JP2013253120A - Metal sulfate salt granule and manufacturing method thereof - Google Patents

Abstract

The present invention provides an oxidized catalyst granulated product that hardly causes solidification and has excellent solubility in water, and a method for producing the same.
An organic binder (A), an anionic surfactant (B), a nonionic surfactant (C) having a melting point of less than 45 ° C., and a transition metal sulfate (D) are added in an amount of 25 to 45. A kneading step of kneading and kneading the metal sulfate granulated product containing 20% by mass and 20% to 50% by mass of the nitrogen-containing chelating agent (E) and the components (A) to (E); The manufacturing method of the metal sulfate granulated product which has a granulation process which extrudes and granulates the kneaded material obtained at a sum process.
[Selection figure] None

Description

  The present invention relates to a metal sulfate granulated product and a method for producing the same.

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, an oxidation catalyst using metal ions is used in combination with an oxygen-based bleaching component.
This oxidation catalyst tends to have a reduced oxidation promotion effect due to interaction with other components in the composition over time. On the other hand, a granulated product of an oxidation catalyst is used from the viewpoint of maintaining the oxidation promoting ability.
For example, an oxidation catalyst granulated product containing a bleaching oxidation catalyst containing a copper and / or manganese compound and a chelating agent and a binder compound is disclosed (see Patent Document 1).

WO09 / 0748459 pamphlet

  However, since the conventional granulated product of an oxidation catalyst itself has a certain level of hygroscopicity, there is a problem that it is likely to cause solidification (so-called caking) when blended in a detergent composition. Further, the granulated product has insufficient solubility in water (particularly solubility in water at a low temperature of about 10 ° C.).

  This invention is made | formed in view of the said situation, and makes it a subject to provide the oxidation catalyst granulated material which was hard to produce solidification, and was excellent in the solubility with respect to water, and its manufacturing method.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the metal sulfate granulated product of the present invention comprises an organic binder (A), an anionic surfactant (B), a nonionic surfactant (C) having a melting point of less than 45 ° C., and a transition metal. It contains 25 to 45% by mass of sulfate (D) and 20 to 50% by mass of nitrogen-containing chelating agent (E).

  The method for producing a metal sulfate granulated product of the present invention is a method for producing the metal sulfate granulated product of the present invention, wherein the organic binder (A) and the anionic surfactant (B ), The nonionic surfactant (C), the transition metal sulfate (D), and the nitrogen-containing chelating agent (E) are kneaded and obtained in the kneading step. And a granulating step of extruding and granulating the kneaded product.

  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”.

According to the metal sulfate granulated product of the present invention, it is possible to provide an oxidation catalyst granulated product that hardly causes solidification and has excellent solubility in water.
In addition, according to the method for producing a metal sulfate granulated product of the present invention, an oxidation catalyst granulated product that hardly causes solidification and has excellent solubility in water can be produced.

<Metal sulfate granules>
The metal sulfate granulated product of the present invention comprises an organic binder (A), an anionic surfactant (B), a nonionic surfactant (C) having a melting point of less than 45 ° C., and a transition metal sulfate. (D) and a nitrogen-containing chelating agent (E) are contained.
Hereinafter, these components are also referred to as component (A), component (B), component (C), component (D), and component (E), respectively.

[Organic binder (A)]
The organic binder (A) has a function as a binder, is a solid at room temperature, and is preferably a water-soluble organic compound that melts when heated.
Among them, as the component (A), 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, 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 (A) does not include the component (B), the component (C), the component (D), and the component (E) in the present invention.

Specific examples of the component (A) 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 these, 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.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type.
In the metal sulfate granulated product, the content of the component (A) 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 (A) is 3% by mass or more, the hygroscopicity of the metal sulfate granulated product can be further suppressed. Further, in the production of a metal sulfate granulated product, fine powder is less likely to be generated during pulverization. On the other hand, when the content of the component (A) is 30% by mass or less, the blending balance of the component (D) and the component (E) is particularly well maintained, and the solubility in water is improved.

[Anionic surfactant (B)]
Examples of the anionic surfactant (B) include linear or branched alkyl (average carbon number 8 to 18) benzene sulfonate, long chain alkyl (average carbon number 10 to 20) sulfonate, long Chain olefin (average carbon number 10-20) sulfonate, long chain monoalkyl (average carbon number 10-20) sulfate ester, polyoxyethylene (average degree of polymerization 1-10) long chain alkyl (average carbon number 10 20) Ether sulfate ester salt, polyoxyethylene (average degree of polymerization 3-30) alkyl (average carbon number 6-12) phenyl ether sulfate ester salt, α-sulfo fatty acid ester salt (average carbon number 12-20); long chain Monoalkyl, dialkyl or sesquialkyl phosphates; polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates are used
Among these, as the component (B), linear or branched alkyl (average carbon number 8 to 18) benzene sulfonate, long chain alkyl (average carbon number 10 to 20) sulfonate, long chain Olefin (average carbon number 10 to 20) sulfonate, long chain monoalkyl (average carbon number 10 to 20) sulfate ester salt, α-sulfo fatty acid ester salt (average carbon number 12 to 20) are preferred, and long chain alkyl ( Particularly preferred are sulfonates having an average carbon number of 10 to 20) and long-chain olefins (average carbon number of 10 to 20).
The above “long chain” may be linear or branched, and may have a saturated or unsaturated bond.
(B) As for the form of the salt in a component, alkali metal salts, such as sodium and potassium, amine salt, ammonium salt, etc. are mentioned, An alkali metal salt is preferable.

As the component (B), one type may be used alone, or two or more types may be used in combination.
In the metal sulfate granulated product, the content of the component (B) is preferably 1 to 20% by mass, more preferably 3 to 18% by mass, and particularly preferably 5 to 15% by mass.
When the content of the component (B) is 1% by mass or more, the solubility of the metal sulfate granulated product in water is improved. On the other hand, when the content of the component (B) is 20% by mass or less, the blending balance of the component (D) and the component (E) is kept good, and the bleaching effect is improved.

[Nonionic surfactant having a melting point of less than 45 ° C. (C)]
When the metal sulfate granulated product of the present invention is produced, the component (C) is easily melted by heating and sufficiently mixed with other raw materials. Thereby, kneading | mixing is performed favorably and the metal sulfate granulated material which has moderate hardness is prepared.
(C) 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 (C) 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 mol (preferably 5 to 50 mol) of ethylene glycol or ethylene oxide is added per 1 mol of aliphatic alcohol having 8 to 20 carbon atoms (preferably 10 to 18), and melting point is less than 45 ° C. Are more preferred.
Specific examples of the component (C) include polyoxyethylene alkyl ethers (preferably those having 5 to 15 moles of ethylene glycol or ethylene oxide added thereto and alkyl having 12 to 18 carbon atoms).

As the component (C), one type may be used alone, or two or more types may be used in combination.
In the metal sulfate granulated product, the content of the component (C) is preferably 1 to 9% by mass, more preferably 2 to 9% by mass, and further preferably 3 to 8% by mass.
When the content of the component (C) is 1% by mass or more, the solubility of the metal sulfate granulated product in water is improved. On the other hand, when the content of component (C) is 9% by mass or less, when producing a metal sulfate granulated product, for example, the extrusion pressure at the time of extrusion from an extruder does not become too low, and the shape of the extrudate is retained. Is better. The obtained metal sulfate granulated product has physical properties that do not easily cause coalescence, and adhesion and solidification during transportation are easily suppressed.

[Transition metal sulfate (D)]
The transition metal sulfate (D) is preferably a sulfate of a metal element of Group 3-12 in the long-period periodic table, and is a metal of Group 3-12 in the long-period periodic table and the fourth period More preferably, it is an elemental sulfate, more preferably a sulfate of manganese, iron, cobalt, nickel, copper or zinc, particularly preferably a sulfate of copper or zinc, and a sulfate of zinc. Most preferably it is.
As the component (D), an anhydrous salt or a hydrated salt may be used. Among them, as the component (D), it is preferable to use a hydrated salt from the viewpoint of productivity and the shape retention of the granulated product, and the number of water molecules constituting the hydrated salt is 1 to 7 ( 1-7 hydrate) is preferred.
When a hydrate salt is used as the component (D), when the dehydration / transition temperature of the component (D) exists in the range of temperature conditions during kneading or granulation when producing the metal sulfate granulated product, The hardness of the metal sulfate granulated product changes abruptly, making it difficult to obtain a uniform (homogeneous) granulated product. Therefore, as the component (D), the dehydration / transition temperature is preferably outside the range of temperature conditions during kneading or granulation, the low temperature side is 55 ° C. or lower, and the high temperature side is 70 ° C. or higher. More preferred are those having a low temperature side of 43 to 50 ° C and a high temperature side of 73 to 280 ° C.

“Dehydration / transition temperature of component (D)” indicates a value observed by transition point measurement by differential scanning calorimetry (DSC). The dehydration / transition 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 transition metal sulfate polyhydrate is placed on the sample side. Measurement temperature range: 0 to 100 ° C., temperature increase rate: 2 ° C./min. The dehydration / transition temperature is the 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 / transition temperature.
In addition, about transition metal sulfate (D) which does not have an endothermic peak at 100 degrees C or less, dehydration and transition temperature are calculated by changing a measurement temperature range to 0-300 degreeC, and measuring similarly.

Specific examples of the component (D) include manganese sulfate monohydrate, manganese sulfate pentahydrate; nickel sulfate hexahydrate, nickel sulfate heptahydrate; copper sulfate pentahydrate; Examples thereof include zinc sulfate monohydrate, zinc sulfate hexahydrate, zinc sulfate heptahydrate and the like.
Of these, copper sulfate pentahydrate, zinc sulfate monohydrate, and zinc sulfate hexahydrate are preferable because the hygroscopicity of the metal sulfate granulated product is easily suppressed, and copper sulfate-5 Hydrates and zinc sulfate monohydrate are more preferred.

As the component (D), one type may be used alone, or two or more types may be used in combination.
In the metal sulfate granulated product, the content of the component (D) is 25 to 45% by mass, preferably 26 to 45% by mass, and more preferably 28 to 44% by mass.
When the content of the component (D) is 25% by mass or more, the hygroscopicity of the metal sulfate granulated product can be further suppressed. On the other hand, when the content of the component (D) is 45% by mass or less, when producing a metal sulfate granulated product, for example, the extrusion pressure at the time of extrusion from an extruder does not become too low, and the extrudate retains its shape. Becomes better. And the metal sulfate granule obtained has a physical property which does not raise | generate coalescence, and generation | occurrence | production of the adhesion | attachment and solidification in the case of transport is suppressed.

[Nitrogen-containing chelating agent (E)]
The nitrogen-containing chelating agent (E) 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 a salt thereof, hydroxyaminocarboxylic acid or a salt thereof.
Specific examples of the component (E) 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の整数を表す。式（ＩＩ）中、Ｘ^１〜Ｘ^４は同一であっても異なっていてもよく、それぞれ水素原子、アルカリ金属原子、アルカリ土類金属原子又はカチオン性アンモニウム基を表す。Ｒは水素原子又は水酸基を表し、Ｑは水素原子又はアルキル基を表し、ｎ_１は０又は１の整数を表す。式（ＩＩＩ）中、Ｙはアルキル基、水酸基又は水素原子を表す。Ｘ^５〜Ｘ^７は同一であっても異なっていてもよく、それぞれ水素原子、アルカリ金属原子、アルカリ土類金属原子又はカチオン性アンモニウム基を表す。ｎ_２は０〜５の整数を表す。］

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

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

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

  Among the compounds represented by the general formula (I), the compound represented by the following chemical formula (1) is preferable because fine powder is less likely to be generated during pulverization in the production of a metal sulfate granulated product. Compound (2-pyridinecarboxylic acid) or a salt thereof, or a compound represented by the following chemical formula (2) (2,6-pyridinedicarboxylic acid (dipicolinic acid)) or a salt thereof.

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

In the general formula (II), R represents a hydrogen atom or a hydroxyl group, and is preferably a hydroxyl group.
Q represents a hydrogen atom or an alkyl group.
In Q, the alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
n ₁ represents an integer of 0 or 1, and is preferably 1.

  Among the compounds represented by the general formula (II), the compound represented by the following chemical formula (3) is preferable because fine powder is less likely to be generated during pulverization in the production of a metal sulfate granulated product. Compound (2,2′-iminodisuccinic acid) or a salt thereof, or a compound represented by the following chemical formula (4) (3-hydroxy-2,2′-iminodisuccinic acid) or a salt thereof.

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

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

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

  Among the compounds represented by the general formula (III), the compound represented by the following chemical formula (5) is preferable because fine powder is less likely to be generated during pulverization in the production of a metal sulfate granulated product. Compound (nitrilotriacetic acid), a compound represented by the following chemical formula (6) (methylglycine diacetic acid (MGDA)), a compound represented by the following chemical formula (7) (serine diacetic acid), 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 metal sulfate granulated product, a part or all of the terminal group “—COOX” is “ -COO ^- ", and the compound acts as a binder, is considered.

(E) A component may be used individually by 1 type and may be used in combination of 2 or more type.
Among the above, as the component (E), the hygroscopicity of the metal sulfate granulated product is suppressed to a lower level, and fine powder is not particularly easily generated during pulverization. Therefore, the general formulas (I) to (I) The compound represented by III) is preferable, and the compound represented by the general formula (III) is more preferable. Among these, methylglycine diacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof is more preferable, and methylglycine diacetic acid or a salt thereof is most preferable.
In addition, as the component (E), since the hygroscopicity of the metal sulfate granulated product can be suppressed to a lower level, it is preferable to use one having an average neutralization degree of 80% or more, and 90% or more. It is more preferable to use, and it is especially preferable to use what is 100%.
As used herein, “degree of neutralization” means the molar fraction of the neutralized carboxylic acid relative to the total carboxylic acid in the molecule. It is 1.0 when all carboxylic acids in the molecule are neutralized, and 0 when all are in acid form (—COOH).

In the metal sulfate granulated product, the content of the component (E) is 20 to 50% by mass, preferably 25 to 45% by mass, and more preferably 30 to 40% by mass.
When the content of the component (E) is 20% by mass or more, when producing a metal sulfate granulated product, for example, the extrusion pressure at the time of extrusion from an extruder does not become too low, and the shape retention of the extrudate is good. It becomes. In addition, fine powder is less likely to be generated during pulverization. On the other hand, when the content of the component (E) is 50% by mass or less, the hygroscopicity of the metal sulfate granulated product is reduced, and solidification hardly occurs.

The total content of the transition metal sulfate (D) and the nitrogen-containing chelating agent (E) is preferably 55 to 85% by mass, and more preferably 60 to 82% by mass.
When the total content of the component (D) and the component (E) is within the above range, the solubility of the metal sulfate granulated product in water is improved, and the bleaching effect during washing is improved.

The mixing ratio of the anionic surfactant (B) and the transition metal sulfate (D) is preferably 0.05 to 0.44 in terms of mass ratio represented by (B) / (D). More preferably, it is 10 to 0.40. When (B) / (D) is at least the lower limit, the effect of suppressing moisture absorption can be easily obtained, and when (B) / (D) is at most the upper limit, solubility in water can be improved.
The blending ratio of the nonionic surfactant (C) having a melting point of less than 45 ° C. and the transition metal sulfate (D) is 0.05 to 0.36 in terms of mass ratio represented by (C) / (D). It is preferable that it is 0.06-0.30. When (C) / (D) is equal to or higher than the lower limit, solubility in water is improved, and when (C) / (D) is equal to or lower than the upper limit, a metal sulfate granulated product is produced. The extrusion pressure at the time of extrusion does not become too low, shape retention is improved, and solidification of the granulated product is easily suppressed.
The mixing ratio of the nitrogen-containing chelating agent (E) and the transition metal sulfate (D) is preferably 0.44 to 2.0 in terms of mass ratio represented by (E) / (D), and More preferably, it is 48-1.9. When (E) / (D) is not less than the lower limit, the extrusion pressure during extrusion does not become too high when producing a metal sulfate granulated product, and (E) / (D) is not more than the upper limit. If so, the hygroscopicity of the metal sulfate granulated product is likely to be suppressed.
The blending ratio of the organic binder (A), the anionic surfactant (B) and the nonionic surfactant (C) having a melting point of less than 45 ° C. is (A) / [(B) + (C)]. It is preferable that it is 0.7-2.0 by the mass ratio represented by these, and it is more preferable that it is 0.8-1.5. When (A) / [(B) + (C)] is within the above range, the shape retention of the metal sulfate granulated product is improved while maintaining good solubility in water, and hygroscopicity. Is easily suppressed.
The “mass ratio represented by (B) / (D)” is the content (mass%) of the component (B) relative to the content (mass%) of the component (D) in the metal sulfate granulated product. Indicates the ratio.
The “mass ratio represented by (C) / (D)” is the content (mass%) of the component (C) relative to the content (mass%) of the component (D) in the metal sulfate granulated product. Indicates the ratio.
The “mass ratio represented by (E) / (D)” is the content (mass%) of the component (E) relative to the content (mass%) of the component (D) in the metal sulfate granulated product. Indicates the ratio.
“Mass ratio represented by (A) / [(B) + (C)]” is the total content (mass%) of the component (B) and the component (C) in the metal sulfate granulated product. The ratio of the content (mass%) of the component (A) with respect to is shown.

[Other ingredients]
The metal sulfate granulated product of the present invention may contain other components other than the above-described components (A) to (E) as necessary.

In the metal sulfate granulated product of the present invention, it is preferable to blend a polyvalent carboxylic acid as a solubility improver, particularly under the condition that the laundry washing solution exhibits alkalinity.
Examples of the polyvalent carboxylic acid include succinic acid and citric acid. In the metal sulfate granulated product, the content of the polyvalent carboxylic acid is preferably 5% by mass or less, and more preferably 3% by mass or less. If it is 5 mass% or less, it will become easy to take especially the blend balance with (D) component. On the other hand, the lower limit value is preferably 1% by mass or more because the effect of improving solubility is easily obtained.

Moreover, what is normally mix | blended with detergents and bleaches for clothes etc. is mentioned as another component. Specifically, cationic surfactants, amphoteric surfactants, aluminosilicate salts such as zeolite as grinding aids; carbonates such as sodium carbonate and calcium carbonate, amorphous silica; calcium silicate, magnesium silicate, etc. Silicates, other inorganic salts (sodium sulfate, sodium chloride, etc.), medium chain or long chain fatty acids or salts thereof, bleach activators such as organic peracid precursors, 1-hydroxyethane-1,1-diphosphone Examples include heavy metal chelating agents other than the component (E) such as acids or salts thereof, clay minerals, fluorescent brighteners, ultraviolet absorbers, antioxidants, antibacterial agents, and pigments.
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 metal sulfate 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.
Organic peracid precursors react with hydrogen peroxide (oxygen-based bleaching component) generated from peroxides such as sodium percarbonate to produce organic peracids with strong bleaching power, thereby bleaching clothing, etc. It is effective. However, the organic peracid precursor is an unstable component that is likely to deteriorate over time, such as when the oxidation promoting effect is reduced due to the interaction with other components when blended in a granular detergent or a bleaching agent. For this reason, since it is difficult to obtain the effect of the blended amount, it is preferable that the metal sulfate granulated product of the present invention does not contain an organic peracid precursor.

The average particle diameter of the metal sulfate granulated product of the present invention is preferably 150 to 2000 μm, and more preferably 200 to 1200 μm.
When the average particle diameter of the metal sulfate 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, first, the 9-stage sieve is stacked above the pan so that the openings gradually increase, and a sample of 100 g / time is placed on the top of the sieve having the top opening of 1680 μm. Next, it was covered and attached to a low-tap type sieve shaker (manufactured by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and after shaking for 10 minutes, it remained on each sieve and saucer. Samples are collected for each mesh and the sample mass is measured.
When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle diameter (mass 50%) is obtained from the following equation, where c is the integration of mass frequency from the sieve to a μm sieve and c% is the mass frequency on the sieve of a μm.

According to the metal sulfate granulated product of the present invention described above, it is possible to provide an oxidation catalyst granulated product that hardly causes solidification and has excellent solubility in water.
The metal sulfate granulated product of the present invention is suitably used as a raw material to be blended in a detergent base and a granular detergent containing an oxygen bleaching component, a bleaching agent containing an oxygen bleaching component, or a dishwasher cleaning agent. it can.
In the metal sulfate granulated product of the present invention, even when blended with a granular detergent or a bleaching agent, the oxidation promoting ability is stably maintained. For this reason, even if the metal sulfate granulated product of the present invention does not further contain an organic peracid precursor, it can exhibit a high oxidation promoting effect when used together with an oxygen-based bleaching component. And the bleaching effect is enhanced.
Further, since the granular detergent or bleach containing the metal sulfate granulated product of the present invention is less likely to solidify, it was washed using a granular detergent or bleach containing an oxidation catalyst granulated product that is likely to solidify. Troubles such as discoloration of clothes that tend to cause problems are unlikely to occur.

As the detergent base in the granular detergent, those usually blended in detergents for clothing and the like can be used.
For example, surfactants, alkali agents, inorganic builders, organic builders, bleaching components, bleach activators, reducing agents such as sulfites and thiosulfates, and particle strength retention such as sulfates are used in detergent bases. Agent (preferably sodium sulfate in granular detergent 1-20% by mass), fluorescent brightener, UV absorber, enzyme (eg protease, lipase, cellulase, amylase etc.), softener (bentonite etc.), recontamination (Deposition) inhibitors, foam control agents (such as silicone), fragrances, surface modifiers, oil absorbents, antioxidants, antibacterial agents, pigments such as ultramarine blue, dyes, and the like.

(Surfactant)
Surfactant will not be specifically limited if it is conventionally used for washing | cleaning agents for clothes etc. Various things 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.
Alkyl ether sulfuric acid having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of ethylene oxide, propylene oxide, butylene oxide or a mixture thereof added to 10 moles or less Salt or alkenyl ether sulfate (AES).
An alkyl ether carboxyl having a linear or branched alkyl 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. Acid salt 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.
An aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 12 to 16 carbon atoms, and an alkylene oxide having 2 to 4 carbon atoms on average 3 to 30 mol, preferably 5 to 20 mol on average, more preferably Polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether (alcohol alkoxylate) added on average 8 to 17 mol. Among these, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether are preferable.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group of the aliphatic alcohol may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.

  Polyoxyethylene alkyl phenyl ether, polyoxyethylene alkenyl phenyl ether.

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

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

Among the above, 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. 8-14.
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 alkyls having a melting point of 50 ° C. or lower and an HLB of 7 to 16. Examples include ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to fatty acid methyl ester, and fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide 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.

As the surfactant, one kind may be used alone, or two or more kinds may be used in combination.
Among the above, since the surfactant improves the cleaning performance, it is preferable to use an anionic surfactant and a nonionic surfactant in combination, and use MES and polyoxyethylene alkyl ether in combination. Is more preferable.
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 65/35. .
The content of the surfactant in the granular detergent 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 granular detergent 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 detergents for clothing, for example, carbonates such as sodium carbonate and potassium carbonate; heavy salts such as sodium bicarbonate and potassium bicarbonate. Carbonates; double salts such as potassium carbonate; silicates such as sodium silicate and potassium silicate; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
An alkali agent may be used individually by 1 type, and may be used in combination of 2 or more type.
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 granular detergent 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 granular detergent improves that it is below an upper limit.

(Inorganic builder)
The inorganic builder is not particularly limited as long as it is conventionally used for cleaning agents 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 metal silicic acid Examples include complexes with salts.
An inorganic builder may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the inorganic builder in the granular detergent 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 as a cleaning agent for clothing, for example, nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, Aminocarboxylates such as methylglycine diacetate and iminodisuccinate; hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxyacetate, Hydroxycarboxylates such as tartrate, citrate, and gluconate; Cyclocarboxylates such as pyromellitic acid salt, benzopolycarboxylate, and cyclopentanetetracarboxylate; carboxymethyl tartronate, carboxymethyloxy Succinate, Oxydisucci And ether carboxylates such as tartaric acid mono- or disuccinate; polyacrylates, salts of acrylic acid-allyl alcohol copolymers, salts of acrylic acid-maleic acid copolymers, polyacetal carboxylic acids such as polyglyoxylic acid Salt; salt of acrylic acid polymer or copolymer such as hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer; maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, Examples include salts of polymers or copolymers such as aspartic acid; polysaccharide oxides such as starch, cellulose, amylose, and pectin; and polysaccharide derivatives such as carboxymethyl cellulose.
The content of the organic builder in the granular detergent 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 stain dispersibility in washing washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid -It is preferable to use together an organic builder such as a salt of maleic acid copolymer and a salt of polyacetal carboxylic acid and 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 granular detergent, 15-25 mass% is more preferable.

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

The content of the metal sulfate granulated product of the present invention in the granular detergent is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass, from the viewpoint of imparting a sufficient bleaching effect. 0.5-5 mass% is further more preferable.
In the granular detergent, the mixing ratio of the oxygen-based bleaching component and the metal sulfate granulated product is preferably oxygen-based bleaching component / metal sulfate granulated product (mass ratio) = 20/1 to 1/1, 15/1 ~ 2/1 is more preferable, and 10/1 to 3/1 is more preferable.

  The manufacturing method of a granular detergent 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 detergent can be obtained.

  Further, a bleaching agent containing the metal sulfate granulated product of the present invention and a percarbonate such as sodium percarbonate or a perborate such as sodium perborate as an oxygen bleaching component is excellent in bleaching effect. Is particularly preferred.

<Method for producing metal sulfate granulated product>
The method for producing a metal sulfate granulated product of the present invention is a method for producing the metal sulfate granulated product of the present invention, wherein a kneading step of kneading and kneading the components (A) to (E), A granulation step of extruding and granulating the kneaded product obtained in the kneading step.

[Kazuwa process]
In the kneading step, the components (A) to (E) 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 that rotates the component (A), the component (B), the component (C), and the component (E) in the vertical direction. It introduce | transduces in a chamber and stir-mixes by heating a batch-type kneader to 40-80 degreeC. Next, a kneaded product is obtained by introducing the component (D) into the horizontal chamber and kneading and kneading.
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 Powdal Co., Ltd.); tabletop kneader (Irie Shokai Co., Ltd.) and the like.

In the case of using a continuous kneader, for example, a closed consolidation apparatus (preferably a horizontal type) heated to a temperature at which the component (C) melts (preferably 25 to 100 ° C., more preferably 40 to 80 ° C.). In the continuous kneader), the above component (A), component (B), component (C), and component (E) are mixed in advance after powder mixing or while component (D) is mixed. A powder mixture is prepared by introduction and powder mixing, and a kneaded product is obtained by applying a shearing force to the powder mixture and kneading gently at that temperature.
Alternatively, a hermetic consolidation apparatus (preferably a horizontal continuous kneader) is continuously heated to a temperature at which the component (A) and the component (C) are melted, and powder mixed therein (A ) To (E) 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.

Among the above methods, the method of using a continuous kneader is preferable because the hygroscopic property of the finally obtained metal sulfate granulated product can be suppressed low and solidification is less likely to occur.
In addition, since it is easy to obtain a metal sulfate granulated product that hardly causes solidification and has excellent solubility in water, the components (A) to (C) and (E) are first powder-mixed, and then (D The method of adding components and kneading gently is preferable.

In the kneading step, the temperature during kneading is preferably a temperature range that does not include the dehydration / transition temperature of component (D), and is a temperature that is 3 ° C. or higher than the melting point of component (C). It is more preferable that the temperature is 5 to 20 ° C. higher than the melting point of the component (A).
By performing kneading in a temperature range that does not include the dehydration / transition temperature of component (D), the extrusion pressure when extruding from the extruder becomes constant (stable), and a homogeneous extrudate is easily obtained, and , Shape retention 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 metal sulfate granulated product is improved.

When kneading the components (A) to (E), the content in the finally obtained metal sulfate granulation is 25 to 45% by mass of the (D) component, and 20 to 50 mass of the (E) component. Each component is blended so as to be%. In addition, it is preferable to use the following for each component.
Both the component (B) and the component (E) are preferably used as they are in a powder form because the storage stability of the metal sulfate granulated product is improved.
The component (B) 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 (B) can be easily powdered. Also good.
As the component (D), a powder having an average particle size of 30 to 800 μm is preferably used, a powder of 50 to 600 μm is more preferably used, and a powder of 60 to 550 μm is more preferably used. (D) When the average particle diameter of a component is more than a lower limit, the powdering of (D) component itself will be suppressed. On the other hand, when the average particle size of the component (D) is not more than the upper limit value, a uniform kneaded product is easily obtained.
As the component (E), a powder having an average particle diameter of 30 to 1500 μm is preferably used, a powder of 50 to 1300 μm is more preferably used, and a powder of 60 to 1200 μm is more preferably used. When the average particle size of the component (E) is equal to or greater than the lower limit, the powdering of the component (E) 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 (E) is not more than the upper limit value, a uniform kneaded product is easily obtained.

The temperature of the kneaded product after the kneading is preferably 50 to 65 ° C, more preferably 53 to 63 ° 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 50 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 (manufactured by Fujiwara Seisakusho).
In order to control the hardness of the kneaded material within the above-described preferable range, for example, the temperature at the time of kneading and kneading may be adjusted, or the blending amount of the component (C) may be adjusted.

[Granulation process]
In the granulation step, the kneaded material obtained in the kneading step is extruded and granulated.
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 temperature of the extrudate after extrusion granulation is preferably 48 to 70 ° C, and more preferably 52 to 67 ° C.
When the temperature of the extrudate is equal to or higher than the lower limit, the extrusion pressure does not become too high, and the burden (load) on the apparatus is easily reduced. On the other hand, when the temperature of the extrudate is equal to or lower than the upper limit value, coalescence of the granulated product is easily suppressed during the granulating (grinding) operation described later.

The extrusion power in the extruder when extruding the kneaded product is preferably 4 to 50 kwh / t, more preferably 4.5 to 48 kwh / t, still more preferably 5 to 45 kwh / t, Particularly preferred is 5.5 to 40 kwh / t.
When the extrusion power is 4 kwh / t or more, the storage stability of the resulting metal sulfate granulated product is improved. On the other hand, if the extrusion power is 50 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 metal sulfate granulated material improves.
Examples of the extruder include pelleter double (manufactured by Fuji Paudal Co., Ltd.), twin dome gran (manufactured by Fuji Powdal 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 in a 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 granulation, 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 Powder Co., Ltd.), a Fitzmill (manufactured by Hosokawa Micron Corporation), 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 size of 200 to 700 μm, more preferably a granulated product having a particle size of 250 to 450 μm. When the particle diameter of the granulated product is not less than the lower limit, the storage stability of the metal sulfate granulated product is improved. On the other hand, the solubility with respect to the water of a metal sulfate granulated material improves that the particle diameter of a granulated material is below an upper limit.
Moreover, it is preferable that the ratio of the granulated particle | grains of particle diameter less than 150 micrometers is 14 mass% or less with respect to the whole metal sulfate granulated material, and it is more preferable to set it as 0.2-10 mass%. When the amount is not more than the upper limit value, dust generation is less likely to occur, and the fluidity of the metal sulfate granulated product is improved.

The manufacturing method of the metal sulfate granulated product of this invention may have other processes other than the kneading | mixing process and granulation process which were mentioned above.
Examples of the other steps include a step of further covering the surface of the granulated product obtained in the granulation step.

According to the above-described method for producing a metal sulfate granulated product of the present invention, it is possible to produce an oxidation catalyst granulated product that is less prone to solidification and excellent in water solubility.
As described above, the granulated product of the conventional oxidation catalyst itself has a certain level of hygroscopicity, and thus is likely to cause solidification (so-called caking) when blended with the detergent composition. Moreover, in the conventional granulated product of an oxidation catalyst, the storage stability has been improved by preparing a tight granulated product using an organic binder or an anionic surfactant. However, on the other hand, since the strength of the granulated product is excessively increased and becomes too hard, the solubility in water is insufficient.
In the production method of the present invention, in addition to the organic binder (A) and the anionic surfactant (B), a nitrogen-containing chelating agent (E ) Acts as a binder to obtain a granulated product with increased flexibility. Moreover, the kneaded material surface is obtained by using the nonionic surfactant (C) having a melting point of less than 45 ° C. and the transition metal sulfate (D) so as to be contained in an amount of 25 to 45% by mass in the granulated product. This increases the lubricity and makes it difficult to apply excessive pressure to the kneaded product when it is extruded by an extruder, so that a granulated product having an appropriate strength can be obtained without becoming too hard. Furthermore, the (D) component is blended more frequently than in the past, making it difficult for particles to adhere to each other. It is presumed that the effects of the present invention can be obtained by these synergistic actions.

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 / transition temperature was measured in the same manner as described above.
The composition of the metal sulfate granulated product produced by the production method of each example is shown in Tables 1-3.
The raw materials used in this example are as follows.

・ Organic binder (A)
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 (B)
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 “Sinoline 90TK-T”, average particle size 150 μm.

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

・ Transition metal sulfate (D)
Zinc sulfate monohydrate: manufactured by Horiike Sangyo Co., Ltd., trade name “ZNS-13”, average particle size 200 μm, dehydration / transition temperature 270 ° C.
Copper (II) sulfate pentahydrate: manufactured by Junsei Chemical Co., Ltd., reagent grade, average particle size 530 μm, dehydration / transition temperature 45 ° C.

・ Nitrogen-containing chelating agent (E)
MGDA: trisodium methylglycine diacetate, manufactured by BASF Japan Ltd., trade name “Trilon M powder”, average particle size 80 μm; average neutralization degree 100%.

-Other ingredients Citric acid: Made by Junsei Co., Ltd., reagent grade.

The granular detergent used in [Evaluation of solidification of detergent] described later was prepared by the preparation method shown below so as to have the following composition.
Composition of granular detergent (blending component blending amount): MES-Na 9.0% by mass, LAS-Na 1.0% by mass, polyoxyethylene alkyl ether 4.0% by mass, soap 5.0% by mass, sodium carbonate balance Potassium carbonate 4.0% by weight, sodium sulfate 13.0% by weight, zeolite 15.0% by weight, acrylic acid-maleic acid copolymer salt 2.0% by weight, fluorescent whitening agent 0.1% by weight, water 7. 0% by mass, enzyme 1.0% by mass, sodium percarbonate granulated product 5.0% by mass, bleach activator granulated product 1.0% by mass, metal sulfate granulated product 1.0% by mass

Preparation method of granular detergent:
[Drying process]
Polyoxyethylene alkyl ether, MES-Na, part of zeolite (for grinding aid, for post-mixing step), enzyme, sodium percarbonate granulated product, bleach activator granulated product, metal An aqueous slurry having a solid content of 62% by mass was obtained by stirring a predetermined amount of all the ingredients except for the sulfate granulate at a preparation temperature of 80 ° C. for 17 minutes.
In addition, a part of the zeolite (for the grinding aid and for the post-mixing step) represents 30% by mass of the total amount of the zeolite.
Subsequently, the aqueous slurry was spray-dried to prepare spray-dried particles having a water content of 5% by mass.
[Granulation process]
Along with the spray-dried particles obtained in the drying step, a part of polyoxyethylene alkyl ether, MES-Na, and a small amount (1 part by weight with respect to 100 parts by weight of the spray-dried particles) of tap water (Edogawa, Tokyo) Was introduced into a continuous kneader (manufactured by Kurimoto Steel Co., Ltd., KRC-S4 type) and kneaded continuously at a temperature of 55 to 65 ° C.
Next, the kneaded material obtained by the kneading kneading was extruded while being continuously fed to a pelleter (made by Fuji Powder, die hole diameter 10 mmφ) to form a pellet-shaped solid detergent.
After that, Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKA-3 type) is arranged in three stages in series, and the solid detergent and a part of the zeolite (for grinding aid) are introduced together with cold air at 15 ° C. The granulated product was obtained by pulverizing and granulating so that the average particle size was 300 to 500 μm. The production capacity at this time was set to 180 kg / hr.
In addition, a part of said polyoxyethylene alkyl ether remove | excludes the part used by a post-mixing process, and shows 70 mass% part of polyoxyethylene alkyl ether whole quantity.
[Post-mixing process]
The granulated product obtained in the granulation step, the remaining polyoxyethylene alkyl ether (for 30% by mass), the remaining zeolite (for post-mixing step), the enzyme, and the sodium percarbonate granulated product, The bleach activator granulated product and the metal sulfate granulated product were mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, inner wall surface of drum of container 131.7 L and clearance 20 mm between the inner wall surface) And having a baffle plate with a height of 45 mm) and mixing for 1 minute under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, and 25 ° C. to produce granular detergents of each example.
At that time, only the polyoxyethylene alkyl ether (30% by mass) was added using a pressure nozzle while spraying so that the droplet diameter was 40 to 150 μm.
The granular detergents obtained in each example had a bulk density in the range of 0.82 to 0.88 g / cm ³ .

The raw materials used for the preparation of the granular detergent are as follows.
MES-Na: α-sulfo fatty acid alkyl ester salt-containing paste [paste composition: α-sulfo fatty acid alkyl ester salt (MES-Na) 63 mass%, nonionic surfactant (polyoxyethylene alkyl ether described later) 16 mass%, Impurities such as di-salt and methyl sulfate, 8% by mass, moisture 13% by mass] were used. The fatty acid chain length of the α-sulfo fatty acid alkyl ester salt (MES-Na) is 16 to 18 carbon atoms, and the mixing ratio of those having 16 carbon atoms and those having 18 carbon atoms is C16 / C18 = 8/2 (mass ratio).
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (LAS-H, manufactured by Lion Corporation, Lipon LH-200, AV value (potassium hydroxide required for neutralizing 1 g of LAS-H) mg number) = 180.0) neutralized with 48 mass% aqueous sodium hydroxide solution.
Polyoxyethylene alkyl ether: ECOROL 26 (trade name, manufactured by ECOGREN; alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (melting point: 40 ° C.). Pure content 90% by mass, moisture content 10% by mass.
Soap: C12-18 fatty acid sodium [manufactured by Lion Corporation, pure content 67 mass%, titer 40-45 ° C; fatty acid composition C12 0.7 mass%, C14 11.4 mass%, C16 29.2 mass% C18F0 (stearic acid) 0.7% by mass, C18F1 (oleic acid) 56.8% by mass, C18F2 (linoleic acid) 1.2% by mass; molecular weight 289].
Sodium carbonate: granular ash (manufactured by Asahi Glass Co., Ltd.) Average particle size 320 μm, bulk density 1.07 g / cm ³ .
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.) average particle size 490 μm, bulk density 1.30 g / cm ³ .
Sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”.
Zeolite: Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 μm.
Acrylic acid-maleic acid copolymer salt: sodium salt of a copolymer of acrylic acid and maleic acid, trade name “Socaran CP7”, manufactured by BASF Japan Ltd.
Fluorescent brightener: Ciba Specialty Chemicals Co., Ltd., trade name “Chino Pearl CBS-X”.
Water Enzyme: Protease (Sabinase 12T) / Amylase (Stainzyme 12T) / Lipase (LIPEX100T) / Cellulase (CellClean 4500T) (all from Novozymes Japan Ltd.) = 2/1/1/1 (mass ratio) Mixture of.
Sodium percarbonate granulated product: manufactured by Zhejiang JINKE CHEMICALS, trade name “SPCC”, effective oxygen amount 13.8% by mass, average particle size 870 μm.
Granulated product of bleach activator: OBS12 (sodium 4-dodecanoyloxybenzenesulfonate), PEG-6000, AOS (sodium α-olefinsulfonate having 14 carbon atoms), and A-type zeolite powder Granulated product having a mass ratio of 70/20/5/5.
Metal sulfate granulated product: Metal sulfate granulated product of Examples 1 to 12 and Comparative Examples 1 to 6 described later.

<Production example of metal sulfate granulated product>
According to the blending components and contents (mass%) of the compositions shown in Tables 1 to 3, metal sulfate granules were produced by the following production methods.
In the table, the content of the component (D) indicates the amount as a hydrated salt containing water molecules. Other components indicate the amount in terms of pure content.
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 pore diameter (mmφ), extrusion power (A), extrudate temperature (° C), air current value (A), extrusion power (kwh / t), extrusion time (minutes), extrusion rate (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 Corporation, and the kneader body was heated to 60 ° C. and maintained at that temperature.
Subsequently, all the components except the component (D) shown in Table 1 were powder-mixed at room temperature, and then the component (D) was 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, a kneaded product was obtained by performing a kneading kneading operation.

[Granulation process]
The obtained kneaded material is continuously put into an extruder (manufactured by Dalton Co., Ltd., multi-gran MG-55 type) equipped with a die having 1.0 mmφ holes, and granulated by extruding through the die. Went.
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 granule was put into a speed mill (Okada Seiko Co., Ltd.) provided with a 2.5 mmφ screen, and pulverized at a rotational speed of 3000 rpm to obtain a metal sulfate granulated product.

(Example 2)
[Kazuwa process]
Hot water was circulated in the jacket of a PNV-5 type table kneader (manufactured by Irie Shokai Co., Ltd.), and the kneader body was heated to 60 ° C. to maintain the temperature.
Next, components other than the component (D) in the composition shown in Table 1 were introduced into a horizontal chamber having stirring blades rotating in the vertical direction.
Next, after performing the kneading operation at a rotating speed of the stirring blade of 45 rpm, the component (D) heated to 58 ° C. was introduced into the horizontal chamber, and the kneading operation (the rotating speed of the stirring blade of 45 rpm) was performed for 50 minutes. A kneaded product was obtained by carrying out the process. At that time, a total amount of 1.5 kg of each component was put into the kneader.
[Granulation process]
The obtained kneaded product was subjected to the same operation as in the granulating step in Example 1 to obtain a metal sulfate granulated product.

(Examples 3-8, 10-12)
According to the composition and production conditions shown in Tables 1 and 2, the same operation as in Example 1 was performed to obtain a metal sulfate granulated product. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components.

Example 9
[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 57 ° C. and maintained at that temperature.
Subsequently, according to the composition and production conditions shown in Table 2, all the components (A) to (E) were powder-mixed together to prepare a powder mixture having a total amount of 1.5 kg. This powder mixture was continuously charged into the kneader while continuing the operation, and after the charging, a kneading operation was performed to obtain a kneaded product. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components.
[Granulation process]
The obtained kneaded product was subjected to the same operation as in the granulating step in Example 1 to obtain a metal sulfate granulated product.

(Comparative Examples 1-4)
According to the composition and production conditions shown in Table 3, by performing the same operation as in Example 9 (powder mixing, kneading kneading, extrusion granulation) together with all the components of (A) to (E), A metal sulfate granulated product was obtained. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components.

(Comparative Example 5)
A (E) component is introduced at 40 ° C. into a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.) having a scissors blade-shaped excavator and a clearance between the shovel and the wall surface of 5 mm, and water while rotating the main shaft at 200 rpm. (1.0 part by mass with respect to 100 parts by mass of component (E)) was sprayed.
After completion of spraying, the component (D) was added at 40 ° C., stirring was performed while the main shaft was rotated at 200 rpm (the chopper was stopped), and a metal sulfate granulated product was obtained 5 minutes after the stirring was started.

(Comparative Example 6)
According to the composition and production conditions shown in Table 3, the same operations as in Example 9 (components (A) to (C), (E) and all components of citric acid were mixed together, kneaded and extruded. Granulation) was performed to obtain a metal sulfate granulated product. The powder mixture was charged for 19 minutes per 1.5 kg of the total amount of the components.

<Evaluation of metal sulfate granules>
The following evaluation was performed on the metal sulfate granulated product obtained by the production method of each example. The results are also shown in Tables 1-3.

[Proportion of particles having a particle diameter of less than 150 μm]
About the metal sulfate granulated product obtained in each example, when classified by the same method as the above-mentioned “Method for measuring average particle diameter”, the granulated product passed through a sieve having an aperture of 149 μm and collected on the tray The mass frequency of the product was measured, and the ratio (mass%) of particles having a particle diameter of less than 150 μm was determined.
It means that the smaller the proportion of particles having a particle diameter of less than 150 μm, the more the granulated product is less likely to generate fine powder.

[Evaluation of solubility of metal sulfate granules in water]
1 g of the metal sulfate 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 exchange water was measured over time with an electric conductivity meter. And after confirming that there was no undissolved residue of the metal sulfate granulated product in ion-exchanged water, the dissolution rate (%) was determined by the following formula.
Dissolution rate (%) = (measured value of electrical conductivity / maximum value of electrical conductivity) × 100
Next, the time required for the dissolution rate (%) to be 90% or more was determined as the dissolution time (seconds). Specifically, taking the time (seconds) on the horizontal axis and the electrical conductivity value on the vertical axis, the measurement is continued until the electrical conductivity is balanced over time, and when all of the metal sulfate granulate is dissolved Assuming that the electrical conductivity is 100%, the time required to reach 90% of the electrical conductivity was determined.
And according to the following evaluation criteria, the solubility with respect to the water of a metal sulfate granulated material was evaluated. The evaluation results were ◎ and ○, respectively.
(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 hygroscopicity of metal sulfate granules]
The hygroscopic property of the metal sulfate granulated product is a characteristic that serves as an indicator of the solidification property of the metal sulfate granulated product itself and the solidification property of the detergent when blended with the detergent. The higher the hygroscopicity, the more likely the metal sulfate granulated product or detergent is to be agglomerated and solidified.
The hygroscopic evaluation of the metal sulfate granulated product was performed as follows.
The metal sulfate granulated product (sample) obtained in each example was spread on a glass petri dish (inner diameter 85 mm) so as to have a thickness of 5 mm, and placed in a thermostat set at a temperature of 45 ° C. and a relative humidity of 80%. .
Next, every 60 minutes, the mass of the glass petri dish with the sample spread was measured in the thermostat and the change with time was recorded.
And the moisture absorption (mass%) was calculated | required by the following Formula (1). In the formula (1), “measured value”, “sample preparation amount”, and “sample collection amount” are as follows.
Measured value: Mass of the glass petri dish with the sample spread, measured after 48 hours in total.
Sample charge: The mass of a glass petri dish with the sample spread, which is measured after standing for 1 minute at a temperature of 25 ° C. before being placed in a thermostatic bath.
Sample collection amount: A value obtained by subtracting the mass of the glass petri dish measured after standing for 1 minute at a temperature of 25 ° C. from the sample preparation amount.

Based on the moisture absorption rate (mass%) obtained from the formula (1), the hygroscopic property of the metal sulfate granulated product was evaluated according to the following evaluation criteria. The evaluation results were “A”, “B”, and “B”.
(Evaluation criteria)
A: The moisture absorption was less than 5% by mass.
○: The moisture absorption was 5% by mass or more and less than 10% by mass.
(Triangle | delta): The moisture absorption was 10 mass% or more and less than 20 mass%.
X: The moisture absorption was 20% by mass or more and less than 40% by mass.
Xx: The moisture absorption was 40% by mass or more.

[Evaluation of solidification of detergent]
The above-mentioned granular detergent is prepared using the metal sulfate granulated product obtained in each example, and 1000 g of the granular detergent is filled into a seal carton detergent container (155 mm long × 95 mm wide × 135 mm high). The later sealed carton detergent container was stored for 2 weeks in a constant temperature bath at a temperature of 45 ° C. and a relative humidity of 60%.
Thereafter, the sealed carton detergent container was taken out of the thermostatic bath and opened, and the solidified state of the contents was confirmed by the following method.
The granular detergent was slowly discharged from the sealed carton detergent container onto a sieve having an opening of 5 mm. And the residual amount of the granular detergent remaining on the sieve was measured, and the solidification property of the detergent was evaluated according to the following evaluation criteria. The evaluation results were ◎ and ○, respectively.
(Evaluation criteria)
A: The remaining amount of the granular detergent remaining on the sieve was less than 50 g.
○: The remaining amount of the granular detergent remaining on the sieve was 50 g or more and less than 100 g.
Δ: The remaining amount of the granular detergent remaining on the sieve was 100 g or more and less than 300 g.
X: The residual amount of the granular detergent remaining on the sieve was 300 g or more.

From the results of Tables 1 to 3, it was confirmed that the metal sulfate granules of Examples 1 to 12 according to the present invention were excellent in solubility in water.
Moreover, the granular detergent which mix | blended the metal sulfate granulated material of Examples 1-12 has also confirmed that it was hard to produce solidification.

Claims (2)

  25-45 mass% of organic binder (A), anionic surfactant (B), nonionic surfactant (C) having a melting point of less than 45 ° C., and transition metal sulfate (D), A metal sulfate granulated product comprising 20 to 50% by mass of a nitrogen-containing chelating agent (E). A method for producing a metal sulfate granulated product according to claim 1,
The organic binder (A), the anionic surfactant (B), the nonionic surfactant (C), the transition metal sulfate (D), and the nitrogen-containing chelating agent (E) Kneading and kneading kneading,
And a granulating step of extruding and granulating the kneaded product obtained in the kneading step. A method for producing a metal sulfate granulated product, comprising: