JPWO2011118340A1 - Granulated product of bleach activator and method for producing the same - Google Patents

Abstract

The present invention relates to a bleach activator (A), an organic binder (B), an anionic surfactant (C), a nonionic surfactant (D) having a melting point of less than 45 ° C., and a sulfate. A bleach activator granulated product containing 1 to 9 hydrate (E) and a nitrogen-containing chelating agent (F); a kneading step of kneading the components (A) to (F); It is related with the manufacturing method of the bleaching activator granulated product which has the extrusion granulation process which performs extrusion granulation using the kneaded material obtained at the said kneading | mixing process. According to the present invention, there are provided a bleach activator granule excellent in solubility in water and storage stability, and a method for producing a bleach activator granule that is less likely to generate fine powder during grinding. can do.

Description

The present invention relates to a granulated product of a bleach activator that is a component that enhances the bleaching effect of an oxygen bleaching component and a method for producing the same.
This application claims priority on March 26, 2010 based on Japanese Patent Application No. 2010-072671 for which it applied to Japan, and uses the content here.

For washing clothes and the like, detergent compositions and bleaching compositions are used.
Some of these compositions exhibit a bleaching effect by an oxidation reaction. As the oxidation reaction component responsible for this oxidation reaction, hydrogen peroxide, oxygen-based bleaching components such as percarbonate that dissolve in water to generate hydrogen peroxide, or chlorine-based bleaching components such as sodium hypochlorite are used. It has been. Recently, oxygen-based bleaching components have attracted attention because they can be used easily.
In order to enhance the bleaching effect, bleach activators such as organic peracid precursors and bleach activation catalysts are used in combination with oxygen-based bleaching components.

A bleaching activator tends to have a reduced bleaching activation ability due to the interaction with other components in the above composition due to storage over time. Therefore, the bleach activator is generally used as a granulated product from the viewpoint of ensuring storage stability.
So far, a bleach activator granulated product produced by granulating using a bleach activator, a water-soluble binder (organic binder) and an anionic surfactant has been proposed (for example, Patent Documents 1 to 3).
Further, a bleaching activator granulated product containing a specific organic peracid precursor and a magnesium salt has been proposed (see Patent Document 4). In the invention described in Patent Document 4, a magnesium salt having a hydration number as low as possible (especially an anhydride) is preferably used from the viewpoint of the effect of magnesium (suppression of inhibition by calcium ions). .

JP-A-9-217089 JP-A-9-272900 JP-A-8-3593 JP 2002-338999 A

However, in the methods described in Patent Documents 1 to 4, the granulated product (extruded product) tends to be too hard. For this reason, when crushing or crushing for the purpose of sizing (hereinafter, these are collectively referred to as “pulverization”), the power of the pulverizer increases, and impact and shear force are strongly applied to the granulated product. There is a problem that fine powder is easily generated. Further, the granulated product still has insufficient solubility in water (particularly, solubility in water at a low temperature of 10 ° C. in a short time (within 5 minutes)).
In the method described in Patent Document 4, the bleaching activation ability tends to be lowered due to storage over time, and the storage stability is insufficient.

  The present invention has been made in view of the above circumstances, and is a bleach activator granulated product excellent in solubility in water and storage stability, and further a bleach activator that is less likely to generate fine powder during grinding. It is an object to provide a method for producing a granulated product.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the bleaching activator granulated product according to the first aspect of the present invention comprises a bleaching activator (A), an organic binder (B), an anionic surfactant (C), and a melting point of 45 ° C. It contains less nonionic surfactant (D), sulfate 1-9 hydrate (E), and nitrogen-containing chelating agent (F).
In the bleaching activator granulated product according to the first aspect of the present invention, the nitrogen-containing chelating agent (F) is preferably 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し；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し；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 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or a cation. It represents sex ammonium group; _{n 2} is an integer of 0-5. ]

  In the bleaching activator granulated product according to the first aspect of the present invention, the bleaching activator (A) is represented by the following general formula (11), the following general formula (12). It is preferably at least one compound selected from the group consisting of a compound and a compound represented by the following chemical formula (13).

［式中、Ｒ_１及びＲ_２は、それぞれ独立に炭素数７以上の直鎖状アルキル基であり；Ｍは塩形成カチオン又は水素原子である。］

[Wherein, R ₁ and R ₂ are each independently a linear alkyl group having 7 or more carbon atoms; M is a salt-forming cation or a hydrogen atom. ]

  In the bleaching activator granulated product according to the first aspect of the present invention, the organic binder (B) is preferably polyethylene glycol having an average molecular weight of 400 to 30,000.

  In the bleaching activator granulated product according to the first aspect of the present invention, the anionic surfactant (C) is a linear or branched alkylbenzene sulfonate (a linear or branched alkyl group). Has an average carbon number of 8-18.), Long-chain alkyl sulfonate (average carbon number of long-chain alkyl group is 10-20), long-chain olefin sulfonate (average of long-chain olefin moiety) Carbon number is 10-20), long-chain monoalkyl sulfate ester salt (average carbon number of long-chain monoalkyl group is 10-20), α-sulfo fatty acid ester salt (average carbon of fatty acid residue) It is preferably at least one compound selected from the group consisting of 12 to 20.

In the bleaching activator granulated product according to the first aspect of the present invention, the nonionic surfactant (D) is ethylene glycol or ethylene oxide 3 per mole of the aliphatic alcohol having 8 to 20 carbon atoms. It is preferably a polyethylene glycol-added nonionic surfactant to which 80 mol has been added and has a melting point of less than 45 ° C.

In the bleaching activator granulated product according to the first aspect of the present invention, the sulfate 1-9 hydrate (E) is vanadium sulfate heptahydrate, manganese sulfate pentapentahydrate, sulfuric acid. Manganese heptahydrate, nickel sulfate heptahydrate, copper sulfate pentapentahydrate, zinc sulfate monohydrate, zinc sulfate hexahydrate, and zinc sulfate heptahydrate Preferably, it is a hydrate of at least one sulfate selected from.

  The bleaching activator granulated product production method according to the second aspect of the present invention is the bleach activator granulated product producing method according to the first aspect of the present invention, wherein the bleach activator is prepared as described above. (A), the organic binder (B), the anionic surfactant (C), the nonionic surfactant (D), and the sulfate 1-9 hydrate (E) And a kneading step of kneading and kneading the nitrogen-containing chelating agent (F), and an extrusion granulation step of performing extrusion granulation using the kneaded product obtained in the kneading step. .

  In the present invention, the “melting point” refers to a value measured by a melting point measurement method described in JIS K0064-1992 “Measuring Method of Melting Point and Melting Range of Chemical Products”.

The bleaching activator granulated product according to the first aspect of the present invention is excellent in water solubility and storage stability.
In addition, according to the method for producing a bleaching activator granulated product in the second aspect of the present invention, bleaching activator granulation that hardly generates fine powder during pulverization and has excellent solubility in water and storage stability. Can manufacture things.

<Granulated bleach activator>
The granulated bleach activator according to the first aspect of the present invention comprises a bleach activator (A), an organic binder (B), an anionic surfactant (C), and a melting point of less than 45 ° C. A nonionic surfactant (D), a sulfate 1-9 hydrate (E), and a nitrogen-containing chelating agent (F) are contained.

[Bleaching activator (A)]
Examples of the bleach activator (A) (hereinafter also referred to as “component (A)”) include organic peracid precursors, bleach activation catalysts, and the like.
Organic peracid precursor, which reacts with hydrogen peroxide generated from peroxides such as sodium percarbonate to produce organic peracids with strong bleaching power, thereby exerting a bleaching effect on clothing, etc. It is.
Examples of the organic peracid precursor include carboxylic acid esters such as alkanoyloxybenzenesulfonic acid, alkanoyloxybenzoic acid, and salts thereof; polyacylated alkylenediamine such as tetraacetylethylenediamine; 1,5-diacetyl-2,4- N-acylated triazines such as dioxohexahydro-1,3,5-triazine, acylated glycolurils such as tetraacetylglycoluril, N-acylated caprolactams such as acetylcaprolactam; hydantoin, hydrazide, triazole, hydrotriazole, Examples thereof include carboxylic anhydrides such as urazole, diketopiperazine, sulfurylamide, cyanurate and phthalic anhydride; acylated sugar derivatives such as pentaacetylglucose.

  Preferred examples of the organic peracid precursor include a compound represented by the following general formula (11), a compound represented by the following general formula (12), and a compound represented by the following chemical formula (13) (N , N, N ′, N′-tetraacetylethylenediamine).

［式中、Ｒ_１及びＲ_２は、それぞれ独立に炭素数７以上の直鎖状アルキル基であり；Ｍは塩形成カチオン又は水素原子である。］

[Wherein, R ₁ and R ₂ are each independently a linear alkyl group having 7 or more carbon atoms; M is a salt-forming cation or a hydrogen atom. ]

In the above formula, R ₁ is preferably a linear alkyl group having 8 to 18 carbon atoms, and more preferably a linear alkyl group having 9 to 15 carbon atoms.
In the above formula, R ₂ is preferably a linear alkyl group having 8 to 18 carbon atoms, and more preferably a linear alkyl group having 9 to 15 carbon atoms.
In the above formula, M is preferably an alkali metal atom such as sodium or potassium, or an amine such as ammonium or alkanolamine, more preferably an alkali metal atom.
In the above formula, the bonding position between the SO ₃ M group and the COOM group may be any of the ortho, meta, and para positions, and the para position is preferred.

The bleach activating catalyst is for activating hydrogen peroxide generated from a peroxide such as sodium percarbonate to enhance the bleaching effect.
Examples of the bleach activating catalyst include a metal ion complex catalyst. Specific examples include pyridine-2,6-dicarboxylic acid-Cu complex.

(A) A component can be used individually by 1 type or in mixture of 2 or more types.
Among these, when producing a granulated product of the bleach activator, the effect of the present invention is remarkable and the technical significance is higher, and therefore, an organic peracid precursor is preferable as the component (A).
In the bleaching activator granulated product, the content of the component (A) is preferably 30 to 60% by mass, more preferably 35 to 60% by mass, and particularly preferably 40 to 55% by mass.
When the content of the component (A) is 30% by mass or more, when blended into the detergent composition or bleach composition, the blended amount of the granulated product does not increase too much, and it is easy to achieve a blending balance with other raw materials. Become. For example, in the case of a detergent composition, since a detergent raw material can be sufficiently blended, a cleaning effect derived from the detergent raw material can be obtained satisfactorily. On the other hand, when the content of the component (A) is 60% by mass or less, the blending balance with other raw materials is maintained, and the storage stability is improved.

[Organic binder (B)]
The organic binder (B) (hereinafter also referred to as “component (B)”) is preferably a water-soluble organic compound that functions as a binder, is solid at room temperature, and melts when heated.
Among these, as the component (B), an organic compound having a melting point of 25 to 100 ° C. is more preferable, an organic compound having a melting point of 25 to 80 ° C. is more preferable, and an organic compound having a melting point of 40 to 80 ° C. is particularly preferable. Is most preferably an organic compound having a temperature of 45 to 75 ° C.
However, the component (B) does not include the component (C), the component (D), the component (E), and the component (F) in the present invention.

Specific examples of the component (B) include polyethylene glycol, polypropylene glycol, block polymers of ethylene oxide and propylene oxide, and nonionic surfactants having a melting point of 45 ° C. or higher. Among them, polyethylene glycol is preferable, Polyethylene glycol having an average molecular weight of 400 to 30000 is more preferable, polyethylene glycol having an average molecular weight of 1000 to 20000 is further preferable, and polyethylene glycol having an average molecular weight of 4000 to 20000 is particularly preferable.
Here, “average molecular weight” indicates a value in terms of polyethylene glycol conversion by gel permeation chromatography.

(B) A component can be used individually by 1 type or in mixture of 2 or more types.
In the bleaching activator granulated product, the content of the component (B) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 8 to 20% by mass.
When the content of the component (B) is 3% by mass or more, fine powder is less likely to be generated during pulverization in the production of the bleach activator granulated product. In addition, the solubility and storage stability of the bleach activator granulated product are improved. On the other hand, when the content of the component (B) is 30% by mass or less, the blending balance with the component (A) is particularly maintained, and the bleaching effect is improved.

[Anionic surfactant (C)]
As an anionic surfactant (hereinafter also referred to as “component (C)”), for example, a linear or branched alkylbenzene sulfonate (the average carbon number of the linear or branched alkyl group is 8 to 8). 18), long chain alkyl sulfonate (the average carbon number of the long chain alkyl group is 10-20), long chain olefin sulfonate (the average carbon number of the long chain olefin portion is 10-20). Long chain monoalkyl sulfate ester salt (average carbon number of long chain monoalkyl group is 10 to 20), polyoxyethylene long chain alkyl ether sulfate salt (average polymerization degree of oxyethylene group is 1) The average carbon number of the long-chain alkyl group is 10 to 20), polyoxyethylene alkylphenyl ether sulfate ester salt (the average degree of polymerization of the oxyethylene group is 3). The average carbon number of the alkyl group is 6 to 12.), α-sulfo fatty acid ester salt (the average carbon number of the fatty acid residue is 12 to 20); long-chain monoalkyl, dialkyl or sesqui Alkyl phosphate; polyoxyethylene monoalkyl, dialkyl, sesquialkyl phosphate and the like are used.
Among these, as the component (C), a linear or branched alkylbenzene sulfonate (the average carbon number of the linear or branched alkyl group is 8 to 18), a long chain alkylsulfone. Acid salt (average carbon number of long chain alkyl group is 10-20), long chain olefin sulfonate (average carbon number of long chain olefin part is 10-20), long chain monoalkyl sulfate ester Salt (average carbon number of long-chain monoalkyl group is 10-20), α-sulfo fatty acid ester salt (average carbon number of fatty acid residue is 12-20), and long-chain alkylsulfonic acid Particularly preferred are salts (the average carbon number of the long-chain alkyl group is 10 to 20) and long-chain olefin sulfonates (the average carbon number of the long-chain olefin moiety is 10 to 20).
The above “long chain” means a group having 10 to 20 carbon atoms, may be linear or branched, and may have a saturated or unsaturated bond.
Here, the “average carbon number” is a compound having a hydrocarbon group, and when compounds having different carbon numbers of the hydrocarbon group are mixed, the total number of carbon atoms of the corresponding hydrocarbon group in all the compounds is It represents the number of carbon atoms converted per molecule (total number of carbon atoms of the corresponding hydrocarbon group in all compounds / number of molecules). “Fatty acid residue” represents a partial structure obtained by removing an alkoxy group from a fatty acid ester.
Examples of the form of the salt in component (C) include alkali metal salts such as sodium and potassium, amine salts, ammonium salts and the like, and alkali metal salts are preferred.

(C) A component can be used individually by 1 type or in mixture of 2 or more types.
In the bleaching activator granulated product, the content of the component (C) is preferably 1 to 15% by mass, more preferably 3 to 12% by mass, and particularly preferably 5 to 10% by mass.
When the content of component (C) is 1% by mass or more, the solubility of the bleach activator granulated product in water is improved. On the other hand, when the content of the component (C) is 15% by mass or less, the blending balance with the component (A) is particularly maintained, and the bleaching effect is improved.

[Nonionic surfactant (D) having a melting point of less than 45 ° C.]
By containing a nonionic surfactant (D) (hereinafter also referred to as “component (D)”) having a melting point of less than 45 ° C., it is easily heated by heating when producing a bleaching activator granulated product. It is melted and mixed with other raw materials, and kneading is performed satisfactorily to prepare a granulated product having an appropriate hardness.
(D) It is preferable that melting | fusing point of a component is 43 degrees C or less, and it is more preferable that it is 15-41 degreeC.
Examples of the component (D) include polyethylene glycol addition type nonionic surfactants and polyethylene glycol-polypropylene glycol addition type nonionic surfactants. Among these, polyethylene glycol addition type nonionic surfactants are exemplified. Preferably, 3 to 80 moles (preferably 5 to 50 moles, more preferably 5 to 30 moles, particularly preferably 5 to 30 moles) of ethylene glycol or ethylene oxide per mole of aliphatic alcohol having 8 to 20 carbon atoms (preferably 10 to 18 carbon atoms) 5 to 20 mol) is added, and a melting point of less than 45 ° C is more preferable.
Specific examples of the component (D) include polyoxyethylene alkyl ethers, preferably those having 5 to 15 moles of ethylene glycol or ethylene oxide added, and alkyl having 12 to 18 carbon atoms. .

(D) A component can be used individually by 1 type or in mixture of 2 or more types.
In the bleaching activator granulated product, the content of the component (D) is preferably 1 to 10% by mass, more preferably 2 to 9% by mass, and particularly preferably 3 to 7% by mass.
When the content of the component (D) is 1% by mass or more, the solubility of the bleach activator granulated product in water is improved. On the other hand, when the content of the component (D) is 10% by mass or less, when the bleaching activator granule is produced, for example, the extrusion pressure at the time of extrusion from the extruder does not become too low, and the shape of the extrudate is retained. Property is improved. And the bleaching activator granule obtained has the physical property which is hard to raise | generate coalescence, and generation | occurrence | production of the adhesion | attachment and solidification in the case of transport is suppressed.

[Sulfate 1-9 hydrate (E)]
The sulfate 1-9 hydrate (hereinafter also referred to as “component (E)”) is preferably a hydrated salt of a group 3-12 metal element in the long-period periodic table, vanadium, manganese, It is more preferably a hydrated salt of nickel, copper or zinc, and even more preferably a hydrated salt of copper or zinc.
The number of water molecules in the hydrated salt is preferably 1 to 7 and more preferably 5 to 7 because the storage stability of the bleach activator granulated product is good.

The component (E) preferably has a dehydration temperature of 41 to 80 ° C, more preferably 45 to 80 ° C, and still more preferably 50 to 75 ° C. When the dehydration temperature is 80 ° C. or lower, the solubility of the bleach activator granulated product in water is improved and fine powder is hardly generated during pulverization. In addition, when the dehydration temperature is 41 ° C. or higher, the storage stability of the bleaching activator granulated product becomes better.
(E) When the bleaching activator granule is produced, the component is dehydrated once during kneading to improve the manufacturability of the granulated product. After granulation, the sulfate is hydrated again as the temperature decreases. It is estimated that this contributes to the improvement of the stability of the granulated product. When the granulated product obtained after granulation is measured by DSC, an endothermic peak corresponding to 1 to 9 hydrate of sulfate is observed.
“Dehydration temperature of component (E)” is 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 a sulfate hydrate is placed 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 hydrate of the sulfate which does not have an endothermic peak below 100 degreeC, it changed and changed the measurement temperature range to 0-300 degreeC, and calculated | required dehydration temperature similarly.

  Specific examples of the component (E) include vanadium sulfate heptahydrate, manganese sulfate pentapentahydrate, manganese sulfate heptahydrate, nickel sulfate heptahydrate, copper sulfate pentapentahydrate, Zinc sulfate monohydrate, zinc sulfate hexahydrate, zinc sulfate heptahydrate can be mentioned. Among them, vanadium sulfate heptahydrate, manganese sulfate pentahydrate, manganese sulfate heptahydrate, nickel sulfate heptahydrate, copper sulfate pentapentahydrate, zinc sulfate hexahydrate Zinc sulfate heptahydrate is preferred. Copper sulfate / pentahydrate, zinc sulfate / hexahydrate, and zinc sulfate / pentahydrate are more preferable.

(E) A component can be used individually by 1 type or in mixture of 2 or more types.
In the bleaching activator granulated product, the content of the component (E) is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, and particularly preferably 9 to 20% by mass.
When the content of the component (E) is 5% by mass or more, the solubility of the bleach activator granulated product in water is improved and fine powder is hardly generated during pulverization. In addition, the bleaching effect of the bleach activator granulated product is easily obtained. On the other hand, when the content of the component (E) is 30% by mass or less, when the bleaching activator granule is produced, for example, the extrusion pressure at the time of extrusion from the extruder does not become too low, and the shape of the extrudate is retained. Property is improved. And the bleaching activator granule obtained has the physical property which is hard to raise | generate coalescence, and generation | occurrence | production of the adhesion | attachment and solidification in the case of transport is suppressed.

[Nitrogen-containing chelating agent (F)]
The nitrogen-containing chelating agent (F) (hereinafter also referred to as “component (F)”) is not particularly limited as long as it is a chelating agent having a nitrogen atom in the molecule. For example, aminocarboxylic acid or a salt thereof, hydroxyaminocarboxylic An acid or its salt is mentioned.
Specific examples of the component (F) include ethylenediaminetetraacetic acid or a salt thereof, β-alanine diacetic acid or a salt thereof, and compounds represented by the following general 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の整数を表し；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し；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し；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し；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; R represents a hydrogen atom or a hydroxyl group; Q represents a hydrogen atom or an alkyl group; 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 Represents 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), preferred are compounds represented by the following chemical formula (1) (2-pyridinecarboxylic acid ( Picolinic 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, And a quaternary ammonium cation such as 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) (2,2′-iminosuccinic acid) is preferable because fine powder is less likely to be generated during pulverization. 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), the compound represented by the following chemical formula (5) (nitrilotriacetic acid) and the following chemical formula are preferable because fine powder is less likely to be generated during pulverization. Examples thereof include a compound represented by (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, for example, a kneading step in producing a bleaching activator granulated product, a part or all of the terminal group “—COOX” It is considered that “—COO ⁻ ” is obtained and the compound acts as a binder.

(F) A component can be used individually by 1 type or in mixture of 2 or more types.
Among the above, as the component (F), a compound represented by the general formula (III) is preferable because fine powder is not particularly easily generated during pulverization, and methylglycine diacetic acid or a salt thereof, nitrilotriacetic acid or Its salt is more preferred, and methylglycine diacetic acid or its salt is most preferred.

In the bleaching activator granulated product, the content of the component (F) is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and particularly preferably 6 to 15% by mass.
When the content of the component (F) is 3% by mass or more, the bleaching effect of the bleach activator granulated product is easily obtained. In addition, fine powder is less likely to be generated during pulverization. On the other hand, when the content of the component (F) is 30% by mass or less, solidification hardly occurs when the bleaching activator granule is stored.

[Other ingredients]
The bleaching activator granulated product in the first aspect of the present invention may contain other components other than the components (A) to (F) described above, as necessary. Examples of other components include those usually used in detergent compositions for clothes and bleaching compositions, such as cationic surfactants, amphoteric surfactants, and aluminosilicates such as zeolite as grinding aids. Acid salts; carbonates such as sodium carbonate and calcium carbonate; silicates such as amorphous silica, calcium silicate and magnesium silicate; other inorganic salts (sodium sulfate, sodium chloride, etc.); medium chain or long chain fatty acids Or a salt thereof; a heavy metal chelating agent other than the component (F) such as 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof; clay mineral, optical brightener, ultraviolet absorber, antioxidant, antibacterial agent, ultra Examples include pigments such as marine blue.
Specific examples of the medium chain or long chain fatty acid include fatty acids having 8 to 10 carbon atoms in the acyl group as the medium chain fatty acid, and long chain fatty acids having 12 to 18 carbon atoms in the acyl group. Fatty acids are mentioned. The “medium chain or long chain” may be linear or branched, and may have a saturated or unsaturated bond. In the bleaching activator granulated product, the content of the medium-chain or long-chain fatty acid is preferably 0.1 to 5% by mass, and more preferably 0.5 to 4% by mass.

The average particle diameter of the bleaching activator granulated product in the first aspect of the present invention is preferably 150 to 2000 μm, and more preferably 200 to 1200 μm.
When the average particle size of the bleaching activator granulated product is not less than the lower limit, powdering is suppressed when the detergent base or the oxygen-based bleaching component is mixed with the powder. On the other hand, the solubility with respect to water improves that the said average particle diameter is below an upper limit.
In the present invention, the “average particle size” can be confirmed by a method of obtaining a particle size distribution using a sieve and calculating from the particle size distribution as shown below.

Measuring 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, the 9-stage sieve is first stacked above the tray so that the openings gradually increase upward, and a sample of 100 g / time is placed on the top of the 1680-μm sieve. 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 size (mass 50%) is obtained from the following formula, where c is the total mass frequency from the screen to a μm sieve and d% is the mass frequency on the a μm sieve.

The bleaching activator granulated product according to the first aspect of the present invention described above is excellent in water solubility and storage stability.
The bleach activator granulated product in the first aspect of the present invention is suitably used as a raw material for a detergent composition containing a detergent base and an oxygen bleaching component, or a bleaching composition containing an oxygen bleaching component. it can.

As the detergent base in the detergent composition, those usually blended in detergent compositions for clothing and the like can be used.
For example, surfactants, alkaline agents, inorganic builders, organic builders, reducing agents such as sulfites and thiosulfates, and particle strength retention agents such as sulfates (preferably sodium sulfate is used as a detergent) 1-20% by mass in the composition), optical brightener, ultraviolet absorber, enzyme agent (eg, protease, lipase, cellulase, amylase, etc.), softener (bentonite, etc.), recontamination (deposition) inhibitor, Examples include foam control agents (such as silicone), fragrances, surface modifiers, oil absorbing agents, antioxidants, antibacterial agents, pigments such as ultramarine blue, and dyes.

(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).

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.

  In addition to the above, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkenyl phenyl ethers, etc. obtained by adding an average of 8 to 20 moles of alkylene oxide having 2 to 4 carbon atoms to an aromatic alcohol having an alkyl group having 8 to 12 carbon atoms Can be mentioned.

Furthermore, the fatty acid alkyl ester alkoxylate represented by the following general formula (IV) etc. which alkylene oxide added between the ester bonds of long-chain fatty acid alkyl ester etc. are mentioned.
R ⁴ CO— (OR ⁵ ) _{n ′} —OR ³ (IV)
[In the formula (IV), R ⁴ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OR ⁵ 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. ]

  Furthermore, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, glycerin fatty acid ester can be mentioned.

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.
Here, “HLB” is a value obtained 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 having 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.

-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 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 surfactants, the surfactant is preferably used in combination with an anionic surfactant and a nonionic surfactant, and more preferably used in combination with MES and polyoxyethylene alkyl ether, since the cleaning performance is improved. .
MES and polyoxyethylene alkyl ether are preferably used in combination with MES / polyoxyethylene alkyl ether (mass ratio) = 95/5 to 60/40, and more preferably in combination with 90/10 to 70/30. .
The content of the surfactant in the detergent composition is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass.
When the content of the surfactant is at least the lower limit value, a good cleaning effect is easily obtained. On the other hand, the solubility with respect to the water of a detergent composition improves that it is below an upper limit.

(Alkaline agent)
The alkali agent is not particularly limited as long as it is conventionally used in a cleaning composition for clothing, for example, carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate, potassium bicarbonate and the like. Bicarbonates such as sodium carbonate; silicates such as sodium silicate and potassium silicate; and 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.
Of these, sodium carbonate and potassium carbonate are preferably used in combination. Sodium carbonate and potassium carbonate are preferably used in combination of sodium carbonate / potassium carbonate (mass ratio) = 95/5 to 60/40, and more preferably in combination of 90/10 to 70/30.
The content of the alkaline agent in the 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 the water of a detergent composition improves that it is below an upper limit.

(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 (for example, 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 A composite with a metal silicate is mentioned.
An inorganic builder can be used alone or in combination of two or more.
The content of the inorganic builder in the 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. On the other hand, when it is not more than the upper limit value, it becomes easy to prevent the detergent particles from solidifying.

(Organic builder)
The organic builder is not particularly limited as long as it is conventionally used in a detergent composition for clothing, for example, nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate. Aminocarboxylates such as salts, methylglycine diacetate and iminodisuccinate; hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine salt; hydroxyacetic acid Hydroxycarboxylates such as salts, tartrate, citrate and gluconate; cyclocarboxylates such as pyromellitic acid salt, benzopolycarboxylate and cyclopentanetetracarboxylate; carboxymethyl tartronate and carboxy Methyloxy succinate, oxydi Ether carboxylates such as succinate, tartaric acid mono- or disuccinate; polyacrylate, salt of acrylic acid-allyl alcohol copolymer, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid such as polyglyoxylic acid ; Acrylic acid polymer such as hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer or salt of copolymer; maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, asparagine Examples include salts of polymers such as acids or copolymers; polysaccharide oxides such as starch, cellulose, amylose, and pectin; and polysaccharide derivatives such as carboxymethylcellulose.
The content of the organic builder in the detergent composition 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.

Among the above-mentioned inorganic and organic builders, the detergency and dirt dispersibility in the washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid It is preferable to use an organic builder such as a maleic acid copolymer salt or a polyacetal carboxylic acid salt in combination with an inorganic builder such as zeolite.
These organic builder and inorganic builder are preferably used in combination of organic builder / inorganic builder (mass ratio) = 5/95 to 30/70, more preferably 10/90 to 20/80.
10-40 mass% is preferable from the point which provides sufficient washing | cleaning performance, and, as for the total content of the inorganic builder and organic builder in a detergent composition, 15-25 mass% is more preferable.

Examples of the oxygen bleaching component in the detergent composition include percarbonates such as sodium percarbonate and perborates such as sodium perborate.
The content of the oxygen bleaching component in the detergent composition is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and even more preferably 5 to 10% by mass from the viewpoint of imparting a sufficient bleaching effect.

In the detergent composition, the content of the bleach activator granulated product in the first embodiment of the present invention is preferably 0.1 to 10% by mass from the viewpoint of imparting a sufficient bleaching effect, 0.3 to 7 mass% is more preferable and 0.5-5 mass% is further more preferable.
In the detergent composition, the mixing ratio of the oxygen bleaching component and the bleach activator granule is preferably oxygen bleaching component / bleach activator granulation (mass ratio) = 20/1 to 1/1. 15/1 to 2/1 is more preferable, and 10/1 to 3/1 is still more preferable.

  The manufacturing method of a detergent composition can be manufactured with a well-known manufacturing method. For example, the surfactant and optional components can be dispersed and dissolved in water and then spray-dried to obtain powdered surfactant particles. In addition, for example, the surfactant and optional components are subjected to kneading, extrusion, stirring granulation, rolling granulation, etc., and subjected to kneading, granulation, compression molding, etc., and further pulverized as necessary Thus, a desired form of the detergent composition can be obtained.

  Moreover, the bleaching agent composition containing the bleaching activator granulated product in the first aspect of the present invention and a percarbonate such as sodium percarbonate or a perborate such as sodium perborate as an oxygen bleaching component. Since the thing is excellent in the bleaching effect, it is especially preferable.

<Method for producing bleach activator granulated product>
The method for producing a bleaching activator granule according to the second aspect of the present invention is the method for producing a bleaching activator granulated product according to the first aspect of the present invention, wherein the above (A) to (F) ) A kneading step for kneading the components, and an extrusion granulation step for carrying out extrusion granulation using the kneaded product obtained in the kneading step.

[Kazuwa process]
In the kneading step, the components (A) to (F) are kneaded.
The method for performing the kneading is not particularly limited, and examples thereof include a method using a conventionally known batch type or continuous type kneader.

In the case of using a batch-type kneader, for example, a horizontal type having a stirring blade rotating in the longitudinal direction, the component (A), the component (E), the component (F), and the component (C). The mixture is introduced into the chamber, and then the components (B) and (D) melted together are introduced into the horizontal chamber and kneaded to obtain a kneaded product.
The stirring blade rotates in the vertical direction with respect to the horizontal axis of the horizontal chamber, and the rotation speed is preferably about 120 to 360 rpm. Various types of stirring blades can be used, and among them, a skid type shovel blade is preferable. It is also preferable to use a chopper blade rotating at 3000 to 6000 rpm together with the stirring blade.
Examples of a kneader having a horizontal chamber equipped with such a stirring blade include, for example, a proshear mixer (manufactured by Taiheiyo Kiko Co., Ltd.); a ladyge mixer, a ribbon mixer, a turbulizer, a pug mixer, a Spartan luzer (above, Fuji Paudal Co., Ltd.).

In the case of using a continuous kneader, for example, all the ingredients (A) to (F) are continuously introduced into a hermetic consolidation apparatus (preferably a horizontal continuous kneader), and the consolidation is performed. After mixing the powder in the chemical treatment apparatus or while mixing, the mixture is heated to a temperature at which the component (B) and the component (D) melt (preferably 25 to 100 ° C., more preferably 40 to 80 ° C.) A kneaded product is obtained by applying a shearing force at a temperature and kneading gently.
Alternatively, a hermetic consolidation apparatus (preferably a horizontal continuous kneader) is continuously heated to a temperature at which the components (B) and (D) are melted, and powder mixed therein (A ) To (F) A powder mixture of components is continuously introduced and kneaded and kneaded to obtain a kneaded product.
Such kneading and kneading can be performed using a single-screw or twin-screw kneading extruder in addition to the kneader. Examples of the continuous kneader used here include a KRC kneader manufactured by Kurimoto Steel Corporation, an extruder manufactured by Nara Machinery, and the like.

In the kneading step, the temperature during kneading is preferably equal to or higher than the dehydration temperature of component (E), more preferably 3 ° C. higher than the melting point of component (D), (B It is further preferred that the temperature is 5 to 20 ° C. higher than the melting point of the component.
By performing the kneading at a temperature equal to or higher than the dehydration temperature of the component (E), the extrusion pressure at the time of extrusion from the extruder does not become too low, and the shape retention of the extrudate becomes good.

In addition, the kneading and kneading in the kneading step is preferably performed substantially without adding water.
By performing kneading and kneading substantially without adding water, the storage stability of the bleach activator granulated product is improved.

When kneading the components (A) to (F), it is preferable to use the following components.
The components (A), (C), and (F) are all preferably used as they are because the storage stability of the bleach activator granule is improved.
If (A) component is a normal manufacturing method, an average particle diameter will be obtained with a plate-shaped crystal | crystallization of about 100-1000 micrometers. The average particle size of the component (A) as a raw material used in the production method in the second aspect of the present invention is not particularly limited, but when the average particle size is smaller than 300 μm, solubility in water and storage stability It becomes easy to obtain a bleaching activator granulated product having excellent properties. Therefore, when the average particle size of the component (A) is 300 μm or more, it is preferably used by pulverization by an ordinary method so that the average particle size is smaller than 300 μm, if necessary, and is about 100 to 200 μm. It is more preferable to use after pulverizing.
The component (C) is used by mixing with a slight amount of inorganic salt (sodium chloride, sodium sulfate, aluminosilicate, calcium carbonate, etc.) from the viewpoint that the component (C) itself can be easily powdered. Also good.
As the component (E), a solid or powder having an average particle size of 50 to 300 μm is preferably used, and a solid or powder of 50 to 250 μm is more preferably used. (E) When the average particle diameter of a component is more than a lower limit, the powdering of (E) component itself is suppressed. On the other hand, when the average particle size of the component (E) is not more than the upper limit value, a uniform kneaded product is easily obtained.
As the component (F), a solid or powder having an average particle size of 50 to 200 μm is preferably used, and a solid or powder having 50 to 150 μm is more preferably used. When the average particle size of the component (F) is equal to or greater than the lower limit, the dusting of the component (F) itself is suppressed, and the caking prevention effect due to hygroscopicity is improved. On the other hand, when the average particle size of the component (F) is not more than the upper limit value, a uniform kneaded product is easily obtained.

The blending ratio of the component (A) to the component (D) is a mass ratio represented by (D) / (A), and (D) / (A) = 0.045 to 0.2 is preferable. 05-0.15 is more preferable.
When it is not more than the upper limit of (D) / (A), the blending ratio of the component (A) in the granulated product is increased, and the bleaching effect is improved. The solubility with respect to the water of a bleaching activator granulation improves as it is more than the lower limit of (D) / (A).

The blending ratio of the component (A) to the component (E) is a mass ratio represented by (E) / (A), and preferably (E) / (A) = 0.16 to 0.55. 2-0.5 is more preferable.
When it is below the upper limit of (E) / (A), the extrusion pressure at the time of extrusion from the extruder does not become too low, and the shape retention of the extrudate becomes good. The solubility with respect to the water of the bleaching activator granulation improves as it is more than the lower limit of (E) / (A).

The blending ratio of the component (A) to the component (F) is a mass ratio represented by (F) / (A), and (F) / (A) = 0.12 to 0.5 is preferable. 15 to 0.45 is more preferable.
When the amount is not more than the upper limit of (F) / (A), the storage stability of the bleach activator granulated product is improved, and a good bleaching effect is easily obtained even after storage over time. When it is at least the lower limit of (F) / (A), the bleaching activator granulated product is less likely to be brittle, and fine powder is less likely to be generated during pulverization.
The blending ratio of the component (D) and the component (E) is a mass ratio represented by (D) / (E), and (D) / (E) = 0.2 to 0.7 is preferable. 3-0.6 are more preferable.
When it is not more than the upper limit of (D) / (E), the extrusion pressure at the time of extrusion from the extruder does not become too low, and the shape retention of the extrudate becomes good. The solubility with respect to the water of a bleaching activator granulation improves as it is more than the lower limit of (D) / (E).
The blending ratio of the component (D) to the component (F) is a mass ratio represented by (D) / (F), and (D) / (F) = 0.2 to 0.7 is preferable. 3-0.6 are more preferable.
When it is below the upper limit of (D) / (F), the extrusion pressure at the time of extrusion from the extruder does not become too low, and the shape retention of the extrudate becomes good. When it is at least the lower limit value of (D) / (F), the storage stability of the bleach activator granulated product is improved, and a good bleaching effect can be easily obtained even after storage over time.

The temperature of the kneaded product after the kneading is preferably 56 to 85 ° C, more preferably 60 to 80 ° C.
When the temperature of the kneaded product is equal to or higher than the lower limit, a homogeneous kneaded product is formed, the solubility is improved, and the storage stability is also improved. On the other hand, when the temperature of the kneaded product is not more than the upper limit value, the shape retention after extrusion granulation is improved and the solubility is also improved.

The hardness of the kneaded product after the kneading is preferably 150 to 900 g, and more preferably 200 to 700 g.
If the hardness of the kneaded product is not less than the lower limit value, the kneaded product will not be too soft, and a decrease in solubility due to coalescence after extrusion can be suppressed, while if the hardness of the kneaded product is not more than the upper limit value, Does not become too hard, and it is possible to suppress a decrease in solubility and deterioration in storage stability due to an increase in power during extrusion.
“Hardness of the kneaded material” indicates a value obtained by converting the hardness of the kneaded material into a load, which is measured using a hard meter (Fujiwara Seisakusho).
In order to control the hardness of the kneaded material within the above-mentioned preferable range, for example, the temperature at the time of kneading and kneading may be adjusted, or the blending amount of the component (D) may be adjusted.

[Extrusion granulation process]
In the extrusion granulation step, extrusion granulation is performed using the kneaded material obtained in the kneading step.
Specifically, the kneaded product obtained in the kneading step is put into a uniaxial or biaxial screw kneading extruder to be extruded to form strands such as a cylindrical shape, a prismatic shape, and a triangular shape; a spherical shape, a plate shape, or a noodle shape. Get a granulate.
Especially, it is preferable to extrude the kneaded material obtained in the kneading step through a die in order to obtain a desired diameter. The hole diameter of the die is preferably about 0.5 to 1.4 mm, and more preferably about 0.8 to 1.2 mm.
The extrusion power in the extruder when extruding the kneaded product is preferably 4 to 40 kwh / t, more preferably 5 to 40 kwh / t, still more preferably 6 to 35 kwh / t, and 6 to It is particularly preferred that it is 25 kwh / t. When the extrusion power is 5 kwh / t or more, the storage stability of the obtained bleach activator granulated product is improved. On the other hand, when the extrusion power is 40 kwh / t or less, the extrudate does not become too hard, and it is difficult for fine powder to be generated during pulverization. Moreover, the solubility with respect to the water of a bleaching activator granulated material improves.
Examples of the extruder include pelleter double (manufactured by Fuji Powder Co., Ltd.), twin dome gran (manufactured by Fuji Powder Co., Ltd.), and multi-gran (manufactured by Dalton Co., Ltd.).

Moreover, you may perform operation which performs kneading kneading | mixing in a kneading process, and obtaining extrusion kneading | mixing in an extrusion granulation process with one apparatus. As this method, for example, a method of attaching a mesh plate to the outlet of the kneaded product in a kneading apparatus and passing the mesh plate to obtain a granulated product can be mentioned.
As an apparatus applicable to this method, for example, Extrude Ohmics manufactured by Hosokawa Micron Corporation can be cited.

After extruding and granulating, in order to make the length of the obtained extrudate, using a crusher (crushing granulator) equipped with a high-speed rotary knife cutter, impact and shear force are applied to the extrudate. It is preferable to adjust the size by giving and pulverizing.
The rotation speed of the high-speed rotary knife cutter is preferably about 30 to 100 m / s.
Examples of the pulverizer include a comminator (manufactured by Fuji Paudal Co., Ltd.), a Fitzmill (manufactured by Hosokawa Micron Co., Ltd.), a speed mill (manufactured by Okada Seiko Co., Ltd.) and the like.
By such sizing, the extrudate is preferably made into a granulated product having an average particle diameter of 200 to 700 μm, more preferably 250 to 450 μm. When the particle size of the granulated product is not less than the lower limit, the storage stability of the bleach activator granulated product is improved. On the other hand, when the particle size of the granulated product is not more than the upper limit, the solubility of the bleach activator granulated product in water is improved.

The manufacturing method of the bleaching activator granulated product in the second aspect of the present invention may have other steps other than the kneading step and the extrusion granulating step described above.
Examples of the other process include a process of further covering the surface of the granulated product obtained in the extrusion granulation process.

According to the bleach activator granulated product production method of the second aspect of the present invention described above, a bleach activator can be produced which is less likely to generate fine powder during pulverization and has excellent water solubility and storage stability. The effect that a granule can be manufactured is acquired. The reason why such an effect is obtained is not clear, but is estimated as follows.
As described above, the bleaching activator tends to have a reduced bleaching activation ability due to the interaction with the detergent composition or other components in the bleaching composition due to storage over time. When a bleach activator is blended in, for example, a detergent composition, the bleach activation ability of the bleach activator decreases with time due to contact with the alkaline agent contained in the detergent base. Therefore, conventionally, the storage stability has been improved by preparing a close granulated product in which the bleaching activator is sufficiently coated with an organic binder or an anionic surfactant. However, on the other hand, the strength of the granulated product is excessively high and too hard, so that the solubility in water is reduced, and in the case of pulverization, impact and shear force are strongly applied, so fine powder is likely to be generated. There's a problem. Thus, until now, it has been difficult to satisfy both storage stability, solubility in water, and generation of fine powder during pulverization.
In the production method according to the second aspect of the present invention, the surface of the kneaded product is slipped by using a specific nonionic surfactant (D) and sulfate 1-9 hydrate (E) in combination. When the viscosity is increased and it becomes difficult to apply excessive pressure to the kneaded product when extruded by an extruder, a granulated product having an appropriate strength can be obtained without becoming too hard. Along with this, it is not necessary to apply impact and shear force strongly during grinding.
Further, by using the nitrogen-containing chelating agent (F), a granulated product having an increased flexibility due to the action of the component (F) as a binder can be obtained. Thereby, since the impact applied at the time of grinding | pulverization is absorbed to some extent, it becomes difficult to generate | occur | produce fine powder.
From the above, it is considered that such an effect can be obtained by the manufacturing method according to the second aspect of the present invention.

Moreover, in the manufacturing method in the 2nd aspect of this invention, the storage stability of the bleaching activator granulated material obtained improves by using the 1-9 hydrate (E) of a sulfate. On the other hand, when the sulfate anhydride is used in place of the component (E) and a deficient amount of water is added separately, the storage stability of the bleach activator granulated product is deteriorated.
The reason for this is not clear, but when an anhydrous sulfate salt is used instead of the component (E) and the insufficient amount of water is added separately, the temperature rise accompanying the generation of heat of hydration of the kneaded product in the kneading process will increase. As a result, the mechanical power during kneading and extruding is increased, so that a granulated product with insufficient coating of the bleach activator and excessively high strength is prepared. It is considered that the storage stability of the granulated product becomes worse.

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.
In addition, the average particle diameter was measured by the same method as the above [Measuring method of average particle diameter]. The dehydration temperature was measured in the same manner as described above.
Tables 1 and 2 show the compositions of the granulated bleach activator produced by the production method of each example.
The raw materials used in this example are as follows.

・ Bleaching activator (A)
OBS: Sodium 4-lauroyloxybenzene sulfonate As raw materials, sodium p-phenolsulfonate (manufactured by Kanto Chemical Co., Ltd .: reagent), N, N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd .: reagent), and lauric acid Using chloride (Tokyo Chemical Industry Co., Ltd .: reagent) and acetone (Kanto Chemical Co., Ltd .: reagent), synthesis was performed by the following method.
100 g (0.51 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of N, N-dimethylformamide, and 111 g (0.51 mol) of lauric acid chloride was stirred at 50 ° C. while stirring with a magnetic stirrer. It was added dropwise over 30 minutes.
After completion of the dropwise addition, the reaction was carried out for 3 hours, N, N-dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), the resulting residue was washed with acetone, and then water / acetone (= (1/1 mol) Recrystallization was performed in a solvent. The yield was 90%.

OBC: 4-decanoyloxybenzoic acid, manufactured by Mitsui Toatsu Chemicals Co., Ltd., trade name “AC agent”.
TAED: Tetraacetylethylenediamine, manufactured by Tokyo Chemical Industry Co., Ltd., trade name “N, N, N ′, N′-tetraacetylethylenediamine”.

・ Organic binder (B)
PEG-6000: manufactured by Lion Corporation, trade name “PEG # 6000M”, average molecular weight 6000, melting point 60 ° C.
PEG-4000: manufactured by Lion Corporation, trade name “PEG # 4000”, average molecular weight 4000, melting point 55 ° C.

・ Anionic surfactant (C)
AOS-Na: α-olefin sulfonic acid Na salt having 14 to 18 carbon atoms, manufactured by Lion Corporation, trade name “Lipolane PJ-400”, average particle size 200 μm.
AS-Na: Alkyl sulfate sodium salt having an alkyl group having 10 to 18 carbon atoms, manufactured by Shin Nippon Rika Co., Ltd., trade name “Cinoline 90TK-T”, average particle size 150 μm.

-Nonionic surfactant (D) having a melting point of less than 45 ° C
POE alkyl ether (EO = 15): a nonionic surfactant obtained by adding 15 mol of EO (ethylene oxide) to a natural alcohol having 12 to 16 carbon atoms, manufactured by Lion Co., Ltd., trade name “LMAO-90”, Pure content 90% by mass, melting point 40 ° C.
POE alkyl ether (EO = 9): a nonionic surfactant obtained by adding 9 mol of EO (ethylene oxide) to a natural alcohol having 12 to 16 carbon atoms, manufactured by Lion Co., Ltd., trade name “Leox CL-90” Pure content 100% by mass, melting point 28 ° C.

・ Sulfate 1-9 hydrate (E)
Zinc sulfate heptahydrate: manufactured by Mitsui Kinzoku Mining Co., Ltd., average particle size 580 μm, dehydration temperature 73 ° C.
Zinc sulfate monohydrate: manufactured by Horiike Sangyo Co., Ltd., trade name “ZNS-13”, average particle size 200 μm, dehydration temperature 270 ° C.
Copper (II) sulfate pentahydrate: manufactured by Junsei Chemical Co., Ltd., reagent grade, average particle size 530 μm, dehydration temperature 45 ° C.
Manganese (II) sulfate heptahydrate: Showa Chemical Co., Ltd., special grade reagent, average particle size 600 μm, dehydration temperature 60 ° C.
Nickel (II) sulfate heptahydrate: manufactured by Mitsui Mining & Smelting Co., Ltd., average particle size 550 μm, dehydration temperature 53 ° C.

Comparative component of sulfate 1-9 hydrate (E) (hereinafter referred to as “(E ′) component”)
Sodium sulfate decahydrate: manufactured by Junsei Chemical Co., Ltd., reagent grade, average particle size 700 μm, dehydration temperature 37-43 ° C.

・ Nitrogen-containing chelating agent (F)
MGDA: trisodium methylglycine diacetate, manufactured by BASF, trade name “Trilon M powder”, average particle size 80 μm.

・ Comparative component of nitrogen-containing chelating agent (F) (hereinafter referred to as “(F ′) component”)
Citric acid: Made by Junsei Chemical Co., Ltd., reagent grade.
Succinic acid: Made by Pure Chemical Co., Ltd., reagent grade.

-Other components The following zeolite was used as a grinding aid.
Zeolite: Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”.

The detergent base powder and the sodium percarbonate granule used in [Evaluation of Storage Stability] described below are as follows.
-Detergent base powder The detergent base powder prepared by the manufacture example shown below was used.
After spray-drying, each component excluding the equivalent of 2% by mass of A-type zeolite was put into a reactor having a stirrer and a jacket (jacket temperature 75 ° C.) so that the following composition was obtained. A mass percent slurry was prepared.
Water: 5.0% by mass, LAS-K: 1.5% by mass, A-type zeolite: 12.7% by mass, acrylic acid-maleic acid copolymer salt: 2.9% by mass, sodium carbonate: 41.1% by mass , Potassium carbonate: 6.9% by mass, sodium sulfate: 20.3% by mass, soap: 7.6% by mass, impurities: 2.0% by mass.

LAS-K: linear alkylbenzene sulfonic acid (the linear alkyl group has 10 to 14 carbon atoms) [manufactured by Lion Co., Ltd., trade name: Raipon LH-200 (LAS-H pure 96 mass%)] Is a compound neutralized with a 48% by mass aqueous potassium hydroxide solution during the slurry preparation.
Acrylic acid-maleic acid copolymer salt: sodium salt of a copolymer of acrylic acid and maleic acid, trade name “Socaran CP7”, manufactured by BASF.
Soap: Fatty acid sodium having 12 to 18 carbon atoms [manufactured by Lion Corporation, pure mass 67% by mass, titer 40 to 45 ° C .; fatty acid composition Fatty acid having 12 carbons: 0.7% by mass, fatty acid having 14 carbons: 11 .4% by mass, fatty acid having 16 carbon atoms: 29.2% by mass, C18F0 (stearic acid): 0.7% by mass, C18F1 (oleic acid): 56.8% by mass, C18F2 (linoleic acid): 1.2 % By weight; molecular weight 289].

Next, the slurry is spray-dried using a countercurrent drying tower under the following drying conditions, and a part (2% by mass) of the A-type zeolite is spray-coated at the lower part of the spray-drying tower. Particles were obtained. The average particle diameter of the obtained spray-dried particles was 300 μm, the bulk density was 0.3 kg / L, and the water content was 5% by mass.
(Drying conditions)
・ Spray dryer: counter-current type, tower diameter 2.0m, effective length 5.0m
・ Atomization method: Pressurized nozzle method ・ Spraying pressure: 30 kg / cm ²
・ Hot air inlet temperature: 250 ℃
-Hot air outlet temperature: 100 ° C

Subsequently, 73.8 parts by mass of the obtained spray-dried particles, 17 parts by mass of an α-sulfo fatty acid alkyl ester salt-containing paste, 1.4 parts by mass of a nonionic surfactant, and 1.3 parts by mass of water were continuously added. Kneading with a kneader (KRC-S4 type, manufactured by Kurimoto Seiko Co., Ltd.) (kneader rotation speed 135 rpm, jacket temperature: jacket inlet 5 ° C., outlet 25 ° C. (cooled by passing water through the jacket)), dough A product was prepared. The temperature of the resulting dough was 55 ± 15 ° C.
Next, the obtained dough-like material is put into a pelleter double (EXD-100 type, manufactured by Fuji Powder Co., Ltd.) and extruded from a die having a hole diameter of 10 mm and a thickness of 10 mm and simultaneously cut (pellet (cutter) cutter) The peripheral speed was 5 m / s) to obtain a pellet-shaped formed body (diameter: about 10 mm, length: 70 mm or less (substantially 5 mm or more)).

α-sulfo fatty acid alkyl ester salt-containing paste: carbon number 16-18 (part derived from fatty acid), manufactured by Lion Co., Ltd., pure content 60 mass%.
Nonionic surfactant: Nonionic surfactant obtained by adding 15 moles of EO (ethylene oxide) to natural alcohol having 12 to 16 carbon atoms, manufactured by Lion Corporation, trade name “LMAO-90”, pure content of 90% by mass.

Fitzmill (DKA-6 type, DKA-6 type, arranged in three stages in series under air blowing was added to 93.5 parts by weight of the obtained pellet-shaped molded body, and A type zeolite as a grinding aid was added. By using Hosokawa Micron Corporation), a detergent base powder was obtained. The grinding conditions were as follows. The temperature of the obtained detergent base powder was 30 ± 10 ° C., the average particle size was 350 μm, the amount of particles having a particle size of 150 μm or less was 10% by mass, and the bulk density was 0.85 kg / L.
(Crushing conditions)
・ Blower temperature: 15 ± 3 ℃
・ Blowing rate (gas / solid ratio): 2.8 ± 0.25 m ³ / kg
・ Screen diameter: 6mm, 4mm, 2mm from 3 steps
・ Crusher rotation speed: 100% = 4700 rpm (circumferential speed about 60 m / s)
・ Processing speed: 230kg / hr

-Sodium percarbonate granulated product: Zhejiang JINKE CHEMICALS, trade name “SPCC”, effective oxygen amount 13.8% by mass, average particle size 870 μm.

<Example of production of granulated product of bleach activator>
A bleaching activator granulated product was produced by the following production method according to the blending components and contents (mass%) of the compositions shown in Tables 1 and 2, respectively.
In the table, the contents of the component (E) and the component (E ′) indicate the amount as a hydrated salt containing water molecules. Others indicate pure equivalents.
The table shows the temperature (° C.) of the kneaded material obtained in the kneading step, the hardness (g) of the kneaded material, and the kneading power (A) when the kneading was performed. The hardness (g) of the kneaded material was measured using a hard meter (manufactured by Fujiwara Seisakusho) with the temperature measurement for the kneaded material immediately after the kneading step.
Die hole diameter (mmφ), extrusion power (A), extrudate temperature (° C.), air current value (A), extrusion power (kwh / t), extrusion time (minutes), extrusion amount ( kg) is shown in the table.

Example 1
[Kazuwa process]
Warm water was circulated in the jacket of an S-1 KRC kneader manufactured by Kurimoto Steel Corporation, and the kneader body was heated to a temperature of 65 ° C. and maintained at that temperature.
Subsequently, all the components except the grinding aid shown in Table 1 were powder mixed to prepare a powder mixture having a total amount of 1.5 kg. This powder mixture was continuously added to the kneader for 15 minutes while continuing the operation, and after the addition, kneading was performed by kneading.

[Extrusion granulation process]
This kneaded product was put into an extruder (manufactured by Dalton Co., Ltd., multi-gran MG-55 type) equipped with a die having a 0.8 mmφ hole, and granulated by extruding through the die.
By such extrusion granulation, a noodle-shaped granule having a length of 2 to 5 mm was obtained as an extrudate.
Thereafter, the noodle-shaped granulated product and the grinding aid are charged into a speed mill (Okada Seiko Co., Ltd.) equipped with a 2.5 mmφ screen, and pulverized at a rotational speed of 3000 rpm. Obtained.

(Examples 2 to 11 and 13, Comparative Examples 1 to 4)
According to the composition shown in Tables 1 and 2, a bleaching activator granulated product was obtained by performing the same operation as in Example 1. The powder mixture was charged for 15 to 30 minutes per 1.5 kg.

(Example 12)
Hot water was circulated in a jacket of a PNV-5 type table kneader (manufactured by Irie Shokai Co., Ltd.), and the kneader body was heated to 65 ° C. to maintain the temperature.
Next, among the compositions shown in Table 1, the components (A), (E), (F), and (C) are introduced into a horizontal chamber having stirring blades that rotate in the vertical direction. did.
Next, the 60 ° C. component (B) and the component (D) melted together were introduced into the horizontal chamber and kneaded for 50 minutes to obtain a kneaded product.
The obtained kneaded product was subjected to the same operation as in the extrusion granulation step in Example 1 to obtain a bleach activator granulated product. At that time, 1.5 kg total amount of each component was put into the kneader.

(Comparative Example 5)
Warm water at 65 ° C. was heated in a jacket of a 20 L Ladige mixer (manufactured by Matsubo Co., Ltd.).
Next, all the components (total amount 5 kg) except for the grinding aid shown in Table 2 were charged into the Laedige mixer and granulated under the conditions of a main shaft of 150 rpm and a chopper of 3000 rpm.
Thereafter, the obtained granulated product and grinding aid are put into a speed mill (Okada Seiko Co., Ltd.) equipped with a 2.5 mmφ screen, and pulverized at a rotational speed of 3000 rpm. Obtained.

<Evaluation of granulated product of bleach activator>
The following evaluation was performed about the bleaching activator granulated material obtained by the manufacturing method of each example, respectively. The results are shown in Tables 1 and 2.

[Evaluation of difficulty in generating fine powder during grinding]
When the bleaching activator granulated product obtained in each example was classified by the same method as the above-mentioned “Method for measuring average particle diameter”, the granulated product recovered through the sieve having a mesh size of 149 μm was collected on the tray. The mass frequency of the granule was measured and evaluated based on the following evaluation criteria.
(Evaluation criteria)
(Double-circle): The sum total of the particle | grains with a particle diameter of less than 149 micrometers was less than 2 mass% of the whole particle | grain.
(Circle): The sum total of the particle | grains with a particle diameter of less than 149 micrometers was 2 mass% or more and less than 7 mass% of the whole particle | grain.
(Triangle | delta): The sum total of particle | grains with a particle diameter of less than 149 micrometers was 7 mass% or more and less than 14 mass% of the whole particle | grain.
X: The sum total of the particle | grains with a particle diameter of less than 149 micrometers was 14 mass% or more of the whole particle | grains, and less than 20 mass%.
XX: The total of particles having a particle diameter of less than 149 μm was 20% by mass or more of the whole particles.

[Evaluation of solubility in water]
1 g of the bleaching activator granulated product obtained in each example was added to a 200 mL beaker (inner diameter 61 mm, height 87 mm) containing 200 mL of ion-exchanged water having a water temperature of 10 ° C., and stirred and mixed with a magnetic stirrer (stirrer). Piece: length 20 mm, diameter 5 mm, rotation speed: 200 rpm), and the change in the electric conductivity of the ion-exchanged water was measured over time with an electric conductivity meter.
After confirming that there was no undissolved residue of the bleach activator granulated product in ion-exchanged water, the dissolution rate (%) was determined by the following formula.
Dissolution rate (%) = (electric conductivity value / maximum value of electric conductivity) × 100
And while showing time required for 90% (mass basis) of a bleaching activator granulation to melt | dissolve as dissolution time (second), it evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The dissolution time was less than 200 seconds.
○: Dissolution time was 200 seconds or more and less than 300 seconds.
Δ: Dissolution time was 300 seconds or more and less than 500 seconds.
X: The dissolution time was 500 seconds or more.

[Evaluation of storage stability]
10 g of the bleach activator granulated product obtained in each example was uniformly mixed with 940 g of detergent base powder and 50 g of sodium percarbonate granulated product, and the same seal carton detergent container (length 155 mm × width 95 mm × The sealed carton detergent container was stored in a thermostatic bath at a temperature of 45 ° C. and a relative humidity of 60% for 2 weeks.
Thereafter, the sealed carton detergent container was taken out from the thermostatic bath and opened, and only the bleaching activator granulated product was selected and taken out from the contents.
The amount of organic peracid in the bleached activator granulated product after storage was measured by the following method.

Measuring method of organic peracid amount:
1 L of ion-exchanged water is put into a 1 L beaker, and 3 mL of 5% by mass aqueous solution of LAS-Na (sodium dodecylbenzenesulfonate), 3 mL of 5% by mass aqueous solution of sodium carbonate, and 0.2% by mass of hydrogen peroxide are added thereto. The aqueous solution added with 10 mL of the aqueous solution was stirred (100 rpm) for 1 minute with a magnetic stirrer (using a cylindrical stirrer piece having a diameter of 5 mm and a length of 20 mm).
Thereafter, 0.05 g of the bleach activator granulated product was added and stirred for 10 minutes, and 10 mL of a 0.3 mass% catalase aqueous solution was added, followed by further stirring for 1 minute.
To this solution, 10 mL of 10% by mass potassium iodide solution and 20 mL of 20% by mass sulfuric acid solution were added.
Next, titration was performed with a 0.02 mol / L sodium thiosulfate solution, and the organic peracid production rate (%) was calculated by the following equation. In the formula, n represents the number of moles of the generated organic peracid (n = 1 for the OBS and OBC, n = 2 for the TAED).

Then, by calculating the ratio of the amount of organic peracid after storage to the amount of organic peracid before storage measured in advance, the residual rate of organic peracid (% by mass) is obtained and evaluated based on the following evaluation criteria. did.
(Evaluation criteria)
(Double-circle): The residual rate of the organic peracid was 85-100 mass%.
(Circle): The residual rate of the organic peracid was 70 mass% or more and less than 85 mass%.
(Triangle | delta): The residual rate of the organic peracid was 50 mass% or more and less than 70 mass%.
X: The residual rate of the organic peracid was less than 50 mass%.

  From the results of Tables 1 and 2, Examples 1 to 13 according to the present invention are capable of producing a bleach activator granulated product that is less likely to generate a fine powder during pulverization and is excellent in water solubility and storage stability. Was confirmed.

The bleaching activator granulated product according to the first aspect of the present invention is excellent in water solubility and storage stability.
In addition, according to the method for producing a bleaching activator granulated product in the second aspect of the present invention, bleaching activator granulation that hardly generates fine powder during pulverization and has excellent solubility in water and storage stability. Can manufacture things.

Claims (8)

  Bleach activator (A), organic binder (B), anionic surfactant (C), nonionic surfactant (D) having a melting point of less than 45 ° C., and 1 to 9 of sulfate A bleaching activator granulated product comprising a hydrate (E) and a nitrogen-containing chelating agent (F). The bleaching activator granulated product according to claim 1, wherein the nitrogen-containing chelating agent (F) 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 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or a cation. It represents sex ammonium group; _{n 2} is an integer of 0-5. ] The bleach activator (A) is selected from the group consisting of a compound represented by the following general formula (11), a compound represented by the following general formula (12), and a compound represented by the following chemical formula (13) The bleach activator granulated product according to claim 1 or 2, which is at least one kind of compound.

[Wherein, R ₁ and R ₂ are each independently a linear alkyl group having 7 or more carbon atoms; M is a salt-forming cation or a hydrogen atom. ]   The bleaching activator granulated product according to any one of claims 1 to 3, wherein the organic binder (B) is polyethylene glycol having an average molecular weight of 400 to 30,000.   The anionic surfactant (C) is a linear or branched alkylbenzene sulfonate (the average carbon number of the linear or branched alkyl group is 8 to 18), long-chain alkyl sulfonic acid Salt (average carbon number of long chain alkyl group is 10 to 20), long chain olefin sulfonate (average carbon number of long chain olefin portion is 10 to 20), long chain monoalkyl sulfate ester salt (The average carbon number of the long-chain monoalkyl group is 10 to 20), at least one selected from the group consisting of α-sulfo fatty acid ester salts (the average carbon number of fatty acid residues is 12 to 20). The bleaching activator granulated product according to any one of claims 1 to 4, which is a compound of The nonionic surfactant (D) is a polyethylene glycol addition type nonionic surfactant in which 3 to 80 mol of ethylene glycol or ethylene oxide is added per 1 mol of an aliphatic alcohol having 8 to 20 carbon atoms. And the bleaching activator granule as described in any one of Claims 1-5 which is melting | fusing point is less than 45 degreeC. 1-9 hydrate (E) of the sulfate is vanadium sulfate heptahydrate, manganese sulfate pentapentahydrate, manganese sulfate heptahydrate, nickel sulfate heptahydrate, copper sulfate The hydrate of at least one sulfate selected from the group consisting of pentahydrate, zinc sulfate monohydrate, zinc sulfate hexahydrate, and zinc sulfate heptahydrate. The bleaching activator granulated product according to any one of 1 to 6. It is a manufacturing method of the bleaching activator granulation according to any one of claims 1 to 7,
1-9 water of the bleach activator (A), the organic binder (B), the anionic surfactant (C), the nonionic surfactant (D), and the sulfate. A kneading step of kneading the Japanese product (E) and the nitrogen-containing chelating agent (F);
An extrusion granulation step in which extrusion granulation is performed using the kneaded product obtained in the kneading step.