KR20130018707A - Bleach activator agglomerated substance and method for producing same - Google Patents

Abstract

The present invention provides 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 1-9 hydrate of sulfate ( E) and the bleaching activator granulated substance containing a nitrogen containing chelating agent (F); The manufacturing method of the bleaching activator granulated material which has the kneading process of kneading and kneading the said (A)-(F) component, and the extrusion granulation process which performs extrusion granulation using the kneaded material obtained by the said kneading process. According to the present invention, it is possible to provide a bleaching activator granulated product having excellent solubility in water and storage stability and a method for producing a bleaching activator granulated product which is hardly generated when pulverized.

Description

Bleach activator assembly and its manufacturing method {BLEACH ACTIVATOR AGGLOMERATED SUBSTANCE AND METHOD FOR PRODUCING SAME}

TECHNICAL FIELD This invention relates to the granulated material of the bleach activator which is a component which enhances the bleaching effect of an oxygen-based bleaching component, and its manufacturing method.

This application claims priority in 2010/03/26 based on Japanese Patent Application No. 2010-072671 for which it applied to Japan, and uses the content for it here.

Detergent compositions and bleach compositions are used for laundry such as medical care.

In these compositions, some of the compositions may exhibit a bleaching effect by an oxidation reaction. As the oxidation reaction component responsible for this oxidation reaction, an oxygen-based bleaching component such as hydrogen peroxide, percarbonate which dissolves in water to generate hydrogen peroxide, or a chlorine-based bleaching component such as sodium hypochlorite is used. In recent years, the oxygen-based bleaching component is attracting attention because it can be used easily.

In addition, in order to enhance the bleaching effect, a bleach activator such as an organic peracid precursor and a bleach activating catalyst is used together with an oxygen-based bleaching component.

The bleach activator tends to be degraded by preservation over time, due to interaction with other components in the composition described above. Therefore, in order to ensure storage stability, a bleach activator is generally used as a granulated material.

Until now, a bleach activator granulated product produced by granulation using a bleach activator, a water-soluble binder (organic binder) and an anionic surfactant has been proposed (see Patent Documents 1 to 3, for example).

Moreover, the bleaching activator granulated body which contains a specific organic peracid precursor and magnesium salt is proposed (refer patent document 4). In the invention described in Patent Literature 4, the magnesium salt is used as a suitable one having as few hydrated waters as possible (especially anhydride) in view of the effect of magnesium (suppression of inhibition by calcium ions).

Patent Document 1: Japanese Patent Application Laid-Open No. 9-217089 Patent Document 2: Japanese Patent Application Laid-Open No. 9-272900 Patent Document 3: Japanese Patent Application Laid-Open No. 8-3593 Patent Document 4: Japanese Patent Application Laid-Open No. 2002-338999

However, in the methods described in Patent Documents 1 to 4, the granulated product (extruded product) tends to be too hard. Therefore, when crushing or pulverizing (hereinafter collectively referred to as "pulverization") for the purpose of sizing, the power of the pulverizer is high, and the impact and shear force are strongly applied to the granulated material, so that fine powder is likely to occur. There is. In addition, in the granulated product, solubility in water (especially solubility in water at a low temperature of 10 ° C for a short time (within 5 minutes)) is still insufficient.

In the method described in Patent Document 4, further, the preservation over time tends to lower the bleaching activation ability, and the storage stability is also insufficient.

This invention is made | formed in view of the said situation, Comprising: It is a subject to provide the bleaching activator granulated material which is excellent in the solubility and storage stability with respect to water, and also the manufacturing method of the bleaching activator granulated material which is hard to produce fine powder at the time of grinding | pulverization. Shall be.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors provide the following means in order to solve the said subject.

That is, the bleaching activator granulated material in the first aspect of the present invention is a nonionic having a bleaching activator (A), an organic binder (B), an anionic surfactant (C), and a melting point of less than 45 ° C. It is characterized by containing surfactant (D), the 1-9 hydrate of sulfate (E), and a nitrogen-containing chelating agent (F).

In the bleaching activator granulated material in 1st aspect of this invention, it is preferable that the said nitrogen-containing chelating agent (F) is a compound represented with 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 cationic ammonium group; n <_2> represents the integer of 0-5.]

In the bleach activator granulated product according to the first aspect of the present invention, the bleach activator (A) is a compound represented by the following general formula (11), a compound represented by the following general formula (12), and the following general formula It is preferable that it is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by (13).

[In formula, R <_1> and R <_2> is respectively independently a C7 or more linear alkyl group; M is a salt forming cation or a hydrogen atom.]

In the bleach activator granulated material in 1st aspect of this invention, it is preferable that the said organic binder (B) is polyethyleneglycol of 400-30000 average molecular weights.

In the bleach activator granulated product according to the first aspect of the present invention, the anionic surfactant (C) has a linear or branched alkylbenzenesulfonate (average carbon number of 8 to 18 is linear or branched alkyl group). ), Long-chain alkylsulfonate (average carbon number of long-chain alkyl group is 10-20), long-chain olefinsulfonate (average carbon number of long-chain olefin moiety is 10-20), long-chain monoalkyl sulfate ester salt (average carbon number of long-chain monoalkyl group) Is 10 to 20) and α-sulfofatty acid ester salt (the average carbon number of the fatty acid residue is 12 to 20).

In the bleach activator granulated product according to the first aspect of the present invention, the nonionic surfactant (D) is a polyethylene glycol addition type in which 3 to 80 moles of ethylene glycol or ethylene oxide is added to 1 mole of aliphatic alcohol having 8 to 20 carbon atoms. It is a nonionic surfactant, and it is preferable that it is less than melting | fusing point 45 degreeC.

In the bleaching activator granulated material in the first aspect of the present invention, the 1-9 hydrate (E) of the sulphate is vanadium sulfate hexahydrate, manganese sulfate hexahydrate, manganese sulfate hexahydrate, nickel sulfate 7. It is preferable that it is a hydrate of at least 1 sort (s) of sulfate selected from the group which consists of a hydrate, copper sulfate pentahydrate, zinc sulfate monohydrate, zinc sulfate pentahydrate, and zinc sulfate heptahydrate.

Moreover, the manufacturing method of the bleaching activator granulated material in the 2nd aspect of this invention is a manufacturing method of the bleaching activator granulated material in the 1st aspect of this invention, The said bleaching activator (A) and the said organic Kneading and kneading a binder (B), the anionic surfactant (C), the nonionic surfactant (D), the 1-9 hydrate (E) of the sulfate salt, and the nitrogen-containing chelating agent (F) It has a kneading process, and the extrusion granulation process which performs extrusion granulation using the kneaded material obtained by the said kneading process, It is characterized by the above-mentioned.

In the present invention, the "melting point" refers to a value measured by the melting point measuring method described in JIS K0064-1992 "Method for Measuring Melting Point and Melting Range of Chemical Product".

According to the bleach activator granulated material in 1st aspect of this invention, it is excellent in the solubility to water and storage stability.

Moreover, according to the manufacturing method of the bleaching activator granulated material in the 2nd aspect of this invention, it is hard to produce fine powder at the time of grinding | pulverization, and the bleaching activator granulated material excellent in the solubility to water and storage stability can be manufactured.

<Bleach Activator Assembly>

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

Bleach Activator (A)

As a bleach activator (A) (henceforth "(A) component"), an organic peracid precursor, a bleach activating catalyst, etc. are mentioned, for example.

An organic peracid precursor reacts with hydrogen peroxide generated from peroxides, such as sodium percarbonate, for example, and organic bleaching power with strong bleaching power produces an bleaching effect on medical care.

As an organic peracid precursor, For example, Carbonic acid ester, such as an alkanoyloxybenzene sulfonic acid, an alkanoyloxy benzoic acid, or these salts; Polyacylated alkylenediamines such as tetraacetylethylenediamine, N-acylated triazines such as 1,5-ziacetyl-2,4-dioxohexahydro-1,3,5-triazine, tetratorylglycoluril N-acylated caprolactams, such as acylated glycoluril and acetyl caprolactam; Carboxylic anhydrides such as hydantoin, hydrazide, triazole, hydrotriazole, urazol, diketopiperazine, sulfuramido, cyanurate, and phthalic anhydride; And acylated sugar derivatives such as pentaacetylglucose.

Among the organic peracid precursors, suitable compounds include compounds represented by the following general formula (11), compounds represented by the following general formula (12), and compounds represented by the following general formula (13) (N, N, N ', N'- Tetraacetylethylenediamine).

[In formula, R <_1> and R <_2> is respectively independently a C7 or more linear alkyl group; M is a salt forming cation or a hydrogen atom.]

In said formula, a C8-18 linear alkyl group is preferable, and, as for R <_1> , a C9-15 linear alkyl group is more preferable.

In said formula, a C8-18 linear alkyl group is preferable, and, as for R <_2> , a C9-15 linear alkyl group is more preferable.

In said formula, M is preferably alkali metal atoms, such as sodium and potassium, amines, such as ammonium and an alkanolamine, and an alkali metal atom is more preferable.

In said formula, any of the ortho, meta, or para position may be sufficient as the coupling | bonding position of SO <_3> M and COOM group, and a para position is preferable.

The bleach activating catalyst further activates hydrogen peroxide generated from a peroxide such as sodium percarbonate to enhance the bleaching effect.

As a bleaching activation catalyst, a metal ion complex catalyst etc. are mentioned, for example. Specifically, a pyridine-2, 6- dicarboxylic acid-Cu complex is mentioned.

(A) A component can be used individually by 1 type or in mixture of 2 or more types.

Among the above, when manufacturing the granulated material of a bleaching activator, since the effect of this invention is remarkable and technical significance is higher, as an (A) component, an organic peracid precursor is preferable.

In a bleaching activator granulated material, 30-60 mass% is preferable, as for content of (A) component, 35-60 mass% is more preferable, 40-55 mass% is especially preferable.

When content of (A) component is 30 mass% or more, when mix | blending with a detergent composition or a bleach composition, the compounding quantity of a granulated material does not increase too much and it becomes easy to match the compounding balance with another raw material. For example, in the case of a detergent composition, since a detergent raw material can also be fully mix | blended, the washing | cleaning effect derived from a detergent raw material is obtained favorably. On the other hand, when content of (A) component is 60 mass% or less, the compounding balance with another raw material is maintained and storage stability improves.

[Organic Binder (B)]

The organic binder (B) (hereinafter also referred to as "(B) component") has a function as a binder, and is a water-soluble organic compound that is solid at room temperature and melts by applying heat.

Especially, as (B) component, the organic compound of 25-100 degreeC of melting | fusing point is more preferable, the organic compound of 25-80 degreeC of melting | fusing point is more preferable, The organic compound of 40-80 degreeC of melting | fusing point is especially preferable, Most preferred are organic compounds having a melting point of 45 to 75 ° C.

However, (B) component shall not contain (C) component, (D) component, (E) component, and (F) component in this 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 more preferable, and polyethylene glycol having an average molecular weight of 4000 to 20000 is particularly preferable.

"Average molecular weight" here shows the value of the polyethyleneglycol conversion standard by gel permeation chromatography.

(B) A component can be used individually by 1 type or in mixture of 2 or more types.

In a bleaching activator granulated material, 3-30 mass% is preferable, as for content of (B) component, 5-25 mass% is more preferable, 8-20 mass% is especially preferable.

When content of (B) component is 3 mass% or more, in the manufacture of a bleaching activator granulated material, it will become hard to produce fine powder at the time of grind | pulverizing. In addition, the solubility and storage stability of the bleach activator granules is improved. On the other hand, when content of (B) component is 30 mass% or less, especially the compounding balance with (A) component is maintained and a bleaching effect improves.

[Anionic Surfactant (C)]

As an anionic surfactant (henceforth "(C) component"), a linear or branched alkylbenzene sulfonate (average carbon number of a linear or branched alkyl group is 8-18), long-chain alkylsulfonic acid Salts (average carbon number of the long chain alkyl group is 10 to 20), long chain olefin sulfonate (average carbon number of the long chain olefin portion is 10 to 20), long chain monoalkyl sulfate ester salt (average carbon number of the long chain monoalkyl group is 10 to 20) ), Polyoxyethylene long chain alkyl ether sulfate ester salt (average degree of polymerization of oxyethylene group is 1 to 10; average carbon number of long chain alkyl group is 10 to 20), polyoxyethylene alkyl phenyl ether sulfate ester salt (oxyoxy group of The average degree of polymerization is 3 to 30, the average carbon number of the alkyl group is 6 to 12), the α-sulfofatty acid ester salt (the average carbon number of the fatty acid residue is 12 to 20); Long-chain monoalkyl, dialkyl or seskialkyl phosphates; Polyoxyethylene monoalkyl, dialkyl or seskialkyl phosphates and the like are used.

Among the above, as (C) component, linear or branched alkylbenzene sulfonate (average carbon number of a linear or branched alkyl group is 8-18), and long chain alkylsulfonate (average carbon number of a long chain alkyl group is 10-20). ), Long chain olefin sulfonates (average carbon number of the long chain olefin portion is 10 to 20), long chain monoalkyl sulfate ester salts (average carbon number of the long chain monoalkyl group is 10 to 20), α-sulfo fatty acid ester salt (of fatty acid residue Average carbon number is 12-20, and long chain alkyl sulfonate (average carbon number of long-chain alkyl group is 10-20) and long chain olefin sulfonate (average carbon number of long-chain olefin part is 10-20) are especially preferable. .

In addition, said "long chain" means a C10-20 group, may be linear or branched, and may have a saturated or unsaturated bond.

Here, "the average carbon number" is a compound which has a hydrocarbon group, and when the compound which carbon number of a hydrocarbon group differs each other is mixed, the sum total of the carbon number of the corresponding hydrocarbon group in all the compounds is calculated | required, The number of carbons converted into one molecule (total number of carbon atoms / molecules of corresponding hydrocarbon groups in all compounds) is shown. A "fatty acid residue" shows the partial structure which removed the alkoxy group from fatty acid ester.

Examples of the form of the salt in the component (C) include alkali metal salts such as sodium and potassium, amine salts and ammonium salts, and alkali metal salts are preferable.

(C) component can be used individually by 1 type or in mixture of 2 or more types.

In a bleaching activator granulated material, 1-15 mass% is preferable, as for content of (C) component, 3-12 mass% is more preferable, 5-10 mass% is especially preferable.

When content of (C) component is 1 mass% or more, the solubility with respect to the water of a bleaching activator granulated material improves. On the other hand, when content of (C) component is 15 mass% or less, especially the compounding balance with (A) component is maintained, and a bleaching effect improves.

[Nonionic Surfactant (D) with Melting Point of less than 45 ° C]

The melting point contains a nonionic surfactant (D) of less than 45 ° C. (hereinafter also referred to as “(D) component”), so that when producing the bleach activator granulated product, it is easily melted by heating and mixed with other raw materials. In this way, kneading and kneading are performed well to prepare a granulated product having an appropriate hardness.

It is preferable that it is 43 degrees C or less, and, as for melting | fusing point of (D) component, it is more preferable that it is 15-41 degreeC.

As (D) component, a polyethyleneglycol addition type nonionic surfactant and a polyethyleneglycol polypropylene glycol addition type nonionic surfactant are mentioned, for example, Among these, a polyethyleneglycol addition type nonionic surfactant is preferable and C8-C20 is preferable. 3 to 80 moles of ethylene glycol or ethylene oxide (preferably 5 to 50 moles, more preferably 5 to 30 moles, particularly preferably 5 to 20 moles) per 1 mole of (preferably 10 to 18) aliphatic alcohols As this addition, it is more preferable that it is less than melting | fusing point 45 degreeC.

Specific examples of the component (D) include polyoxyethylene alkyl ethers. Preferably, 5 to 15 moles of ethylene glycol or ethylene oxide is added, and examples of alkyl having 12 to 18 carbon atoms are mentioned.

(D) component can be used individually by 1 type or in mixture of 2 or more types.

In a bleaching activator granulated material, 1-10 mass% is preferable, as for content of (D) component, 2-9 mass% is more preferable, and its 3-7 mass% is especially preferable.

When content of (D) component is 1 mass% or more, the solubility with respect to the water of the bleaching activator granulated material improves. On the other hand, when content of (D) component is 10 mass% or less, when manufacturing a bleach activator granulated material, for example, the extrusion pressure at the time of extruding from an extruder will not become low too much, and the shape retention of an extrudate becomes favorable. . And the bleaching activator granulated material obtained has the physical property which is hard to bring about coalescence, and generation | occurrence | production of adhesion and solidification at the time of transport are suppressed.

1 to 9 hydrates of sulfates (E)

It is preferable that the 1-9 hydrate of a sulfate (henceforth a "(E) component") is a hydrous salt of the metal elements of group 3-12 in a long-period type | mold periodic table, and it is vanadium, manganese, nickel, It is more preferable that it is a hydrous salt of copper or zinc, and it is still more preferable that it is a hydrous salt of copper or zinc.

It is preferable that it is 1-7, and, as for the number of the water molecules of the said hydrous salt, since the storage stability of a bleaching activator granulated material is favorable, it is more preferable that it is 5-7.

It is preferable that the dehydration temperature of (E) component is 41-80 degreeC, It is more preferable that it is 45-80 degreeC, It is still more preferable that it is 50-75 degreeC. When the dehydration temperature is 80 ° C. or less, solubility in water of the bleaching activator granules is improved, and fine powder is less likely to occur during grinding. Moreover, when dehydration temperature is 41 degreeC or more, the storage stability of a bleaching activator granulated material will become more favorable.

The component (E) is dehydrated at the time of kneading kneading when producing a bleach activator granulated product to improve the manufacturability of the granulated product, and after the granulation, the sulfate is hydrated again to improve the stability of the granulated product. It is estimated to contribute. In addition, when the granulated material obtained after granulation is measured by DSC, the endothermic peak corresponding to the 1-9 hydrate of sulfate is observed.

"Dehydration temperature of (E) component" shows the value observed by the transition point measurement by DSC. In addition, this dehydration temperature is determined by making into the temperature of the peak top of the endothermic peak obtained by DSC. As for the DSC measurement, any type of commercially available heat flux type or heat guaranteed type may be used. As an example of the measurement, α-alumina is used for the reference, and the hydrate of sulfate is placed on the sample side. Measurement temperature range: 0-100 degreeC, temperature rising rate: It carries out on conditions of 2 degree-C / min. The dehydration temperature is taken as the temperature of the peak top of the endothermic peak of 10 mJ / min or more observed at 20 degreeC or more. When there exists a plurality of endothermic peaks, the endothermic peak observed on the highest temperature side of 100 ° C or lower is regarded as the dehydration temperature.

In addition, about the hydrate of the sulfate which does not have an endothermic peak below 100 degreeC, it measured by changing the measurement temperature range to 0-300 degreeC, and computed dehydration temperature similarly.

Specifically as (E) component, vanadium sulfate heptahydrate, manganese sulfate heptahydrate, manganese sulfate heptahydrate, nickel sulfate heptahydrate, copper sulfate pentahydrate, zinc sulfate monohydrate, zinc sulfate heptahydrate And zinc sulfate-hexahydrate. Among them, vanadium sulfate heptahydrate, manganese sulfate pentahydrate, manganese sulfate heptahydrate, nickel sulfate heptahydrate, copper sulfate pentahydrate, zinc sulfate heptahydrate and zinc sulfate heptahydrate are preferred. Copper sulfate pentahydrate, zinc sulfate pentahydrate, 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 a bleaching activator granulated material, 5-30 mass% is preferable, as for content of (E) component, 8-25 mass% is more preferable, 9-20 mass% is especially preferable.

When content of (E) component is 5 mass% or more, while the solubility with respect to the water of a bleaching activator granulated material will improve, it will become difficult to produce fine powder at the time of grind | pulverizing. In addition, the bleaching effect of the bleach activator granulated material is easily obtained. On the other hand, when content of (E) component is 30 mass% or less, when manufacturing a bleach activator granulated material, for example, the extrusion pressure at the time of extruding from an extruder will not become low too much, and the shape retention of an extrudate becomes favorable. . In addition, the resulting bleach activator granulated material has physical properties that are hard to cause coalescence, and the occurrence of adhesion and solidification during transportation are suppressed.

Nitrogen-containing chelating agent (F)

The nitrogen-containing chelating agent (F) (hereinafter also referred to as "(F) component") is not particularly limited as long as it is a chelating agent having a nitrogen atom in the molecule, and examples thereof include aminocarboxylic acid or salts thereof and hydroxyaminocarboxes. Main acid or its salt can be mentioned.

Specific examples of the component (F) include ethylenediaminetetraacetic acid or salts thereof, β-alanine diacetic acid or salts thereof, and compounds represented by the following general formulas (I) to (III).

[In 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> -X <^4> may be same or different and shows a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cationic ammonium group, respectively; 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 a cationic ammonium group; n ₂ represents an integer of 0 to 5.]

Compound represented by the above general formula (I)

In said general formula (I), X represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.

Examples of alkali metal atoms include sodium and potassium.

Examples of alkaline earth metals include calcium and magnesium. For example, in the case of calcium (Ca), in the formula (I) '- (COOX) _p "is - it is represented by" (COOCa _{1/2) p} ".

Especially, it is preferable that X is a hydrogen atom.

p represents the integer of 1 or 2, and it is preferable that it is 1.

When p is 2, some X may mutually be same or different.

When p is 1, it is preferable that the coupling | bonding position of a "-COOX" group to a pyridine ring is (alpha) position with respect to a nitrogen atom. Even when p is 2, it is preferable that at least one "-COOX" group is bonded to the α-position. The remaining "-COOX" groups may be bonded to either the β- or γ-position.

Among the compounds represented by the above general formula (I), fine powders are less likely to occur when pulverized, and therefore, the compounds represented by the following general formula (1) (2-pyridine carboxylic acid (picolinic acid)) or salts thereof Or the compound (2, 6-pyridine dicarboxylic acid (dipicolinic acid)) represented by following General formula (2), or its salt is mentioned.

Compound represented by general formula (II)

In said general formula (II), X <^1> -X <^4> may be same or different and shows a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cationic ammonium group, respectively.

In X ¹ to X ⁴ , examples of the alkali metal atom and the alkaline earth metal atom include the same ones as the alkali metal atom and alkaline earth metal atom in X in the formula (I).

Further, X ¹ to X ⁴ is when any one of an alkaline earth metal atom, for example, in the case of X ¹ the calcium (Ca), expression "-COOX ^1" in (Ⅱ) is a "-COOCa _1/2" Is displayed.

Cationic ammonium groups as, for example, ^{"(R 11) (R 12)} (R 13) (R 14) N + " (where, R ¹¹ to R ¹⁴ are identical to FIG different, each a hydrogen atom, Quaternary ammonium cation, such as an alkyl group of 1 to 4 or a phenyl group).

Among the above, it is preferable that all of X <^1> -X <^4> are alkali metal atoms, and it is more preferable that they are sodium or potassium.

X ¹ to X ⁴ may be the same as or different from each other.

In said general formula (II), R represents a hydrogen atom or a hydroxyl group, and it is preferable that it is a hydroxyl group.

Q represents a hydrogen atom or an alkyl group.

In Q, as an alkyl group, it is preferable that it is C1-C4, and it is more preferable that it is C1-C3. Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, etc. are mentioned.

n <_1> represents the integer of 0 or 1 and it is preferable that it is 1.

Among the compounds represented by the general formula (II), fine powders are less likely to be generated when pulverized, and therefore, the compounds represented by the following general formula (3) (2,2'-iminodiobacic acid) or salts thereof; or The compound (3-hydroxy-2,2'- iminodihobic acid) represented by following General formula (4) or its salt is mentioned.

Compound represented by the general formula (III)

In said general formula (III), Y represents an alkyl group, a hydroxyl group, or a hydrogen atom.

In Y, as an alkyl group, it is preferable that it is C1-C4, and it is more preferable that it is C1-C3. Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, etc. are mentioned.

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 are the same as the alkali metal atom, the alkaline earth metal atom and the cationic ammonium group in X ¹ to X ⁴ in the formula (II). Can be mentioned.

In addition, X ⁵ to when any one of X ⁷ is an alkaline earth metal atom, for example, if X ⁵ is calcium (Ca), "-COOX ^5" in the formula (Ⅲ) is a "-COOCa _1/2" Is displayed.

Among the above, it is preferable that all of X <^5> -X <^7> are alkali metal atoms, and it is more preferable that they are sodium or potassium.

X ⁵ to X ⁷ may be the same as or different from each other.

n <_2> represents the integer of 0-5 and it is preferable that it is 0-2.

Among the compounds represented by the above general formula (III), fine powders are less likely to be generated when pulverized, so that the compounds represented by the following general formula (5) (nitrilotriacetic acid) and the following general formula (6) The compound (methylglycine diacetic acid (MGDA)), the compound (serine diacetic acid) represented by following General formula (7), or its salt is mentioned. Especially, methylglycine diacetic acid or its salt is more preferable.

When the compounds represented by the above general formulas (I) to (III) are blended in, for example, a kneading step when producing a bleach activator granulated product, part or all of the "-COOX" of the terminal group is "-COO". -", And the said compound is considered to act 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 (F) component, since fine powder hardly arises at the time of grinding | pulverization, the compound represented by the said General formula (III) is preferable, Methyl glycine diacetic acid or its salt, nitrilo triacetic acid, or its salt is more preferable. Preferably, methylglycine diacetic acid or its salt is most preferred.

In a bleaching activator granulated material, 3-30 mass% is preferable, as for content of (F) component, 5-20 mass% is more preferable, 6-15 mass% is especially preferable.

If content of (F) component is 3 mass% or more, the bleaching effect of a bleaching activator granulated material will become easy to be obtained. In addition, fine powder becomes less likely to occur during grinding. On the other hand, when content of (F) component is 30 mass% or less, solidification will not occur when the bleaching activator granulated material is preserve | saved.

[Other Ingredients]

The bleaching activator granulated material in 1st aspect of this invention may contain other components other than (A)-(F) component mentioned above as needed. As another component, what is normally used for detergent compositions and bleach compositions, such as a medical grade, For example, Aluminosilicates, such as a cationic surfactant, an amphoteric surfactant, and a zeolite as a grinding aid; Carbonates such as sodium carbonate and calcium carbonate; Silicates such as amorphous silica, calcium silicate and magnesium silicate; In addition, inorganic salts (sodium sulfate, sodium chloride, etc.); Medium or long chain fatty acids or salts thereof; Heavy metal chelating agents other than (F) component, such as 1-hydroxy ethane- 1, 1- diphosphonic acid or its salt; Pigments such as clay minerals, fluorescent brighteners, ultraviolet absorbers, antioxidants, antibacterial agents, ultramarine blue, and the like.

Specific examples of the medium or long chain fatty acid include fatty acids having 8 to 10 carbon atoms in the acyl group and fatty acids having 12 to 18 carbon atoms in the acyl group as the long chain fatty acids. And "heavy chain or long chain" may be linear or branched chain, and may have a saturated or unsaturated bond. In a bleach activator granulated material, 0.1-5 mass% is preferable, and, as for content of a medium or long chain fatty acid, 0.5-4 mass% is more preferable.

It is preferable that it is 150-2000 micrometers, and, as for the average particle diameter of the bleaching activator granulated material in 1st aspect of this invention, it is more preferable that it is 200-1200 micrometers.

When the average particle diameter of a bleach activator granulated material is more than a lower limit, powder fluffing is suppressed, etc. when mixing with a detergent base or an oxygen-based bleach component, and powders. On the other hand, the solubility to water improves that the said average particle diameter is below an upper limit.

In addition, in this invention, 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.

Method of measuring average particle size:

First, a 9-step sieve and pedestal of a mesh size of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm was used for the measurement object (sample). Classification operation.

In the classification operation, first, the sieves of the above nine stages are stacked on the upper side of the pedestal so that the size of the eye is gradually increased, and 100 g / time sample is put on the top of the size of the eye size of 1680 µm. Subsequently, the lid was capped and attached to a low-top sieve shaker (manufactured by Iida Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), vibrated for 10 minutes, and the samples remaining on each sieve and pedestal were removed. Collect each body and measure the mass of the sample.

When the mass frequency of the pedestal and each sieve is integrated, the diameter of the first sieve whose cumulative mass frequency is 50% or more is set to a µm, and the sieve size of the sieve one step larger than a µm is set to b µm. The average particle diameter (mass 50%) is obtained by the following formula, with c% as the integration of the mass frequency from the pedestal to the sieve of a micrometer and d% as the mass frequency on the sieve of amicrometer.

According to the bleaching activator granulated material in 1st aspect of this invention demonstrated above, it is excellent in the solubility to water and storage stability.

The bleach activator granulated material in 1st aspect of this invention can be used suitably as a raw material for the detergent composition containing a detergent base and an oxygen-based bleaching component, or the bleach composition containing an oxygen-based bleaching component.

As a detergent base in the said detergent composition, what is normally mix | blended with detergent compositions, such as medical grade, can be used.

The compounding component used for the detergent base may be, for example, a surfactant, an alkaline agent, an inorganic builder, an organic builder, a reducing agent such as sulfite or thiosulfate, or a particle strength retainer such as sulfate (preferably sodium sulfate in the detergent composition). To 20 mass%), fluorescent brightener, ultraviolet absorber, enzyme (e.g. protease, lipase, cellulase, amylase, etc.), softening agent (bentonite, etc.), recontamination (deposition) inhibitor, foam control agent (e.g. silicone Etc.); pigments such as paints, surface modifiers, oil absorbents, antioxidants, antibacterial agents, ultramarine blue, and the like.

(Surfactants)

The surfactant is not particularly limited as long as it is conventionally used in detergent compositions such as medical grades, and various kinds can be used.

As surfactant, anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant are mentioned, for example.

Anion surfactant

Examples of the anionic surfactants include those shown below.

Α-olefin sulfonates (AOS) having 10 to 20 carbon atoms.

Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.

Straight or branched alkylbenzenesulfonate having an alkyl group having 8 to 18 carbon atoms (LAS, ABS).

Alkanesulfonates (SAS) having 10 to 20 carbon atoms.

Alkyl ether sulfate or alkenyl ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average added mole number of 10 mol or less added to ethylene oxide, propylene oxide, butylene oxide or a mixture thereof. Sulfate (AES).

Alkyl ether carbonates or eggs having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average added mole number of 10 moles or less added to ethylene oxide, propylene oxide, butylene oxide or a mixture thereof. Kenyl ether carbonate.

Alkyl polyhydric-alcohol ether sulfates, such as a C10-C20 alkyl glyceryl ether sulfonic acid.

Higher fatty acid salts (soaps) having 10 to 20 carbon atoms.

α-sulfofatty acid salts or ester salts thereof. Preferably, saturated or unsaturated α-sulfofatty acid salts or ester salts thereof having 8 to 20 carbon atoms (preferably 12 to 18) (preferably methyl ester salt (MES), ethyl ester salt or propyl ester salt) .

Nonionic Surfactant

As a nonionic surfactant, what is shown below is mentioned, for example;

Polyoxyalkylene alkyl ether having an average of 3 to 30 moles, preferably 5 to 20 moles 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 poly Oxyalkylene alkenyl ether (alcohol alkoxylate). Among them, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether are suitable.

As an aliphatic alcohol used here, a primary alcohol and a secondary alcohol are mentioned. The alkyl group of the aliphatic alcohol may have a branched chain. As aliphatic alcohol, primary alcohol is preferable.

In addition to the above, polyoxyethylene alkylphenyl ether, polyoxyethylene alkenylphenyl ether, etc. which added 8-20 mol of C2-C4 alkylene oxides to the aromatic alcohol which has a C8-C12 alkyl group on average are mentioned. .

Moreover, the fatty acid alkyl ester alkoxylate etc. which the alkylene oxide added between ester bonds of a long-chain fatty-acid alkylester, represented by following General formula (IV) are mentioned, for example.

R ⁴ CO- (OR ⁵ ) _{n '} -OR ³ ... (Ⅳ)

[In formula (IV), R <^4> CO represents a C6-C22, Preferably 8-18 fatty acid residue; OR <^5> represents the addition unit of C2-C4, Preferably 2-3 alkylene oxide (for example, ethylene oxide, a propylene oxide, etc.); n 'represents the average added mole number of alkylene oxide, Preferably it is 3-30, More preferably, it is the number of 5-20. R <^3> represents the lower (C1-C4) alkyl group which may have a C1-C3 substituent.]

Moreover, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hardened castor oil, glycerin fatty acid ester is mentioned.

Among these, as a nonionic surfactant, it is preferable that melting | fusing point is 50 degrees C or less, More preferably, it is 40 degrees C or less, Moreover, it is preferable that HLB is 7-16, More preferably, it is 8-14.

Here, "HLB" is a value calculated by Griffin's method (refer to Yoshida Shindo, Ogaki and Yamanaka Co., "New Surfactant Handbook", KKK, 1991, p. 234).

As a specific example of such a nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene whose melting | fusing point is 50 degrees C or less and HLB is 7-16. Polyoxypropylene alkenyl ether, fatty acid methyl ester ethoxylate which ethylene oxide added to fatty acid methyl ester, fatty acid methyl ester ethoxy propoxylate which ethylene oxide and propylene oxide added to fatty acid methyl ester, etc. are mentioned.

Cationic surfactant

As the cation surfactant, for example, mono, di or trialkyl cation having 1 to 3 long-chain (preferably 8 or more carbon atoms) hydrocarbon groups can be used. In particular, cationic surfactants containing 1 to 2 ester groups and 1 to 2 long chain hydrocarbon groups in the molecule are preferable.

Positive surfactant

As the amphoteric surfactant, sulfobetaine or carboxybetaine having one or two long-chain (preferably 8 or more carbon atoms) hydrocarbon groups can be used.

The form of the salt in surfactant is salt of alkali metals, such as sodium and potassium; Salts of alkaline earth metals such as calcium and magnesium; Alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine; Ammonium salts are mentioned, and these may be mixed. Among them, salts of alkali metals are preferred.

Surfactant can be used individually by 1 type or in combination of 2 or more types.

Among these, since surfactant improves washing | cleaning performance, it is preferable to use an anionic surfactant and a nonionic surfactant together, and it is more preferable to use MES and polyoxyethylene alkyl ether together.

It is preferable to use together MES and polyoxyethylene alkyl ether at MES / polyoxyethylene alkyl ether (mass ratio) = 95/5-60/40, and it is more preferable to use together at 90/10-70/30.

It is preferable that content of surfactant in a detergent composition is 1-50 mass%, It is more preferable that it is 5-30 mass%, It is still more preferable that it is 10-25 mass%.

If content of surfactant is more than a lower limit, favorable washing | cleaning effect will become easy to be acquired. On the other hand, the solubility with respect to the water of a detergent composition improves that it is below an upper limit.

(Alkaline)

As an alkali chemicals, if it is conventionally used for detergent compositions, such as medical use, it will not specifically limit, For example, Carbonates, such as sodium carbonate and potassium carbonate; Bicarbonates such as sodium bicarbonate and potassium bicarbonate; Double salts such as sodium carbonate; Silicates such as sodium silicate and potassium silicate; Alkanolamine, such as a monoethanolamine, diethanolamine, and a triethanolamine, are mentioned.

Alkali agent can be used individually by 1 type or in combination of 2 or more types.

Especially, it is preferable to use sodium carbonate and potassium carbonate together. It is preferable to use together sodium carbonate and potassium carbonate at sodium carbonate / potassium carbonate (mass ratio) = 95/5-60/40, and it is more preferable to use together at 90/10-70/30.

It is preferable that it is 15-60 mass%, and, as for content of the alkali chemicals in a detergent composition, it is more preferable that it is 25-50 mass%.

If content of an alkali chemicals is more than a lower limit, a washing | cleaning effect will improve. On the other hand, the solubility with respect to the water of a detergent composition improves that it is below an upper limit.

(Weapon builder)

The inorganic builder is not particularly limited as long as it is conventionally used in detergent compositions for medical use. For example, crystalline aluminosilicates (for example, A-type zeolites, P-type zeolites, X-type zeolites, etc.) and amorphous aluminas No silicate; Phosphates such as oxophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytin salts; And complexes of crystalline silicates, carbonates and amorphous alkali metal silicates.

An inorganic builder can use 1 type individually or in combination of 2 or more types.

It is preferable that it is 10-45 mass%, and, as for content of the inorganic builder in a detergent composition, it is more preferable that it is 10-30 mass%.

If content of an inorganic builder is more than a lower limit, the washing | cleaning effect will improve. On the other hand, if it is below an upper limit, the prevention of freezing of detergent particle | grains will become easy.

(Organic builder)

The organic builder is not particularly limited as long as it is conventionally used in detergent compositions for medical use. For example, nitrilotriacetic acid salt, ethylenediaminetetraacetic acid salt, β-alanine diacetic acid salt, aspartic acid diacetate, methylglycine Amino carboxylates such as diacetate and iminodi pumpkin salts; Hydroxyamino carboxylic acid salts such as serine diacetate, hydroxyethylimino diacetate, hydroxyethyl ethylenediamine triacetate, and dihydroxyethylglycine salt; Hydroxy carbonates such as hydroxyacetate, tartarate, citrate and gluconate; Cyclocarbonates such as pyromellitate, benzopolycarbonate, and cyclopentane tetracarboxylic acid; Carboxymethyl tartronate,

Ether carbonates such as carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono or disuccinate; Salts of polyacetalcarboxylic acids such as polyacrylates, salts of acrylic acid-allyl alcohol copolymers, salts of acrylic acid-maleic acid copolymers, and polyglyoxylic acids; Salts of acrylic acid polymers or copolymers such as hydroxyacrylic acid polymers and polysaccharide-acrylic acid copolymers; Salts of polymers or copolymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid and aspartic acid; Polysaccharide oxides such as starch, cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethyl cellulose.

It is preferable that it is 0.1-10 mass%, and, as for content of the organic builder in a detergent composition, it is more preferable that it is 1-5 mass%.

If content of an organic builder is more than a lower limit, a washing | cleaning effect will improve. On the other hand, if it is below an upper limit, the prevention of freezing of detergent particle | grains will become easy.

Among the inorganic builders and organic builders described above, since the cleaning power and the soil dispersibility in washing liquids are improved, citrate, aminocarboxylic acid salts, hydroxyaminocarboxylic acid salts, polyacrylates, salts of acrylic acid-maleic acid copolymers, poly It is preferable to use together organic builders, such as a salt of acetal carboxylic acid, and inorganic builders, such as a zeolite.

It is preferable to use these organic builders and inorganic builders together in organic builder / inorganic builder (mass ratio) = 5 / 95-30 / 70, and it is more preferable to use them together in 10 / 90-20 / 80.

10-40 mass% is preferable, and, as for content of the sum total of the inorganic builder and organic builder in a detergent composition, 15-25 mass% is more preferable.

Examples of the oxygen-based bleaching component in the detergent composition include percarbonates such as sodium percarbonate and perborates such as sodium perborate.

1-20 mass% is preferable, as for content of the oxygen type bleaching component in a detergent composition, 3-15 mass% is more preferable, and its 5-10 mass% is still more preferable.

As for content of the bleaching activator granulated material in the 1st aspect of this invention in a detergent composition, since it gives sufficient bleaching effect, 0.1-10 mass% is preferable, 0.3-7 mass% is more preferable, 0.5 5 mass% is more preferable.

In the detergent composition, the mixing ratio of the oxygen-based bleaching component and the bleaching activator granulated material is preferably an oxygen-based bleaching component / bleaching activator granulated product (mass ratio) = 20/1 to 1/1, and 15/1 to 2/1 More preferably, 10/1-3/1 are more preferable.

The manufacturing method of a detergent composition can be manufactured by a well-known manufacturing method. For example, after disperse | distributing and dissolving surfactant and arbitrary components in water, it can spray-dry and obtain powdery surfactant particle. In addition, for example, the surfactant and the optional components are provided to devices such as kneading / extrusion, stirring granulation, rolling granulation, and the like, and subjected to kneading, granulation, compression molding, and the like by grinding or the like as desired. Detergent compositions in the form can be obtained.

Moreover, since the bleach activator granulated material in the 1st aspect of this invention and the bleach composition containing percarbonate, such as sodium percarbonate, or perborate, such as sodium perborate, as an oxygen type bleaching component are excellent in a bleaching effect, , Especially preferred.

<Method of Manufacturing Bleach Activator Granules>

The manufacturing method of the bleaching activator granulated material in the 2nd aspect of this invention is a manufacturing method of the bleaching activator granulated material in the 1st aspect of this invention, Comprising: It kneading and kneading the said (A)-(F) component It has a kneading process and the extrusion granulation process which performs extrusion granulation using the kneaded material obtained by the said kneading process.

[Chemical process]

In a kneading process, kneading kneading | mixing of the said (A)-(F) component is carried out.

The method of performing said kneading kneading | mixing is not specifically limited, For example, the method of using a conventionally well-known batch type or continuous kneading machine is mentioned.

When using a kneading machine of a batch type, the horizontal type which has a stirring blade which rotates a longitudinal direction inside, for example, said (A) component, (E) component, (F) component, and (C) component The kneaded product can be obtained by introducing into the chamber and subsequently introducing (B) component and (D) component melted together into the horizontal chamber to kneading and kneading.

It is preferable that the stirring blade rotates in the vertical direction with respect to the horizontal axis of a horizontal chamber, and the rotation speed is about 120-360 rpm. Various things can be used for the stirring blade, Especially, a ski-type shovel wing is preferable. Moreover, it is also preferable to use together the chopper blade which rotates at 3000-6000 rpm with a stirring blade.

As a kneader which has a horizontal chamber provided with such stirring blades, For example, Flow share mixer (made by Pacific Pore Corporation); And a radig mixer, a ribbon mixer, a turbulizer, a pug mixer, and a spartanizer (above, manufactured by Fuji Powder Co., Ltd.).

In the case of using a continuous kneader, for example, all the raw materials (A) to (F) are continuously fed into a hermetic compaction apparatus (preferably a horizontal continuous kneader). At the temperature (preferably 25-100 degreeC, more preferably 40-80 degreeC) which (B) component and (D) component melt, after introducing and mixing powder in the said compaction processing apparatus, or mixing. The kneaded material can be obtained by heating and applying kneading and kneading kneading under the temperature.

Or (A) thru | or the sealing-type compaction-processing apparatus (preferably horizontal type | mold kneader) is continued to heat at the temperature which (B) component and (D) component melt | dissolve, and previously mixed-powdered there. A kneaded product can be obtained by continuously introducing the powder mixture of (F) component and kneading kneading | mixing.

Such kneading kneading may be performed using a single screw or twin screw kneading extruder or the like in addition to the kneader. As a continuous kneader used here, KRC kneader by Kurimoto Iron Works Co., Ltd., an extruder made by Nara Machinery, etc. are mentioned, for example.

In the kneading step, the temperature at the time of kneading kneading is preferably equal to or higher than the dehydration temperature of the component (E), more preferably 3 ° C or more higher than the melting point of the component (D), and more than the melting point of the component (B). It is more preferable that it is 5-20 degreeC high temperature.

By performing kneading kneading above the dehydration temperature of (E) component, the extrusion pressure at the time of extruding from an extruder does not become low too much, and the shape retention of an extrudate becomes favorable.

In addition, it is preferable to perform kneading kneading in a kneading process, without adding water substantially.

By carrying out kneading kneading without substantially adding water, the storage stability of the bleaching activator granulated material becomes favorable.

When kneading and kneading the said (A)-(F) component, it is preferable that each component uses the following.

Since the storage stability of (B) component, (C) component, and (F) component improves the bleaching activator granulated material, it is preferable to use a powdery thing as it is.

(A) component is obtained with plate shape of about 100-1000 micrometers in average particle diameter, if it is a normal manufacturing method. Although the average particle diameter of (A) component as a raw material used by the manufacturing method in the 2nd aspect of this invention is not specifically limited, When the average particle diameter is smaller than 300 micrometers, it is excellent in both solubility to water and storage stability. It is easy to obtain bleach activator granules. Therefore, when the average particle diameter of (A) component is 300 micrometers or more, it is preferable to grind and use so that an average particle diameter may become smaller than 300 micrometers by a daily method as needed, and it grind | pulverizes so that it may be about 100-200 micrometers. It is more preferable to.

Since the component (C) can be easily powdered, the component (C) may be mixed with a small amount of inorganic salts (sodium chloride, sodium sulfate, aluminosilicate, calcium carbonate, etc.). good.

It is preferable to use the solid or powder of 50-300 micrometers of average particle diameters, and, as for (E) component, it is more preferable to use the solid or powder of 50-250 micrometers. If the average particle diameter of (E) component is more than a lower limit, the powder flying of (E) component itself is suppressed. On the other hand, if the average particle diameter of (E) component is below an upper limit, it will become easy to obtain a uniform kneaded material.

It is preferable to use solid or powder of 50-200 micrometers of average particle diameters, and, as for (F) component, it is more preferable to use solid or powder of 50-150 micrometers. When the average particle diameter of (F) component is more than a lower limit, the powder flying of (F) component itself is suppressed, and the freezing prevention effect by hygroscopicity improves. On the other hand, if the average particle diameter of (F) component is below an upper limit, it will become easy to obtain a uniform kneaded material.

(D) / (A) = 0.045-0.2 are preferable and, as for the compounding ratio of (A) component and (D) component, the mass ratio represented by (D) / (A) is 0.05-0.15. .

If it is below the upper limit of (D) / (A), the compounding ratio of (A) component in a granulated material will become high and a bleaching effect will improve. If it is more than the lower limit of (D) / (A), the solubility with respect to the water of a bleaching activator granulated body will improve.

(E) / (A) = 0.16-0.55 is preferable and, as for the mixture ratio of (A) component and (E) component, the mass ratio represented by (E) / (A) is 0.2-0.5 more preferable. .

If it is below the upper limit of (E) / (A), the extrusion pressure at the time of extruding from an extruder will not become low too much, and the shape retention of an extrudate will become favorable. If it is more than the lower limit of (E) / (A), the solubility with respect to the water of a bleaching activator granulated body will improve.

(F) / (A) = 0.12-0.5 are preferable and, as for the compounding ratio of (A) component and (F) component, the mass ratio represented by (F) / (A) is 0.15-0.45. .

If it is below the upper limit of (F) / (A), the storage stability of a bleaching activator granulated material will improve, and a favorable bleaching effect will become easy to be acquired even after a lapse of time storage. If it is more than the lower limit of (F) / (A), a bleaching activator granulated material will become difficult to become weak, and it will become difficult to produce fine powder at the time of grinding | pulverization.

(D) / (E) = 0.2-0.7 are preferable and, as for the mixture ratio of (D) component and (E) component, the mass ratio represented by (D) / (E) is 0.3-0.6 more preferable. .

If it is below the upper limit of (D) / (E), the extrusion pressure at the time of extruding from an extruder will not become low too much, and the shape retention of an extrudate will become favorable. If it is more than the lower limit of (D) / (E), the solubility with respect to the water of a bleaching activator granulated body will improve.

(D) / (F) = 0.2-0.7 are preferable and, as for the mixture ratio of (D) component and (F) component, the mass ratio represented by (D) / (F) is 0.3-0.6 more preferable. .

If it is below the upper limit of (D) / (F), the extrusion pressure at the time of extruding from an extruder will not become low too much, and the shape retention of an extrudate will become favorable. If it is more than the lower limit of (D) / (F), the storage stability of a bleaching activator granulated material will improve, and a favorable bleaching effect will become easy to be acquired even after a lapse of time storage.

It is preferable that it is 56-85 degreeC, and, as for the temperature of the kneaded material after kneading kneading | mixing, it is more preferable that it is 60-80 degreeC.

If the temperature of a kneaded material is more than a lower limit, a homogeneous kneaded material will be formed and solubility will improve and storage stability will also improve. On the other hand, if the temperature of the kneaded material is below the upper limit, the shape retention after extrusion granulation is improved, and the solubility is also improved.

It is preferable that it is 150-900g, and, as for the hardness of the kneaded material after kneading kneading | mixing, it is more preferable that it is 200-700g.

If the hardness of the kneaded product is not less than the lower limit, the kneaded product will not become too soft, and the decrease in solubility due to coalescence after extrusion can be suppressed. It is possible to suppress the deterioration in solubility and deterioration in storage stability due to the increase in power.

"Hardness of the kneaded material" shows the value which carried out load conversion of the hardness of the kneaded material measured using a hard meter (made by Fujiwara Corporation).

In order to control the hardness of a kneaded material to the said suitable range, it is good to adjust the temperature at the time of kneading kneading | mixing, or to adjust the compounding quantity of (D) component, for example.

[Extrusion Assembly Process]

In an extrusion granulation process, extrusion granulation is performed using the kneaded material obtained by the said kneading process.

Specifically, strands, such as a cylinder, a footnote, and a delta, are thrown into the kneading | mixing material obtained by the said kneading process, and thrown into an uniaxial or biaxial screw kneading extruder; Obtain granules in the form of spheres, plates or noodle.

Especially, it is preferable to extrude the kneaded material obtained by the said kneading process through a die so that a desired diameter can be obtained. About 0.5-1.4 mm in diameter is preferable, and, as for the hole diameter of dice | dies, about 0.8-1.2 mm in diameter is more preferable.

The extrusion power in the extruder when extruding the kneaded material 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 25 kwh / t. Particularly preferred is t. If the extrusion power is 5 kwh / t or more, the storage stability of the resulting 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 fine powder hardly occurs when pulverized. In addition, the solubility in water of the bleach activator granules is improved.

As an extruder, a ferret double (made by Fuji Powder Co., Ltd.), a twin dome gran (made by Fuji Powder Co., Ltd.), a multi-grain (made by Dalton Corporation), etc. are mentioned, for example.

In addition, you may perform operation which obtains kneaded material by kneading kneading in a kneading process, and operation which performs extrusion granulation in an extrusion granulation process with one apparatus. As this method, the method of providing a granulated material by providing a mesh board in the discharge port of kneaded material in the apparatus for kneading kneading | mixing, and passing this mesh board, for example is mentioned.

As an apparatus applicable to this method, the extrude ohmic made from Hosokawa Micron Corporation is mentioned, for example.

After performing extrusion granulation, in order to trim the length of the obtained extrudate, it is squeezed by imparting impact and shear force to the extrudate using a grinder (crushing granulator) equipped with a high speed rotary knife cutter or the like. It is preferable to carry out.

It is preferable that the rotation speed of a high speed rotary knife cutter is about 30-100 m / s in circumferential speed.

Examples of the pulverizer include communators (manufactured by Fuji Powder Co., Ltd.), fits mill (manufactured by Hosokawa Micron Co., Ltd.), speed mill (manufactured by Okada Precision Co., Ltd.), and the like.

By this sizing, it is preferable to make the said extrudate into the granulated material of 200-700 micrometers of average particle diameters, and it is more preferable to set it as the granulated material of 250-450 micrometers. The storage stability of a bleach activator granulated material will improve that the particle diameter of a granulated material is more than a lower limit. On the other hand, when the particle diameter of a granulated material is below an upper limit, the solubility with respect to the water of a bleaching activator granulated body improves.

The manufacturing method of the bleaching activator granulated material in the 2nd aspect of this invention may have other processes other than the above-mentioned printing process and extrusion granulation process.

As another process, the process of recoating the surface of the granulated material obtained by the extrusion granulation process, etc. are mentioned.

According to the manufacturing method of the bleaching activator granulated material in the 2nd aspect of this invention demonstrated above, fine powder hardly arises at the time of grinding | pulverization, and the bleaching activator granulated material excellent in the solubility in water and storage stability can be manufactured, You can get the effect. The reason why such an effect can be obtained is not clear, but it is assumed as follows.

As described above, the bleach activator tends to be degraded by preservation over time, and by the interaction with other components in the detergent composition or the bleach composition. When a bleach activator is mix | blended with a detergent composition, for example, the bleaching activating ability of a bleach activator falls with time with contact with the alkali agent contained in a detergent base. Therefore, the storage stability has been improved by preparing a dense granulated material in which a bleach activator is sufficiently coated with an organic binder or an anionic surfactant. However, on the other hand, since the strength of the granulated material becomes excessively high and becomes too hard, solubility in water decreases, and there is a problem in that fine powder is liable to be generated because the impact and shear force are strongly applied when pulverizing. As described above, it has been difficult until now to satisfy all of the storage stability, the solubility in water, and the generation of fine powder in pulverization.

In the manufacturing method in the 2nd aspect of this invention, the lubrication of the surface of a kneaded material increases by using together a specific nonionic surfactant (D) and the 1-9 hydrate of sulfate. When it is extruded by an extruder, it becomes difficult to apply excessive pressure to a kneaded material, and the granulated material which has moderate strength can be obtained without becoming too hard. In connection with this, when grinding | pulverization, it is also unnecessary to apply strong impact and a shear force.

In addition, by using the nitrogen-containing chelating agent (F), the component (F) acts as a binder to obtain a granulated article having increased flexibility. As a result, the impact or the like applied to the pulverization is absorbed to some extent, so that fine powder is hardly generated.

By the above, it is thought that such an effect is acquired by the manufacturing method in the 2nd aspect of this invention.

Moreover, in the manufacturing method in the 2nd aspect of this invention, the storage stability of the obtained bleaching activator granule improves by using the 1-9 hydrate (E) of a sulfate. On the other hand, when using the anhydride of sulfate instead of using (E) component, and mix | blends insufficient water separately, the storage stability of a bleaching activator granule worsens.

Although this reason is not clear, if anhydride of sulfate is used instead of (E) component and mix | blends insufficient water separately, the temperature rise accompanying generation | occurrence | production of the heat of hydration of a kneaded material will arise, and kneading kneading and extrusion It is thought that the storage stability of the bleach activator granules is deteriorated because the mechanical power at the time of preparation increases the coating of the bleach activator is insufficient and the granules having excessively high strength are prepared.

Example

Although an Example is used to demonstrate this invention further in detail below, this invention is not limited to these Examples. In addition, unless otherwise indicated, "%" shows the "mass%."

In addition, the average particle diameter was measured by the method similar to the above-mentioned [Measurement method of average particle diameter]. Dehydration temperature was measured similarly to the method mentioned above.

The composition of the bleaching activator granules manufactured by the manufacturing method of each example is shown in Tables 1 and 2.

The raw material used in the present Example is as follows.

Bleach activator (A)

OBS: 4-lauroyloxybenzene sulfonate sodium

As raw materials, p-phenol sulfonic acid sodium (Kanto Chemical Co., Ltd. reagent), N, N-dimethylformamide (Kanto Chemical Co., Ltd. reagent), and lauric acid chloride (Tokyo Chemical Co., Ltd. make) : It synthesize | combined by the following method using the reagent) and acetone (manufactured by Kanto Chemical Co., Ltd.).

100 g (0.51 mol) of previously dehydrated p-phenol sulfonic acid was dispersed in 300 g of N, N-dimethylformamide, and 111 g (0.51 mol) of lauric acid chloride was stirred at 50 DEG C for 30 minutes while stirring with a magnetic steerer. It dripped.

After completion of the dropwise addition, the reaction was carried out for 3 hours, the N, N-dimethylformamide was distilled off under reduced pressure (0.5 to 1 mmHg) at 100 ° C, and the obtained residue was washed with acetone, after which water / Recrystallized in acetone (= 1/1 mol) solvent. Yield 90%.

OBC: 4-decanoyloxybenzoic acid, the Mitsui Totsu Chemical Co., Ltd. make, a brand name "AC agent."

TAED: Tetraacetylethylenediamine, the Tokyo Chemical Industry Co., Ltd. make, a brand name "N, N, N ', N'- tetraacetylethylenediamine."

Organic binder (B)

PEG-6000: Lion Corporation make, brand name "PEG # 6000M", the mean molecular weight 6000, melting | fusing point 60 degreeC.

PEG-4000: Lion Co., Ltd. product, a brand name "PEG # 4000", an average molecular weight 4000, 55 degreeC of melting | fusing point.

Anionic surfactant (C)

AOS-Na: C14-C18 (alpha)-olefin sulfonic acid Na salt, the Lion Co., Ltd. make, brand name "Liporan PJ-400", an average particle diameter of 200 micrometers.

AS-Na: The alkyl sodium sulfate salt which has a C10-C18 alkyl group, the synonymization agent, a brand name "shinorin 90TK-T", an average particle diameter of 150 micrometers.

Nonionic surfactant (D) with melting point below 45 ° C

POE alkyl ether (EO = 15): Nonionic surfactant in which 15 mol of EO (ethylene oxide) was added to the C12-C16 natural alcohol, Lion Co., Ltd. product, brand name "LMAO-90", 90 mass% of pure parts Melting point 40 ° C.

POE alkyl ether (EO = 9): Nonionic surfactant in which 9 mol of EO (ethylene oxide) was added to the C12-C16 natural alcohol, Lion Co., Ltd. product, brand name "Reox CL-90", pure 100 Mass%, melting | fusing point 28 degreeC.

1 to 9 hydrates of sulfates (E)

Zinc sulfate, heptahydrate: Mitsui Metals Mining Co., Ltd. make, average particle diameter 580 micrometers, dehydration temperature 73 degreeC.

Zinc sulfate monohydrate: Horiike Industries, Ltd. make, brand name "ZNS-13", 200 micrometers of average particle diameters, 270 degreeC of dehydration temperature.

Copper sulfate (II), pentahydrate: Pure Chemical Co., Ltd., reagent grade, average particle size 530㎛, dehydration temperature 45 ℃.

Manganese sulfate (II) hexahydrate: Digestion Chemical Co., Ltd., reagent grade, average particle diameter 600㎛, dehydration temperature 60 ℃.

Nickel sulfate (II) hexahydrate: manufactured by Mitsui Metal Mining Co., Ltd., average particle size 550 µm, dehydration temperature 53 ℃.

Comparative component of 1-9 hydrate (E) of sulfate (it shows as "(E ') component" hereafter)

Sodium sulfate 10-hydrate: Pure Chemical Co., Ltd., reagent grade, average particle diameter 700㎛, dehydration temperature 37 ~ 43 ℃.

Nitrogen-containing chelating agent (F)

MGDA: Methylglycine diacetic acid trisodium, the BASF Corporation make, brand name "Trilon M powder", an average particle diameter of 80 micrometers.

Comparative component of nitrogen-containing chelating agent (F) (hereinafter referred to as "(F ') component")

Citric acid: Pure Chemical Co., Ltd., Reagent Express.

Succinic acid: Pure Chemical Co., Ltd., Reagent Express.

Other ingredients

The following zeolite was used as the grinding aid.

Zeolite: A-type zeolite, the product made by Tisilicate, the brand name "zeolite Na-4A".

The detergent base powder and sodium percarbonate granulated material used in [evaluation of storage stability] mentioned later are as follows.

Detergent base

The detergent base powder prepared by the manufacture example shown below was used.

After spray drying, each component except 2 mass% equivalency A-type zeolite was thrown into the reaction apparatus which has a stirrer and a jacket (jacket temperature 75 degreeC) so that it may become the following composition, and the slurry of 60 mass% of solid content concentration is prepared. It was.

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 mass%, soap: 7.6 mass%, impurities: 2.0 mass%.

LAS-K: Linear alkylbenzenesulfonic acid (The carbon number of a linear alkyl group is 10-14.) [The Lion Corporation make, brand name: Ripon LH-200 (96 mass% of LAS-H pure components)] at the time of the said slurry preparation The compound neutralized with 48 mass% potassium hydroxide aqueous solution is shown.

Acrylic acid maleic acid copolymer salt: The sodium salt of the copolymer of acrylic acid and maleic acid, a brand name "Socharan CP7", the BASF Corporation make.

Soap: C12-C18 fatty acid sodium [Lion Co., Ltd. product, 67 mass% of pure parts, Titer 40-45 degreeC; Fatty acid compositionC12 fatty acid: 0.7 mass%, C14 fatty acid: 11.4 mass%, C16 fatty acid: 29.2 mass%, C18F0 (stearic acid): 0.7 mass%, C18F1 (oleic acid): 56.8 mass%, C18F2 (linoleic acid) ): 1.2 mass%; Molecular weight 289].

Subsequently, the slurry was spray dried using the countercurrent drying tower under the following drying conditions, and a portion (2% by mass) of the A-type zeolite was sprayed to the lower part of the spray drying tower to obtain spray dried particles. . The average particle diameter of the obtained spray dried particle | grains was 300 micrometers, the bulk density was 0.3 kg / L, and the water content was 5 mass%.

(Dry condition)

Spray drying equipment: countercurrent, tower diameter 2.0m, effective length 5.0m

Atomization method: pressure nozzle method

Spray pressure: 30㎏ / ㎠

Hot air inlet temperature: 250 ℃

Hot air outlet temperature: 100 ℃

Subsequently, 73.8 mass parts of obtained spray-dried particle | grains, 17 mass parts of (alpha)-sulfo fatty acid alkyl ester salt containing pastes, 1.4 mass part of nonionic surfactants, and 1.3 mass parts of water are continuous kneader (KRC-S4 type, Kurimoto Co., Ltd.). Iron mill) was kneaded (kneader rotation speed 135rpm, jacket temperature: jacket inlet 5 ℃, outlet 25 ℃ (cooling through the jacket to cool)) to prepare a dough state. The temperature of the obtained dough state was 55 +/- 15 degreeC.

Subsequently, the obtained kneaded product was put into a ferret double (EXD-100 type, manufactured by Fuji Powder Co., Ltd.), extruded from a die having a hole diameter of 10 mm and a thickness of 10 mm and cut at the same time (cutter of cutter (cutter)). The circumferential speed was 5 m / s, and the pellet-shaped molded object (diameter about 10 mm, length 70 mm or less (substantially 5 mm or more)) was obtained.

(alpha)-sulfo fatty acid alkyl ester salt containing paste: C16-C18 (part derived from a fatty acid), the Lion Co., Ltd. product, 60 mass% of pure parts.

Nonionic surfactant: The nonionic surfactant in which 15 mol of EO (ethylene oxide) was added to the C12-C16 natural alcohol, the Lion Co., Ltd. product, brand name "LMAO-90", and 90 mass% of pure parts.

6.5 parts by mass of A-type zeolite as a grinding aid is added to 93.5 parts by mass of the obtained pellet-shaped molded product, and it is pulverized by using a Fitz mill (DKA-6 type, manufactured by Hosokawa Micron Co., Ltd.) arranged in three stages in a blower. Base powder was obtained. Grinding conditions were as follows. As for the temperature of the obtained detergent base powder, the particle amount of 30 +/- 10 degreeC, the average particle diameter of 350 micrometers, and the particle diameter of 150 micrometers or less was 10 mass% of the whole, and the bulk density was 0.85 kg / L.

(Milling conditions)

Blowing temperature: 15 ± 3 ℃

Air flow rate (ratio of air / high): 2.8 ± 0.25㎥ / kg

Screen diameter: 6mm, 4mm, 2mm from 3rd stage

Crusher rotation speed: 100% = 4700rpm (circumference speed about 60m / s)

Processing speed: 230㎏ / hr

Sodium percarbonate granulated product: A product made by Zhejiang JINKE CHEMICALS, trade name "SPCC", an amount of effective oxygen of 13.8% by mass, and an average particle diameter of 870 µm.

<Example of Preparation of Bleach Activator Granules>

According to the compounding component of the composition shown to Table 1, 2, and content (mass%), the bleaching activator granulated material was manufactured by the following manufacturing method, respectively.

In table, content of (E) component and (E ') component shows the quantity as a hydrous salt (as it is) containing a water molecule. Others represent the amount of pure parts converted.

The temperature (degreeC) of the kneaded material obtained by the kneading process, the hardness (g) of kneaded material, and the kneading power (A) at the time of kneading kneading | mixing were shown in the table, respectively. The hardness (g) of the kneaded material was measured in addition to the temperature measurement on the kneaded material immediately after the kneading step, using a hard meter (manufactured by Fujiwara Corporation).

The hole diameter (mmφ) of the die in the extrusion assembly process, the extrusion power (A), the temperature of the extrudate (° C), the current value (A), the extrusion power (kwh / t), the extrusion time (minutes), the extrusion amount ( Kg) are shown in the table, respectively.

(Example 1)

[Chemical process]

The hot water was circulated in the jacket of S-1KRC kneader by Kurimoto Iron Works Co., Ltd., the kneader main body was heated to the temperature of 65 degreeC, and it maintained at this temperature.

Subsequently, all components except the grinding aid shown in Table 1 were powder mixed to prepare a powder mixture with a total amount of 1.5 kg. This powder mixture was thrown into the said kneader continuously for 15 minutes, continuing operation, and after kneading, kneaded material was obtained by kneading kneading | mixing.

[Extrusion Assembly Process]

This kneaded material was sequentially put into the extruder (Dalton Co., Ltd. product made by Dalton, Multi Gran MG-55 type | mold) with a die which has a hole of 0.8 mm (phi), and granulated by extrusion through the said die.

By this extrusion granulation, a noodle-like granulated product having a length of 2 to 5 mm was obtained as an extrudate.

Then, the said noodle-like granulated material and the grinding aid were put into the speed mill (Okada Precision Co., Ltd.) which provided the screen of 2.5 mm (phi), and it grind | pulverized at 3000 rpm and the bleaching activator granulated material was obtained.

(Examples 2 to 11, and 13, Comparative Examples 1 to 4)

According to the composition shown in Tables 1 and 2, the same operation as in Example 1 was carried out to obtain a bleach activator granulated product. The powder mixture was added in 15 to 30 minutes per 1.5 kg.

(Example 12)

Hot water was circulated in the jacket of the PNV-5 type desk kneader (manufactured by New Eze Co., Ltd.), and the kneader main body was heated to 65 ° C, and the temperature was maintained.

Subsequently, in the composition shown in Table 1, (A) component, (E) component, (F) component, and (C) component were introduce | transduced in the horizontal chamber which has the inside of the stirring blade which rotates in a longitudinal direction.

Subsequently, (B) component and (D) component of 60 degreeC which melted together were introduce | transduced in the said horizontal chamber, and the kneaded material was obtained by kneading and kneading for 50 minutes.

The kneaded material obtained was subjected to the same operations as in the extrusion granulation step in Example 1 to obtain a bleach activator granulated product. At that time, 1.5 kg of the total amount of each component was added to the kneader.

(Comparative Example 5)

65 degreeC hot water was poured into the jacket of a 20-L-ready mixer (Matsubo Corporation), and was heated.

Subsequently, all components (5 kg of total quantity) except the grinding aid shown in Table 2 were put into the said reggae mixer, and granulation was carried out on the conditions of a spindle 150 rpm and a chopper 3000 rpm.

Then, the obtained granulated material and grinding aid were put into the speed mill (Okada Precision Co., Ltd.) which provided the screen of 2.5 mm (phi), and it grind | pulverized at rotation speed 3000rpm, and obtained the bleaching activator granulated material.

<Evaluation of Bleach Activator Assembly>

The following evaluation was performed about the bleach activator granulated material obtained by the manufacturing method of each case, respectively. The results were written together in Tables 1 and 2.

[Evaluation of Difficulty in Differentiating at the Time of Grinding]

About the bleaching activator granulated material obtained by each example, when classifying operation by the method similar to the said "measurement method of average particle diameter", the mass frequency of the granulated material collect | recovered on the base through the sieve of 149 micrometers in size is measured. And it evaluated based on the following evaluation criteria.

(Evaluation standard)

(Double-circle): The sum total of particle | grains of less than 149 micrometers of particle diameters was less than 2 mass% of the whole particle | grains.

(Circle): The sum total of particle | grains of less than 149 micrometers of particle diameters was 2 mass% or more and less than 7 mass% of the whole particle | grains.

(Triangle | delta): The sum total of particle | grains of less than 149 micrometers of particle diameters was 7 mass% or more and less than 14 mass% of the whole particle | grains.

X: The sum total of particle | grains of less than 149 micrometers of particle diameters was 14 mass% or more and less than 20 mass% of the whole particle | grains.

Xx: The sum total of the particle | grains of less than 149 micrometers of particle diameters was 20 mass% or more of the whole particle | grains.

[Evaluation of Solubility in Water]

To a 200 ml beaker (inner diameter 61 mm, height 87 mm) containing 200 ml of ion-exchanged water at a water temperature of 10 ° C., 1 g of the bleaching activator granules obtained in each example was added, and stirred and mixed with a magnetic steerer (steerer). Piece: length 20 mm, diameter 5 mm, rotation speed: 200 rpm), and the change in the electrical conductivity of the ion-exchanged water was measured over time with an electrical conductivity meter.

After confirming that there was no molten residue of the bleaching activator granulated material in ion-exchanged water, the dissolution rate (%) was calculated | required by following Formula.

Dissolution rate (%) = (maximum value of electric conductivity / electric conductivity) * 100

And while showing the time required for 90% (mass reference | standard) of the bleaching activator granulated material to melt | dissolve as a dissolution time (second), it evaluated based on the following evaluation criteria.

(Evaluation standard)

(Double-circle): The dissolution time was less than 200 second.

○: The dissolution time was 200 seconds or more and less than 300 seconds.

(Triangle | delta): Dissolution time was 300 second or more and less than 500 second.

X: The dissolution time was 500 seconds or more.

[Evaluation of Preservation Stability]

A mixture of 10 g of the bleach activator granulated product obtained in each example and 940 g of a detergent base powder and 50 g of a sodium percarbonate granule was uniformly mixed into one same carton carton detergent container (155 mm x 95 mm x 135 mm in height). Was filled, and this silk carton detergent container was preserve | saved for two weeks in the thermostat of 45 degreeC of temperature, and 60% of a relative humidity.

Thereafter, the seal carton detergent container was taken out from the thermostat and opened, and then only the bleach activator granulated material was sorted out from the contents.

The amount of organic peracid in the bleaching activator granulated product after extraction was measured by the following method.

How to measure the amount of organic peracid:

1 L of ion-exchanged water was placed in a 1 L beaker, and 3 ml of 5 mass% aqueous solution of LAS-Na (sodium dodecylbenzenesulfonate), 3 ml of 5 mass% aqueous solution of sodium carbonate, and 0.2 mass% aqueous solution of hydrogen peroxide were added thereto. The aqueous solution to which mL was added was stirred (100 rpm) for 1 minute with a magnetic steerer (using a cylindrical steerer piece having a diameter of 5 mm and a length of 20 mm).

Thereafter, 0.05 g of a bleach activator granulated product was added, stirred for 10 minutes, 10 ml of 0.3 mass% catalase aqueous solution was added, and stirred for 1 minute.

10 ml of 10 mass% potassium iodide solution and 20 ml of 20 mass% sulfuric acid solution were added to this solution.

Next, titration was performed with 0.02 mol / L sodium thiosulfate solution, and the organic peracid production rate (%) was computed by the following formula. In the formula, n represents the number of moles of the generated organic peracid (wherein OBS and OBC are n = 1 and TAED is n = 2).

And the residual ratio (mass%) of organic peracid was calculated | required by calculating the ratio of the organic peracid amount after storage with respect to the organic peracid amount before storage measured beforehand, and it evaluated based on the following evaluation criteria.

(Evaluation standard)

(Double-circle): The residual ratio of organic peracid was 85-100 mass%.

(Circle): The residual ratio of organic peracid was 70 mass% or more and less than 85 mass%.

(Triangle | delta): The residual ratio of organic peracid was 50 mass% or more and less than 70 mass%.

X: The residual ratio of organic peracid was less than 50 mass%.

From the results of Tables 1 and 2, Examples 1 to 13 according to the present invention, it was confirmed that the fine powder is hardly generated during the pulverization, it is possible to produce a bleach activator granule excellent in solubility in water and storage stability. there was.

(Industrial availability)

According to the bleach activator granulated material in 1st aspect of this invention, it is excellent in the solubility to water and storage stability.

Moreover, according to the manufacturing method of the bleaching activator granulated material in the 2nd aspect of this invention, it is hard to produce fine powder at the time of grinding | pulverization, and the bleaching activator granulated material excellent in the solubility to water and storage stability can be manufactured.

Claims (8)

Bleach activator (A), organic binder (B), anionic surfactant (C), nonionic surfactant (D) having a melting point of less than 45 ° C, sulfates 1-9 hydrate (E), A bleach activator granulated product comprising a nitrogen-containing chelating agent (F). The method of claim 1,
The bleaching activator granulated product wherein said 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 cationic ammonium group; n <_2> represents the integer of 0-5.] 3. The method according to claim 1 or 2,
The bleach activator (A) is at least one 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 general formula (13). Bleach activator granules, characterized in that the compound.

[In formula, R <_1> and R <_2> is respectively independently a C7 or more linear alkyl group; M is a salt forming cation or a hydrogen atom.] 4. The method according to any one of claims 1 to 3,
The organic binder (B) is a bleach activator granulated, characterized in that the polyethylene glycol of the average molecular weight 400 to 30000. The method according to any one of claims 1 to 4,
The anionic surfactant (C) is a linear or branched alkylbenzenesulfonate (average carbon number of the straight or branched alkyl group is 8 to 18), long chain alkylsulfonate (the average carbon number of the long chain alkyl group is 10 to 20) Long chain olefin sulfonates (average carbon number of the long chain olefin portion is 10 to 20), long chain monoalkyl sulfate ester salts (average carbon number of the long chain monoalkyl group is 10 to 20), α-sulfofatty acid ester salt (fatty acid residue) And at least one compound selected from the group consisting of 12 to 20 carbon atoms in average. The method according to any one of claims 1 to 5,
The said nonionic surfactant (D) is a polyethyleneglycol addition type nonionic surfactant which added 3 to 80 mol of ethylene glycol or ethylene oxide to 1 mol of C8-C20 aliphatic alcohols, and is less than 45 degreeC of melting | fusing point, It is characterized by the above-mentioned. Bleach activator assembly made. 7. The method according to any one of claims 1 to 6,
1-9 hydrate (E) of the said sulfate is vanadium sulfate heptahydrate, manganese sulfate pentahydrate, manganese sulfate pentahydrate, nickel sulfate heptahydrate, copper sulfate pentahydrate, zinc sulfate monohydrate, zinc sulfate Bleaching activator granulated body which is a hydrate of at least 1 sort (s) of sulfate selected from the group which consists of a hexahydrate and zinc sulfate and a hexahydrate. A method for producing a bleach activator granulated product according to any one of claims 1 to 7,
The bleach activator (A), the organic binder (B), the anionic surfactant (C), the nonionic surfactant (D), and the 1-9 hydrate (E) of the sulfate, A kneading step of kneading and kneading the nitrogen-containing chelating agent (F),
It has an extrusion granulation process which performs extrusion granulation using the kneaded material obtained by the said kneading process, The manufacturing method of the bleaching activator granulated material characterized by the above-mentioned.