of the said situation, and provides the manufacturing method of the granular detergent composition which is excellent in the solubility with respect to water even if content of surfactant is less than 30 mass% and a low density | concentration. This is the issue.

As a result of intensive studies, the inventors of the present invention have found that when the surfactant concentration is low in the production of the granular detergent composition, the detergent particles in which the detergent raw materials are mixed unevenly are prepared, so that the solubility in water becomes poor. I understood. On the other hand, the present inventors have further studied, and by blending a detergent raw material mixture having a specific water content with a sulfate hydrate and a specific organic chelating agent, granulation is performed. Has been found to solve the problem, and the present invention has been completed.
That is, the present invention relates to a method for producing a granular detergent composition containing less than 30% by weight of a surfactant, an inorganic builder and an alkaline agent, and the surfactant, the inorganic builder and the alkaline agent are mixed, A pretreatment step of preparing a mixture having a content of 15% by mass or less, a granulation step of granulating by blending the mixture with a sulfate hydrate and an organic chelating agent containing a nitrogen atom in the molecule; It is a manufacturing method of the granular detergent composition characterized by having.
In the manufacturing method of the granular detergent composition of this invention, it is preferable that the said organic chelating agent is a compound represented by the following general formula (III).

［式中、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、それぞれ独立して水素原子、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。］

[Wherein 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 independently 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. ]

  According to the method for producing a granular detergent composition of the present invention, the solubility in water is excellent even when the surfactant content is less than 30% by mass.

  The method for producing a granular detergent composition of the present invention is a method for producing a granular detergent composition containing less than 30% by weight of a surfactant, an inorganic builder and an alkaline agent, and includes a pretreatment step and a granulation step which will be described later. Have. In the granulation step, sulfate hydrate and an organic chelating agent containing a nitrogen atom in the molecule are blended.

(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 (preferably 12 to 18) or an ester salt thereof (preferably a methyl ester salt (MES), an ethyl ester salt or a propyl ester salt).
Among these, as the anionic surfactant, since the washing performance is improved, an α-sulfo fatty acid salt or an ester salt thereof, and a linear or branched alkylbenzene having an alkyl group having 8 to 18 carbon atoms It is preferable to use soap together with at least one selected from the group consisting of sulfonates, and it is more preferable to use soap together with at least one selected from MES and LAS. In the granular detergent composition, the mixing ratio of MES, LAS and soap is preferably 0.5 to 5 and more preferably 1 to 3 in terms of mass ratio represented by (MES + LAS) / soap. “Mass ratio represented by (MES + LAS) / soap” indicates the ratio of the total content (mass%) of MES and LAS to the soap content (mass%) in the granular detergent composition.

Nonionic surfactant Nonionic surfactants include, for example, those shown below.
An average of 3 to 30 moles, preferably an average of 5 to 20 moles, particularly preferably an average of 12 to 18 moles of an alkylene oxide having 2 to 4 carbon atoms was added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl ether or polyoxyalkylene 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 (IV), 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 ··· (IV)
[In the formula (IV), 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 these, as the nonionic surfactant, the melting point is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and HLB is preferably 7 to 16, more preferably 8 to 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 may be used individually by 1 type and may be used in combination of 2 or more type.
Among the above, it is preferable to use an anionic surfactant and a nonionic surfactant in combination because the surfactant improves the cleaning performance. In the granular detergent composition, the mixing ratio of the anionic surfactant and the nonionic surfactant is preferably 0.5 to 10 in terms of a mass ratio represented by the anionic surfactant / nonionic surfactant, 8 is more preferable, and 3 to 5 is even more preferable. "Mass ratio represented by anionic surfactant / nonionic surfactant" is the content of anionic surfactant (mass%) relative to the content of nonionic surfactant (mass%) in the granular detergent composition. Indicates the ratio.
The content of the surfactant in the granular detergent composition is less than 30% by mass, preferably 5 to 28% by mass, and more preferably 10 to 25% by mass.
The present invention has technical significance for the production of a granular detergent composition having a surfactant content of less than 30% by mass. Thus, even if content of surfactant is less than 30 mass% and low concentration, according to this invention, the granular detergent composition excellent in the solubility with respect to water can be manufactured.
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.

(Inorganic builder)
The inorganic builder is not particularly limited as long as it is conventionally used in a detergent composition for clothing, for example, crystalline aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, etc.) , Amorphous aluminosilicates; orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phytates, etc .; crystalline silicates, carbonates and amorphous alkali metals A complex with silicate can be mentioned.
An inorganic builder may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the inorganic builder in the granular detergent composition 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 at a pre-processing process 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.

(Alkaline agent)
The alkaline agent is not particularly limited as long as it is conventionally used in a detergent composition for clothing, for example, carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate, potassium bicarbonate and the like. Bicarbonates; double salts such as potassium carbonate; silicates such as sodium silicate and potassium silicate; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
An alkali agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the alkaline agent in the granular detergent composition 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.

(Sulfate hydrate)
The number of water molecules in the sulfate hydrate is preferably 1 to 9 because gelation / aggregation of the detergent particles is less likely to occur when the granular detergent composition is dissolved in water, and is easily available. 2-9 are more preferable and 5-7 are still more preferable.
The sulfate hydrate preferably has a dehydration temperature of 40 to 280 ° C, more preferably 40 to 120 ° C, still more preferably 41 to 80 ° C, and 50 to 75 ° C. Particularly preferred. The solubility with respect to the water of a granular detergent composition improves that a dehydration temperature is below a preferable upper limit, More preferably, it is 80 degrees C or less. Further, when the dehydration temperature is at least the preferred lower limit value, more preferably at least 41 ° C., the storage stability when the granular detergent composition is stored for a long period of time becomes better.

This sulfate hydrate is dehydrated once during granulation to improve the manufacturability of the granulated product, and after granulation, the sulfate hydrates again as the temperature decreases, improving the stability of the granulated product. Estimated to contribute. When a granulated product obtained by granulation is measured by DSC, an endothermic peak corresponding to sulfate hydrate is observed.
“Dehydration temperature of sulfate hydrate” indicates a value observed by transition point measurement by DSC. The dehydration temperature is determined by setting the temperature at the peak top of the endothermic peak obtained by DSC. For the DSC measurement, any commercially available heat flow rate type or heat guarantee type may be used. As an example of measurement, α-alumina is used as a reference, and sulfate hydrate is arranged on the sample side. Measurement temperature range: 0 to 100 ° C., temperature increase rate: 2 ° C./min. The dehydration temperature is a peak top temperature of an endothermic peak of 10 mJ / min or more observed at 20 ° C. or more. When there are a plurality of endothermic peaks, the endothermic peak observed on the highest temperature side of 100 ° C. or lower is defined as the dehydration temperature.
In addition, about the sulfate hydrate which does not have an endothermic peak in 100 degrees C or less, a dehydrating temperature is computed by changing a measurement temperature range into 0-300 degreeC, and measuring similarly.

The sulfate in the sulfate hydrate is preferably one that dissolves in water and releases metal ions.
The metal that provides the metal ions is preferably a simple substance produced by a group 3-12 metal element in the long-period periodic table, more preferably a simple substance produced by a group 7-12 metal element.
Specific examples of the sulfate include copper sulfate, zinc sulfate, manganese sulfate, iron sulfate, cobalt sulfate, nickel sulfate, vanadium sulfate, and silver sulfate. Among them, from the influence on the environment and easy availability. Copper sulfate, zinc sulfate, and manganese sulfate are preferable.

A sulfate hydrate may be used individually by 1 type, and may be used in combination of 2 or more type.
Among the above, as sulfate hydrate, gelation and aggregation of detergent particles are less likely to occur when the granular detergent composition is dissolved in water, so copper sulfate pentahydrate, zinc sulfate hexahydrate. At least one selected from the group consisting of zinc sulfate heptahydrate, manganese sulfate pentahydrate and manganese sulfate heptahydrate is preferred, and zinc sulfate heptahydrate is most preferred.

The content of the sulfate hydrate in the granular detergent composition is preferably 0.01 to 3% by mass, more preferably 0.02 to 0.8% by mass, and 0.2 to 0.00. More preferably, it is 6 mass%.
When the content of the granular detergent composition is not less than 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 Will improve. On the other hand, if it is below the upper limit value, the blending effect is sufficiently obtained.

(Organic chelating agent containing nitrogen atom in the molecule)
Examples of the organic chelating agent containing a nitrogen atom in the molecule (hereinafter simply referred to as “organic chelating agent”) include aminocarboxylic acid or a salt thereof, hydroxyaminocarboxylic acid or a salt thereof.
Specific examples of the organic chelating agent include ethylenediaminetetraacetic acid or a salt thereof, β-alanine diacetic acid or a salt thereof, compounds represented by the following general formulas (I) to (III), and the like.

［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 general formula (I), X represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom.
Examples of the alkali metal atom include sodium and potassium.
Examples of the alkaline earth metal 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.

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 represented by the following chemical formula (1) is preferable because stirring (kneading and kneading) of the detergent raw material can be performed better. 2-pyridinecarboxylic acid) or a salt thereof, 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 general formula (II), X ^{1 to} X ⁴ may be the same or different, and each is a hydrogen atom, an alkali metal atom, or an alkaline earth metal. Represents an atom or a cationic ammonium group.
In X ^{1 to} X ⁴ , examples of the alkali metal atom and the alkaline earth metal atom are the same as the alkali metal atom and the alkaline earth metal atom in X in the formula (I).
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 general formula (II), R represents a hydrogen atom or a hydroxyl group, and is preferably a hydroxyl group.
Q represents a hydrogen atom or an alkyl group.
In Q, the alkyl group preferably has 1 to 4 carbon atoms, and 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.
n ₁ represents an integer of 0 or 1, and is preferably 1.

  Among the compounds represented by the general formula (II), a compound represented by the following chemical formula (3) is preferable because stirring (kneading and kneading) of the detergent raw material can be performed more favorably. 2,2′-iminodisuccinic acid) or a salt thereof, or 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 general formula (III), Y represents an alkyl group, a hydroxyl group or a hydrogen atom.
In Y, the alkyl group preferably has 1 to 4 carbon atoms, and 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.

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.
In X ^{5 to} X ⁷ , the alkali metal atom, the alkaline earth metal atom and the cationic ammonium group include an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group in X ^{1 to} X ⁴ in the formula (II). Any of the same groups may be 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), a compound represented by the following chemical formula (5) is preferable because stirring (kneading and kneading) of the detergent raw material can be performed more favorably. Nitrilotriacetic acid), a compound represented by the following chemical formula (6) (methylglycine diacetate (MGDA)), a compound represented by the following chemical formula (7) (serine diacetate), or a salt thereof. Of these, methylglycine diacetic acid or a salt thereof is more preferable.

When the compounds represented by the general formulas (I) to (III) are blended in the granulation step, part or all of the terminal group “—COOX” becomes “—COO ⁻ ”. It is considered that it acts as a binder during stirring (kneading kneading).

An organic chelating agent may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these, as the organic chelating agent, the compound represented by the general formula (III) is preferable because stirring (kneading and kneading) of the detergent raw material can be performed particularly favorably, and methylglycine diacetic acid or its Most preferred are salts.
The organic chelating agent is preferably used as it is because it has a good blending effect and is easy to handle during blending.

The content of the organic chelating agent in the granular detergent composition is preferably 0.01 to 1.5% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0.5%. It is more preferable that it is mass%, and it is especially preferable that it is 0.2-0.4 mass%.
When the content in the granular detergent composition is at least the lower limit value, the detergent raw material can be well stirred (kneaded and kneaded), and the detergent raw material is more uniformly mixed. As a result, the solubility of the granular detergent composition in water is improved. On the other hand, if it is below an upper limit, stirring (kneading kneading | mixing) of a detergent raw material can be performed favorably, and a compounding effect will fully be acquired.

In particular, when methylglycine diacetic acid or a salt thereof is used as the organic chelating agent, the content of methylglycine diacetic acid or a salt thereof in the granular detergent composition is preferably 0.01 to 1.5% by mass, More preferably, it is 0.1-0.5 mass%.
When the content of methylglycine diacetic acid or a salt thereof is in the above range, the solubility of the granular detergent composition in water is particularly improved. This is considered to be because the efficiency of stirring (kneading kneading) of the detergent raw material is particularly increased by setting the content of methylglycine diacetic acid or a salt thereof in the above range.

The mixing ratio of the sulfate excluding water molecules of the sulfate hydrate and the organic chelating agent is a molar ratio represented by sulfate / organic chelating agent, and sulfate / organic chelating agent = 350/1 to 1/1 /. 150 is preferable, 50/1 to 1/20 is more preferable, and 5/1 to 1/1 is particularly preferable.
When the molar ratio is not less than the lower limit (the ratio of sulfate increases), gelation / aggregation of the detergent particles hardly occurs when dissolved in water, while it is not more than the upper limit (ratio of organic chelating agent) When the detergent material is increased, the detergent material can be well stirred (kneaded and kneaded), and the detergent material is easily mixed uniformly.

(Other ingredients)
The granular detergent composition produced by the production method of the present invention requires the detergent, inorganic builder, alkaline agent, sulfate hydrate and other detergent raw materials other than the organic chelating agent containing a nitrogen atom in the molecule. It may be contained accordingly.
Other detergent materials include those commonly used in detergent compositions for clothing, for example, organic builders excluding organic chelating agents containing nitrogen atoms in the molecule; sulfites, thiosulfates, etc. Reducing agents: Particle strength retention agents such as sulfates, optical brighteners, UV absorbers, enzyme agents, bleaches, bleach activators, bleach activation catalysts, softeners such as bentonite, carboxymethylcellulose salts, etc. Contamination (deposition) inhibitors, foam control agents, fragrances, surface modifiers, and oil absorbing agents are included.
In particular, a granular detergent composition containing a combination of a percarbonate or perborate as a bleaching agent and an organic peracid precursor as a bleaching activator is preferable because of its excellent bleaching effect.
Examples of the percarbonate include sodium percarbonate, and examples of the perborate include sodium perborate.
Examples of organic peracid precursors include alkanoyloxybenzenesulfonate (sodium 4-dodecanoyloxybenzenesulfonate (OBS12), sodium 4-nonanoyloxybenzenesulfonate, etc.), alkanoyloxybenzoic acid (4-decanoyloxy). Benzoic acid (OBC10) and the like), polyacylated alkylenediamine (N, N, N ′, N′-tetraacetylethylenediamine (TAED) and the like) and the like.
Examples of organic builders excluding organic chelating agents containing nitrogen atoms in the molecule include polyacrylates, acrylic acid-maleic acid copolymer salts, citrates, polyacetal carboxylates, and the like. Acid-maleic acid copolymer salts are preferred. The content of the organic builder in the granular detergent composition is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and further preferably 3 to 6% by mass. When the content of the organic builder is equal to or higher than the lower limit, the solidification preventing property during long-term storage is improved. On the other hand, if it is below the upper limit value, the blending effect is sufficiently obtained.

[Pretreatment process]
In the pretreatment step, the surfactant, the inorganic builder, and the alkali agent are mixed to prepare a mixture having a water content of 15% by mass or less.
As a method for mixing the detergent raw material, a conventionally known method is used. For example, a method of preparing a detergent slurry by uniformly mixing a surfactant, an inorganic builder, an alkaline agent and other detergent raw materials with water; A method of preparing a granulated product while mixing a builder, an alkali agent and other detergent materials; a method of simply mixing a surfactant, an inorganic builder, an alkali agent and other detergent materials.
The usage amount of the surfactant, inorganic builder and alkaline agent is a part or all of the predetermined blending amount, and the usage amount when blending a part of the predetermined blending amount is appropriately determined throughout the whole process. Good.

The mixture of the detergent raw materials prepared in this step has a water content of 15% by mass or less, preferably 1 to 10% by mass, and more preferably 2 to 8%. When the water content of the mixture is 15% by mass or less, the blending effect of the sulfate hydrate and the organic chelating agent blended in the next granulation step can be obtained.
The method for controlling the water content in the detergent raw material mixture is, for example, a method of spray-drying a detergent slurry, a method of drying the detergent raw material after mixing in the method of simply mixing, or mixing. A method for controlling the water content of each detergent raw material in advance is mentioned.
In the present invention, the moisture content is a value measured with an infrared moisture meter (manufactured by Kett Scientific Laboratory) at a sample surface of 5 g and a sample surface temperature of 130 ° C. for 20 minutes.

[Granulation process]
In the granulation step, the mixture obtained in the pretreatment step is blended with sulfate hydrate and an organic chelating agent containing a nitrogen atom in the molecule for granulation.
In this step, by mixing the sulfate hydrate and the organic chelating agent into a mixture having a specific water content, the detergent raw material is well stirred (kneaded and kneaded) and sheared into the detergent raw material. A sufficient force can be applied, and the detergent raw material can be uniformly mixed.

As the granulation method in the present invention, a conventionally known crushing granulation method (kneading / extrusion / pulverization), stirring granulation method, rolling granulation method and the like can be used.
Among them, since the shearing force applied to the detergent raw material is large and the detergent raw material is easily mixed uniformly, the crushing granulation method (kneading / extrusion / pulverization) and the stirring granulation method are preferable, and the crushing granulation method (kneading) -Extrusion / pulverization is particularly preferred.

When the crushing granulation method (kneading / extrusion / pulverization) is used as the granulation method in this step, granulation is performed as follows.
For example, using a kneading and kneading machine such as a continuous or batch kneader, the sulfate hydrate, the organic chelating agent, and other components are blended into the mixture obtained in the pretreatment step. Perform kneading.
The blending order of the sulfate hydrate and the organic chelating agent is not particularly limited, and may be blended separately or premixed.
Examples of other components 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 better, 0.01 to 10 parts by mass of water is preferably added to 100 parts by mass of the mixture obtained in the pretreatment step. It is more preferable to add 1 to 5 parts by mass of water, and it is more preferable to add 0.5 to 2 parts by mass 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.
Subsequently, the kneaded material obtained by the kneading kneading is extruded from a small hole using an extruder to obtain a pellet.
Then, a granular detergent composition is manufactured by grind | pulverizing the obtained pellet-form thing using hammers, such as a Fitzmill and a speed mill, and a cutter mill type grinder, and performing granulation.
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. Preferably, the average particle size is less than 200 μm, more preferably less than 50 μm, and still more preferably less than 10 μm.
In addition, the average particle diameter in a grinding | pulverization adjuvant can be calculated | required similarly to the average particle diameter of the below-mentioned granular detergent composition. However, when the particle diameter is smaller than 150 μm, it is a value measured by a laser light scattering method (for example, a particle size distribution measuring device (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.)), and average particles The diameter is a volume-based median diameter.

Further, when the agitation granulation method is used as the granulation method, the mixture obtained in the pretreatment step, the sulfate hydrate, the organic chelating agent, and other components are conventionally known batchwise or continuous. A granular detergent composition is produced by introducing into a stirring granulator of the formula and stirring.
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.
When the fluid number is 1 or more, consolidation is promoted. On the other hand, when the fluid number is 4 or less, 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 ].

The manufacturing method of the granular detergent composition of this invention may have other processes other than the pre-processing process and granulation process which were mentioned above.
Examples of the other steps include a step of coating the surface of the granulated product obtained in the granulation step with zeolite, a surfactant, a fragrance or the like.

The average particle size of the granular detergent composition produced by the production method of the present invention is preferably 200 to 1500 μm, and more preferably 250 to 1000 μm. When the average particle size is 200 μm or more, dusting is suppressed during use. On the other hand, the solubility to water improves that it is 1500 micrometers or less.
In addition, an average particle diameter can be confirmed by the method of calculating | requiring a particle size distribution using a sieve, and calculating from the particle size distribution as shown below.

[Measurement method of average particle size]
First, the measurement object (sample) is classified using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, first, the 9-stage sieve is stacked above the pan so that the openings gradually increase, and a sample of 100 g / time is placed on the top of the sieve having the top opening of 1680 μm. Next, it was covered and attached to a low-tap type sieve shaker (manufactured by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and after shaking for 10 minutes, it remained on each sieve and saucer. Samples are collected for each mesh and the sample mass 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%) is calculated from the following formula (1), where c is the sum of the mass frequency from the screen to a μm sieve and c% is the mass frequency on the a μm sieve.

The bulk density of the granular detergent composition produced by the production method of the present invention is preferably 0.3 g / cm ³ or more, more preferably 0.5 to 1.2 g / cm ³ , still more preferably 0.00. 6 to 1.1 g / cm ³ . When the bulk density is 0.3 g / cm ³ or more, the space (storage location) required for storing the granular detergent composition can be reduced, which is advantageous. On the other hand, if it is 1.2 g / cm ³ or less, the solubility of the granular detergent composition in water will be good.
In addition, the said bulk density shows the value measured according to JISK3362-1998.

According to the method for producing the granular detergent composition of the present invention described above, the solubility in water is excellent even when the surfactant content is as low as less than 30% by mass. The reason why such an effect is obtained is not clear, but is estimated as follows.
In the method for producing a granular detergent composition, when the surfactant concentration is low, there is little surfactant acting as a binder when granulating, so the shearing force applied to the detergent raw material by stirring (kneading kneading) is weakened. Thereby, detergent particles in which the detergent raw materials are mixed non-uniformly are prepared, and in particular, the surfactant tends to be unevenly distributed in the detergent particles.
In the granular detergent composition produced by the conventional production method, when the surfactant is unevenly distributed, the detergent particles are gelled because the surfactant concentration is high when the surfactant is unevenly distributed. It is considered that the solubility in water was deteriorated by causing aggregation of the detergent particles. This problem has not been solved even when the operation is performed with the power of the kneading and kneading machine such as a kneader being increased during granulation.
In the production method of the present invention, when granulation is carried out, gelation / aggregation of detergent particles is less likely to occur by adding sulfate hydrate to a detergent raw material mixture having a specific water content. This is because, in the detergent particles, there is a sulfate hydrate having water molecules around the surfactant, so that the surfactant in the detergent particles becomes a large amount when the granular detergent composition is used. Since gelation is less likely to occur even when in contact with water, or because stirring (kneading kneading) is well performed with water dehydrated from sulfate hydrate, it is difficult for uneven distribution of surfactants to occur. Conceivable.
Further, in the production method of the present invention, when granulating, a specific organic chelating agent is blended with a detergent raw material mixture having a specific water content, thereby mixing at the time of stirring (kneading kneading). Becomes better. This is presumably because the specific organic chelating agent easily interacts with the detergent raw material in water and acts as a binder when the detergent raw material is agitated (kneading kneading).
When granulation is performed, the effect of mixing both the above-described sulfate hydrate and the specific organic chelating agent is exerted, so that it is difficult for the surfactant to be unevenly distributed in the detergent particles. Therefore, it is considered that the granular detergent composition produced by the production method of the present invention is excellent in solubility in water.

  In addition, the method for producing the granular detergent composition of the present invention is a granular detergent composition that meets the demands required in recent years due to changes in the laundry situation and increased environmental awareness, such as reducing the amount of surfactant used and saving water. Is a suitable method for producing

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.
The composition of the granular detergent composition manufactured by the manufacturing method of each example is shown in Tables 1-3.
The raw materials used in this example are as follows.

Surfactant MES-Na: α-sulfo fatty acid alkyl ester salt-containing paste [paste composition: 63% by mass of α-sulfo fatty acid alkyl ester salt, 16% by mass of nonionic surfactant (polyoxyethylene alkyl ether described later), di Salt and methyl sulfate 8% by mass impurities, 13% by mass moisture], α-sulfo fatty acid alkyl ester salt fatty acid chain lengths of 16 and 18 carbons, a mixture of 16 and 18 carbons Ratio C16 / C18 = 8/2 (molar 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% by mass)] [Pretreatment step] The compound neutralized with 48 mass% sodium hydroxide aqueous solution at the time of the aqueous slurry preparation in.
LAS-H: linear alkyl (C10-C14) benzenesulfonic acid [manufactured by Lion Corporation, Lipon LH-200 (LAS-H pure content 96% by mass)].
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 mass%, C18F0 (stearic acid) 0.7 mass%, C18F1 (oleic acid) 56.8 mass%, C18F2 (linoleic acid) 1.2 mass%; molecular weight 289].

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.

-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 (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ ).

Sulfate hydrate Zinc sulfate heptahydrate: Zinc sulfate (Mitsui Metal Mining Co., Ltd.) heptahydrate, average particle size 580 μm, dehydration temperature 73 ° C.
Copper sulfate pentahydrate: Copper (II) sulfate pentahydrate (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) reagent special grade, average particle size 530 μm, dehydration temperature 45 ° C.
Zinc sulfate monohydrate: manufactured by Horiike Sangyo Co., Ltd., trade name “ZNS-13”, average particle size 200 μm, dehydration temperature 270 ° C.

・ Comparative component of sulfate hydrate Sulfate anhydride: Zinc sulfate (trade name, manufactured by Wako Pure Chemical Industries, Ltd.).

-Organic chelating agent containing nitrogen atom in the molecule Methyl glycine diacetate (powder): Trisodium methyl glycine diacetate, manufactured by BASF Japan Ltd., trade name “Trilon M Powder”, coordination position 4, average particle size 80 μm; Pure content 87% by mass.
Methyl glycine diacetic acid (compactate): trisodium methyl glycine diacetate, manufactured by BASF Japan Ltd., trade name “Trilon M Compactact”, coordination position 4, average particle size 1300 μm; pure content 86 mass%.
Hydroxyiminodisuccinic acid tetrasodium: HIDS (trade name, manufactured by Nippon Shokubai Co., Ltd.) dried to a powder of 5% by mass and powdered, pure content of 95% by mass.

Other components Sodium sulfate: neutral anhydrous sodium sulfate A0 (trade name, manufactured by Shikoku Kasei Co., Ltd.).
Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
Acrylic acid-maleic acid copolymer salt: Aqualic TL-400 (trade name, manufactured by Nippon Shokubai Co., Ltd.)
Fluorescent whitening agent: Chinopearl CBS-X / Chinopearl AMS-GX = 3/1 (mass ratio) (trade name, manufactured by Ciba Japan Co., Ltd.).
Enzyme A: A mixture of protease (sabinase 12T) / lipase (LIPEX100T) / amylase (stainzyme 12T) (all manufactured by Novozymes Japan Ltd.) = 5/4 (mass ratio).
Enzyme agent B: Protease (sabinase 12T) / Amylase (Stainzyme 12T) / Lipase (LIPEX100T) / Cellulase (CellClean 4500T) (all manufactured by Novozymes Japan Ltd.) = 4/1/4 (mass ratio) ).
Sodium percarbonate granulated product: manufactured by Zhejiang JINKE CHEMICALS, trade name “SPCC”, effective oxygen amount 13.8% by mass, average particle size 870 μm.
Granulated product of bleach activator: mass ratio of OBS12 (sodium 4-dodecanoyloxybenzenesulfonate), PEG6000, AOS (sodium α-olefinsulfonate having 14 carbon atoms) and A-type zeolite powder 70/20/5/5 granulated product. It was prepared as follows.

First, sodium 4-dodecanoyloxybenzenesulfonate was synthesized as a bleach activator. Sodium p-phenolsulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Ltd.), lauric acid chloride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and acetone (Kanto Chemical Co., Ltd.) Synthesis was carried out by the following method using a reagent manufactured by the company.
100 g (0.46 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of dimethylformamide, and lauric acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a magnetic stirrer.
After completion of the dropwise addition, the reaction was carried out for 3 hours. Dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), washed with acetone, and then recrystallized in a water / acetone (= 1/1 mol) solvent. . The yield was 90%.
70 parts by mass of sodium 4-dodecanoyloxybenzenesulfonate thus obtained, 20 parts by mass of PEG 6000 [polyethylene glycol # 6000M (manufactured by Lion Corporation)], 14-carbon α-olefin sodium sulfonate powder product (Lipolane PJ- 400 (manufactured by Lion Co., Ltd.)) is supplied to the Extrude Ohmic EM-6 model manufactured by Hosokawa Micron Co., Ltd. so as to have a ratio of 5 parts by mass, and is kneaded and extruded (kneading temperature 60 ° C.) to give a diameter of 0. An 8 mmφ noodle-like extruded product was obtained.
This extruded product (cooled to 20 ° C. with cold air) was introduced into Fitzmill DKA-3 manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of A-type zeolite powder was similarly supplied as an auxiliary agent and pulverized to obtain an average particle size. Gave a granulation product of about 700 μm of bleach activator.

  Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.

<Production example of granular detergent composition>
According to the compounding components and contents (mass%) of the compositions shown in Tables 1 to 3, granular detergent compositions were produced by the following production methods (crushed granulation and stirring granulation), respectively.
In the table, the contents of zinc sulfate heptahydrate, copper sulfate pentahydrate and zinc sulfate monohydrate indicate the amount as a hydrated salt containing water molecules. About methyl glycine diacetate (powder) and methyl glycine diacetate (compactate), all show the quantity (pure equivalent amount) of methyl glycine diacetate. The other compounding components indicate pure equivalent amounts.
The “common composition” indicates a common composition S1, a common composition S2, and a common composition S3 described below. "Mass%" here shows content in a granular detergent composition. “Balance” means the content of sodium carbonate in the composition formulated such that the total amount of each component contained in the granular detergent composition is 100% by mass.

Common composition S1:
MES-Na 8.0 mass%, LAS-Na 3.0 mass%, polyoxyethylene alkyl ether 5.0 mass%, soap 7.0 mass%, sodium carbonate balance, potassium carbonate 10.0 mass%, sodium sulfate 5.0% by mass, sodium sulfite 1.0% by mass, zeolite 20.0% by mass, acrylic acid-maleic acid copolymer salt 2.0% by mass, fluorescent whitening agent 0.02% by mass, water 7.0% by mass , Enzyme agent A 1.0% by mass, sodium percarbonate granulated product 6.0% by mass, bleach activator granulated product 0.5% by mass

Common composition S2:
LAS-H 17.0% by mass, polyoxyethylene alkyl ether 5.0% by mass, soap 7.0% by mass, sodium carbonate balance, sodium sulfate 25.0% by mass, zeolite 20.0% by mass, acrylic acid-malein Acid copolymer salt 4.0% by mass, optical brightener 0.02% by mass, water 7.0% by mass, enzyme A 1.0% by mass, sodium percarbonate granulated product 6.0% by mass, bleach activation Granules 0.5% by mass

Common composition S3:
MES-Na 9.0% by mass, LAS-Na 1.0% by mass, polyoxyethylene alkyl ether 4.0% by mass, soap 5.0% by mass, sodium carbonate balance, potassium carbonate 4.0% by mass, sodium sulfate 13.0% by mass, zeolite 15.0% by mass, acrylic acid-maleic acid copolymer salt 2.0% by mass, fluorescent whitening agent 0.1% by mass, water 7.0% by mass, enzyme agent B 1.0% by mass %, Sodium percarbonate granulated product 10.0% by mass, bleach activator granulated product 0.5% by mass, perfume 0.3% by mass

(Examples 1 to 10, 12, 13, 15, 16)
[Pretreatment process]
Among the compositions shown in the table, polyoxyethylene alkyl ether, MES-Na, part of zeolite (for grinding aid, for post-mixing step), enzyme agent, sodium percarbonate granulated product, bleaching activity All ingredients except for granulating agent, perfume, zinc sulfate heptahydrate, copper sulfate pentahydrate or zinc sulfate monohydrate, and methylglycine diacetate powder or compactate By stirring at 80 ° C. for 17 minutes, an aqueous slurry having a solid content of 62% by mass was obtained.
In addition, a part of the zeolite (for the grinding aid and for the post-mixing step) represents 30% by mass of the total amount of the zeolite.
Subsequently, the aqueous slurry was spray-dried to prepare spray-dried particles having a water content of 5% by mass.

[Granulation process]
Along with the spray-dried particles obtained in the drying step, a part of polyoxyethylene alkyl ether, MES-Na, zinc sulfate heptahydrate or copper sulfate pentahydrate or zinc sulfate monohydrate, methyl Glycine diacetate powder or compact and a small amount (1 part by mass with respect to 100 parts by mass of the spray-dried particles) of tap water (Edogawa-ku, Tokyo), a continuous kneader (manufactured by Kurimoto Steel Works, KRC S4 type) and kneaded and kneaded continuously at a temperature of 55 to 65 ° C. for 40 seconds.
Next, the kneaded material obtained by the kneading kneading was extruded while being continuously fed to a pelleter (made by Fuji Powder, die hole diameter 10 mmφ) to form a pellet-shaped solid detergent.
After that, Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKASO-6 type) was placed in series, and the solid detergent and a part of the zeolite (for grinding aid) were introduced into it together with cold air at 15 ° C. The granulated product was obtained by pulverizing and granulating so that the average particle size was 300 to 500 μm.
In addition, a part of said polyoxyethylene alkyl ether remove | excludes the part used by a post-mixing process, and shows 70 mass% part of polyoxyethylene alkyl ether whole quantity.

[Post-mixing process]
The granulated product obtained in the granulation step, the remaining polyoxyethylene alkyl ether (30% by mass), a part of the zeolite (for post-mixing step), an enzyme agent, and sodium percarbonate granulation And a bleach activator granulated product, a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, inner wall surface clearance: 20 mm, height: 45 mm) The mixture was mixed for 1 minute under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. to prepare a granular detergent composition of each example. At that time, only the polyoxyethylene alkyl ether (30% by mass) was added using a pressure nozzle while spraying so that the droplet diameter was 40 to 150 μm. In Examples 15 and 16, the fragrance was added while spraying at the same time.
The granular detergent composition obtained in each example had a bulk density in the range of 0.82 to 0.92 g / cm ³ .
The average particle size was measured by the same method as the above [Measuring method of average particle size] (hereinafter the same). The bulk density was measured by a method according to JIS K3362-1998 (hereinafter the same).

(Example 11)
[Pretreatment process]
Of the compositions shown in the table, LAS-Na, part of zeolite (for granulation aid, for post-mixing step), enzyme agent, sodium percarbonate granule, bleach activator granule All the ingredients except zinc sulfate heptahydrate and methylglycine diacetic acid powder were stirred at a preparation temperature of 80 ° C. for 17 minutes to obtain an aqueous slurry having a solid content of 62% by mass.
In addition, a part of the zeolite (for the grinding aid and for the post-mixing step) represents 30% by mass of the total amount of the zeolite.
Subsequently, the aqueous slurry was spray-dried to prepare spray-dried particles having a water content of 5% by mass.

[Granulation process]
Spray-dried particles obtained in the drying step, zeolite (for granulation aid, 25% by mass of the total amount of zeolite), LAS-H, part of polyoxyethylene alkyl ether, and zinc sulfate heptahydrate A mixture of methyl glycine diacetate powder and a small amount of tap water (1 part by mass with respect to 100 parts by mass of the spray-dried particles) (Edogawa-ku, Tokyo) (Matsubo Co., Ltd., Model M20) was charged (filling rate: 30% by volume), and 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 by controlling the fluid number (Fr) to 0.2.
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.
In addition, a part of said polyoxyethylene alkyl ether remove | excludes the part used by a post-mixing process, and shows 70 mass% part of polyoxyethylene alkyl ether whole quantity.

[Post-mixing process]
The granulated product obtained in the granulation step, the remaining polyoxyethylene alkyl ether (30% by mass), a part of the zeolite (for post-mixing step), an enzyme agent, and sodium percarbonate granulation And a bleach activator granulated product, a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, inner wall surface clearance: 20 mm, height: 45 mm) The granular detergent composition of each example was manufactured by mixing for 1 minute under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. At that time, only the polyoxyethylene alkyl ether (30% by mass) was added using a pressure nozzle while spraying so that the droplet diameter was 40 to 150 μm.
The obtained granular detergent composition had an average particle size of 410 μm and a bulk density of 0.80 g / cm ³ .

(Example 14)
A granular detergent composition was produced in the same manner as in the production method of Example 1 except that in the granulation step, tetrasodium hydroxyiminodisuccinate was blended in place of methylglycine diacetate powder.

(Comparative Example 1)
A granular detergent composition was produced in the same manner as in the production method of Example 1 except that methylglycine diacetate powder was not blended in the granulation step.

(Comparative Example 2)
A granular detergent composition was produced in the same manner as in the production method of Example 2, except that zinc sulfate heptahydrate was not blended in the granulation step.

(Comparative Example 3)
Granularity is the same as in the production method of Example 1, except that none of the zinc sulfate heptahydrate or copper sulfate pentahydrate and the methylglycine diacetic acid powder or compactate are blended in the granulation step. A detergent composition was prepared.

(Comparative Example 4)
The production method of Example 1 except that zinc sulfate heptahydrate and methylglycine diacetic acid powder were blended not in the kneading kneading in the granulation step but in the preparation of the aqueous slurry in the pretreatment step. A granular detergent composition was produced in the same manner as described above.

(Comparative Example 5)
A granular detergent composition was produced in the same manner as in the production method of Example 1, except that zinc sulfate anhydride was blended in place of zinc sulfate heptahydrate in the granulation step.

(Comparative Example 6)
A granular detergent composition in the same manner as in the production method of Example 1 except that zinc sulfate monohydrate was blended in place of zinc sulfate heptahydrate in the granulation step and methylglycine diacetate powder was not blended. The thing was manufactured.

(Comparative Example 7)
A granular detergent composition in the same manner as in the production method of Example 1 except that zinc sulfate heptahydrate and methylglycine diacetate powder were blended in the post-mixing step, not in the kneading kneading in the granulation step. The thing was manufactured.

<Evaluation of granular detergent composition>
About the granular detergent composition obtained by the manufacturing method of each example, evaluation of "solubility in water" was performed by the following cloth adhesion evaluation method. The results are also shown in Tables 1-3.

Cloth adhesion evaluation method:
Put 30L of tap water at 5 ° C into a two-tank washing machine (CW-C30A1-H, manufactured by Mitsubishi Electric Corporation), 6 cotton shirts, 2 polyester shirts and 2 acrylic shirts (collectively these The bath ratio was adjusted to 20 times using a "washing object"), and the shirts were folded and floated on the water surface in a stacked state.
Then, 30 g of granular detergent composition was placed near the center of the uppermost stacked shirt, and the entire laundry object was immersed for 5 minutes, and then drained by stirring for 5 minutes with a weak water flow. . After draining, the laundry object was dehydrated for 1 minute.
Then, the undissolved residue of the granular detergent composition remaining in the washing object and the two-tank washing machine was picked up, and the undissolved amount was visually observed and evaluated based on the following evaluation criteria. From the viewpoint of usability at home, an evaluation of B or higher is preferable for practical use.
(Evaluation criteria)
A: No undissolved residue was observed.
B: Although there is some undissolved residue, it fell clean if it was wiped off.
C: A small lump of about 1 mm ³ was included in the unmelted residue, and it remained faintly white even when it was removed.
D: There were innumerable small lumps of about 1 mm ^{3 in the} unmelted residue, and it remained so white that it was noticeable even if it was removed.
E: Aggregated undissolved residue was present and re-washing was necessary.

  From the evaluation results shown in Tables 1 to 3, the granular detergent compositions produced by the production methods of Examples 1 to 16 were all compared even when the surfactant content was as low as less than 30% by mass. It turns out that it is excellent in the solubility with respect to water compared with the granular detergent composition manufactured by the manufacturing method of Examples 1-7.

Claims (2)

In the method for producing a granular detergent composition containing less than 30% by weight of a surfactant, an inorganic builder and an alkaline agent,
A pretreatment step of mixing the surfactant, the inorganic builder, and the alkali agent to prepare a mixture having a water content of 15% by mass or less;
A method for producing a granular detergent composition, comprising the step of granulating the mixture by blending a sulfate hydrate and an organic chelating agent containing a nitrogen atom in the molecule. The method for producing a granular detergent composition according to claim 1, wherein the organic chelating agent is a compound represented by the following general formula (III).

[Wherein 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 independently 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. ]