WO2012043859A1 - Particles each containing aminocarboxylic acid (salt), and granular detergent composition - Google Patents

Abstract

Particles each containing an aminocarboxylic acid (salt), each of which comprises (a) a zinc compound and (b) an aminocarboxylic acid or a salt thereof, and which are characterized in that the (a)/(b) ratio is 0.5-6 by mole.

Description

Aminocarboxylic acid (salt) -containing particles and granular detergent composition

The present invention relates to aminocarboxylic acid (salt) -containing particles and granular detergent compositions.
This application claims priority based on Japanese Patent Application No. 2010-224126 filed in Japan on October 1, 2010 and Japanese Patent Application No. 2011-049624 filed on March 7, 2011 in Japan. , The contents of which are incorporated herein.

In recent years, due to increasing consumer awareness of cleanliness, detergent compositions for clothing and the like are required to have a sterilizing effect in addition to a cleaning effect.
As such a detergent composition, a composition in which an oxidation catalyst containing a chelating agent having a coordination position of 5 or less and a metal compound and a surfactant are blended has been proposed. As the chelating agent, aminocarboxylates such as methylglycine diacetate, iminodisuccinate, and hydroxyiminodisuccinate are used (see Patent Document 1).

However, since aminocarboxylate itself has a hygroscopic property, it tends to be agglomerated with other detergent raw materials when blended into a granular detergent composition. Therefore, the granular detergent composition containing an aminocarboxylate has a problem that solidification is likely to occur (so-called caking is likely to occur). In order to improve such a problem, at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof, or methyl alcohol glycine diacetate (x) as an aminocarboxylate salt, or polyvinyl alcohol, polyvinyl pyrrolidone, polyalkylene glycol And a mixed powder or mixed granule in which a polymer (y) selected from the group consisting of derivatives thereof is used in combination has been proposed (see Patent Document 2).

In addition, the conventional granulated product of the oxidation catalyst has insufficient solubility in water (particularly solubility in water at a low temperature of about 10 ° C.).

WO09 / 0748459 pamphlet Special table 2008-505236 gazette

However, with the technique described in Patent Document 2, the hygroscopicity of the aminocarboxylate is not reduced, and solidification of the granular detergent composition cannot be sufficiently prevented.
This invention is made | formed in view of the said situation, and makes it a subject to provide the aminocarboxylic acid (salt) containing particle | grains and granular detergent composition which are hard to produce solidification.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.

(1) A zinc compound (a) and an aminocarboxylic acid or a salt thereof (b) are contained, and the molar ratio represented by (a) / (b) is 0.5-6. Aminocarboxylic acid (salt) -containing particles.
(2) The aminocarboxylic acid (salt) -containing particles according to (1) above, wherein the zinc compound is a sulfate.
(3) The above (1), further comprising an organic binder (c), an anionic surfactant (d), and a nonionic surfactant (e) having a melting point of less than 45 ° C. Or the aminocarboxylic acid (salt) containing particle | grains as described in (2).
(4) The above (1), wherein the content of the zinc compound (a) is 10 to 80% by mass, and the content of the aminocarboxylic acid or a salt thereof (b) is 10 to 80% by mass. The aminocarboxylic acid (salt) -containing particles according to any one of (3) to (3). (5) A granular detergent composition comprising the aminocarboxylic acid (salt) -containing particles according to any one of (1) to (4).

According to the present invention, it is possible to provide aminocarboxylic acid (salt) -containing particles and a granular detergent composition that hardly cause solidification.

In the present invention, “aminocarboxylic acid (salt) -containing particles” means particles containing one or both of aminocarboxylic acid and aminocarboxylic acid salt.

In the present invention, “melting point” refers to a value measured by the melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical products”.

(Aminocarboxylic acid (salt) -containing particles)
The aminocarboxylic acid (salt) -containing particles of the present invention contain a zinc compound (a) and an aminocarboxylic acid or a salt thereof (b).
Since the aminocarboxylic acid (salt) -containing particles have low hygroscopicity, solidification hardly occurs even when they are blended into a granular detergent composition (caking is not likely to occur). Therefore, the aminocarboxylic acid (salt) -containing particles are suitable for blending into a powdery composition (cleaning agent, bleaching agent) for use in fiber processing or residential cleaning, especially for clothing. It is suitable for blending into a granular detergent composition (including those having bleaching performance).

The moisture absorption rate of the aminocarboxylic acid (salt) -containing particles is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
When the moisture absorption is less than or equal to the upper limit, solidification is less likely to occur when blended in a granular detergent composition or the like.

In the present invention, the “moisture absorption rate” refers to a value measured by the following procedure. First, the sample is spread on a glass petri dish (inner diameter: 85 mm) so as to have a thickness of 5 mm, and is placed in a thermostat set at a temperature of 45 ° C. and a relative humidity of 80%.
Next, at every elapsed time (every 60 minutes), the mass of the glass petri dish with the sample spread is measured in the thermostat and the change with time is recorded.
And a moisture absorption rate (mass%) is calculated | required by Formula (1) shown below. In the formula (1), “sample collection amount”, “sample preparation amount”, and “measurement value” 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.

The average particle size of the aminocarboxylic acid (salt) -containing particles is usually 150 to 2000 μm, preferably 200 to 1200 μm, more preferably 50 to 500 μm, still more preferably 70 to 350 μm, and more preferably 80 to 300 μm. Particularly preferred. When the average particle size is equal to or greater than the lower limit, dusting is suppressed when mixing with other detergent raw materials. On the other hand, the solubility to water improves that it is below an upper limit.
In the present invention, the “average particle diameter” is measured as a volume-based median diameter by a laser light scattering method using a particle size distribution analyzer (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.). It is a value (measurement method 1) or a value obtained by the following method (measurement method 2).
(Measurement method of average particle diameter) (Measurement method 2)
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.

The water content of the aminocarboxylic acid (salt) -containing particles is preferably 8% by mass or less, more preferably 5% by mass or less, and further preferably 0.3 to 4% by mass.
In the present invention, the moisture content indicates a value measured using an infrared moisture meter (product name: Kett moisture meter, manufactured by Kett Scientific Laboratory).

<Zinc compound (a)>
As the zinc compound (a) (hereinafter also referred to as “component (a)”), since granular detergent compositions and the like are usually used by being put into water, those which are easily dissolved in water are preferable. Includes a water-soluble salt of zinc.
Examples of the water-soluble salts include nitrates, sulfates, chlorides, acetates, perchlorates, cyanides, ammonium chlorides, tartrates, gluconates, and hydrates thereof. Can do.
As the component (a), zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, zinc chloride ammonium, zinc tartrate, zinc perchlorate, zinc gluconate, etc. are preferable. In view of safety, safety, and price, zinc sulfate is more preferable, and anhydrous zinc sulfate, zinc sulfate monohydrate, and zinc sulfate heptahydrate are particularly preferable.

When a hydrate salt is used as the component (a), the dehydration / transition temperature of the component (a) exists within the range of temperature conditions during kneading or granulation when producing aminocarboxylic acid (salt) -containing particles. Then, the hardness of the aminocarboxylic acid (salt) -containing particles changes abruptly, making it difficult to obtain a uniform (homogeneous) granulated product. Therefore, as the component (a), 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 preferably, the low temperature side is 43 to 50 ° C., and the high temperature side is 73 to 280 ° C.

“Dehydration / transition temperature of component (a)” 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 polyhydrate of zinc compound (a) is arranged 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.
For the zinc compound (a) having no endothermic peak at 100 ° C. or lower, the dehydration / transition temperature is calculated by changing the measurement temperature range to 0 to 300 ° C. and performing the same measurement.

(A) A component may be used individually by 1 type and may use 2 or more types together.
In the aminocarboxylic acid (salt) -containing particles, the content of the component (a) is preferably 10 to 80% by mass, more preferably 20 to 55% by mass in terms of anhydride.
When the content of the component (a) is equal to or higher than the lower limit, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is further reduced and solidification hardly occurs. On the other hand, when it is at most the upper limit value, it becomes easy to achieve a blending balance with an aminocarboxylic acid or a salt thereof (b) described later, and the effect of the present invention is improved.

<Aminocarboxylic acid or salt thereof (b)>
The aminocarboxylic acid or its salt (b) (hereinafter also referred to as “component (b)”) includes ethylenediaminetetraacetic acid or its salt, β-alanine diacetic acid or its salt, the following general formula (b1) or (b2 ) And the like.

[In the formula (b1), X ¹¹ to X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or a cationic ammonium, R represents a hydrogen atom or a hydroxyl group, and n ₁ represents 0 or 1 Represents an integer. In the formula (b2), A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group or a hydrogen atom, and X ²¹ to X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal or a cation. N ₂ represents an integer of 0 to 5. ]

In the formula (b1), examples of the alkali metal in X ¹¹ to X ¹⁴ include sodium and potassium.
Examples of the alkaline earth metal in X ¹¹ to X ¹⁴ include calcium and magnesium. Note that when at least one of X ¹¹ to X ¹⁴ is an alkaline earth metal, it corresponds to 1/2 atom. For example, when X ¹¹ is calcium, —COOX ¹¹ becomes “—COO ⁻ 1/2 (Ca)”.
Examples of the cationic ammonium in X ¹¹ to X ¹⁴ include alkanolamines such as monoethanolamine and diethanolamine, and specific examples include those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. . The alkanol group preferably has 1 to 3 carbon atoms.
Among the above, X ¹¹ to X ¹⁴ are preferably alkali metals.
X ¹¹ to X ¹⁴ may be the same or different from each other.

In the formula (b1), R may be a hydrogen atom or a hydroxyl group.
In the formula (b1), n ₁ is preferably 1.

Specific examples of the compound represented by the formula (b1) include iminodisuccinic acid, 3-hydroxy-2,2′-iminodisuccinic acid or a salt thereof, and iminodisuccinic acid or a salt thereof is preferable.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt, alkanolamine salts such as monoethanolamine salt and diethanolamine salt, and sodium salt and potassium salt are particularly preferable.

In the formula (b2), the alkyl group in A may be either linear or branched.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 18 carbon atoms. In the alkyl group, a part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group (—SO ₃ H), an amino group (—NH ₂ ), a hydroxyl group, and a nitro group (—NO ₂ ).
A may be any of an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group, and a hydrogen atom, and a hydrogen atom is particularly preferable.

In the formula (b2), the alkali metal, alkaline earth metal and cationic ammonium in X ²¹ to X ²³ are the same as the alkali metal, alkaline earth metal and cationic ammonium in X ¹¹ to X ¹⁴ respectively. Things.
Among these, X ²¹ to X ²³ are preferably alkali metals.
X ²¹ to X ²³ may be the same or different from each other.

In the formula (b2), n ₂ is preferably an integer of 0 to 2, and 1 is particularly preferable.

Specific examples of the compound represented by the formula (b2) include, for example, nitrilotriacetic acid, methylglycine diacetic acid, dicarboxymethylglutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid or salts thereof. Among them, nitrilotriacetic acid, methylglycine diacetic acid or a salt thereof is preferable, and methylglycine diacetic acid or a salt thereof is particularly preferable.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt, alkanolamine salts such as monoethanolamine salt and diethanolamine salt, and sodium salt and potassium salt are particularly preferable.

(B) A component may be used individually by 1 type and may use 2 or more types together.
Among these, as the component (b), since the solidification is less likely to occur, the compound represented by the general formula (b1) or (b2) is preferable, and the compound represented by the general formula (b2) is more preferable. preferable.
In the aminocarboxylic acid (salt) -containing particles, the content of the component (b) is preferably 10 to 80% by mass, and more preferably 35 to 75% by mass. When the content of the component (b) is equal to or higher than the lower limit, the blending effect of the component (b) (the effect of forming a chelate compound by coordination with metal ions) is more easily obtained. On the other hand, when it is at most the upper limit value, it becomes easy to achieve a blending balance with the component (a), and the effect of the present invention is improved.

When the compounds represented by the general formulas (b1) to (b2) are blended in, for example, a kneading step when producing aminocarboxylic acid (salt) -containing particles, a part or all of the terminal group “—COOX” Becomes “—COO ⁻ ” and the compound is considered to act as a binder.

Further, as the component (b), since the hygroscopicity of the aminocarboxylic acid (salt) -containing particles can be kept lower, it is preferable to use those having an average neutralization degree of 80% or more, and 90% or more. It is more preferable to use a thing, 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 present invention, “(a) / (b)” indicates the content ratio (molar ratio) of the component (a) to the component (b).
The mixing ratio of the component (a) and the component (b) in the aminocarboxylic acid (salt) -containing particles is such that the molar ratio represented by (a) / (b) is 0.5 to 6, Is preferably ˜5.8, more preferably 0.5˜5.5.
When the molar ratio represented by (a) / (b) is equal to or greater than the lower limit, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is reduced, and solidification hardly occurs. On the other hand, when the molar ratio represented by (a) / (b) is not more than the upper limit, the concentration of the component (b) is sufficiently secured.

<Other ingredients>
The aminocarboxylic acid (salt) -containing particles may contain other components as needed in addition to the components (a) and (b).
Other components include bases such as sodium bicarbonate, sodium hydroxide and potassium hydroxide; crystalline aluminosilicates (A-type zeolite, P-type zeolite, X-type zeolite, etc.), amorphous aluminosilicates, clay minerals ( Coating components such as talc and montmorillonite); binders such as polyethylene glycol, polyvinyl pyrrolidone and polyvinyl alcohol.
In the aminocarboxylic acid (salt) -containing particles, the content of the base is preferably 0.001 to 10% by mass, more preferably 0.002 to 1% by mass, and further preferably 0.003 to 0.1% by mass. When the content of the base is at least the lower limit value, when preparing the aminocarboxylic acid (salt) -containing particles, the component (b) tends to change to a structure that hardly absorbs moisture. On the other hand, if it is below the upper limit, it becomes easy to balance with other blending components, and the concentration of the component (b) is sufficiently secured.
In the aminocarboxylic acid (salt) -containing particles, the content of the coating component is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass. When the content of the coating component is equal to or more than the lower limit, the aminocarboxylic acid (salt) -containing particles are unlikely to be agglomerated and the fluidity is improved. On the other hand, if it is below the upper limit, it becomes easy to balance with other blending components, and the concentration of the component (b) is sufficiently secured.

As the binder, an organic binder (c) is preferable.

[Organic binder (c)]
The organic binder (c) 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 (c), 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 (c) does not include the component (d), the component (e), the component (a), and the component (b) in the present invention.

Specific examples of the component (c) 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.

(C) A component may be used individually by 1 type and may be used in combination of 2 or more type.
In the aminocarboxylic acid (salt) -containing particles, the content of the binder (c) 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 binder (c) is 3% by mass or more, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles can be further reduced. Further, in the production of aminocarboxylic acid (salt) -containing particles, fine powder is less likely to be generated during pulverization. On the other hand, when the content of the binder (c) is 30% by mass or less, the blending balance of the component (a) and the component (b) is particularly well maintained, and the solubility in water is improved.

The aminocarboxylic acid (salt) -containing particles may also contain an anionic surfactant (d) and a nonionic surfactant (e) having a melting point of less than 45 ° C.

[Anionic surfactant (d)]
Examples of the anionic surfactant (d) 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 10-10) 20) Ether sulfate ester salt, polyoxyethylene (average degree of polymerization 3 to 30) alkyl (average carbon number 6 to 12) phenyl ether sulfate ester salt, α-sulfo fatty acid ester salt (average carbon number 12 to 20); long chain Monoalkyl, dialkyl or sesquialkyl phosphates; polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates are used
Among the above, as the component (d), 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 salt, α-sulfo fatty acid ester salt (average carbon number 12-20) 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.
Examples of the salt form in the component (d) include alkali metal salts such as sodium and potassium, amine salts, ammonium salts and the like, and alkali metal salts are preferable.

(D) A component may be used individually by 1 type and may be used in combination of 2 or more type.
In the aminocarboxylic acid (salt) -containing particles, the content of the component (d) 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 (d) is 1% by mass or more, the solubility of the aminocarboxylic acid (salt) -containing particles in water is improved. On the other hand, when the content of the component (d) is 20% by mass or less, the blending balance of the component (a) and the component (b) is kept good, and the bleaching effect is improved.

[Nonionic surfactant (e) having a melting point of less than 45 ° C.]
When the aminocarboxylic acid (salt) -containing particles of the present invention are produced, the component (e) is easily melted by heating and sufficiently mixed with other raw materials. Thereby, kneading | mixing is performed favorably and the aminocarboxylic acid (salt) containing particle | grains which have moderate hardness are prepared.
The melting point of the component (e) is preferably 43 ° C. or less, more preferably 15 to 41 ° C.
Examples of the component (e) include polyethylene glycol addition type nonionic surfactants and polyethylene glycol-polypropylene glycol addition type nonionic surfactants. Among these, polyethylene glycol addition type nonionic surfactants are exemplified. Preferably, 3 to 80 moles (preferably 5 to 50 moles) of ethylene glycol or ethylene oxide are added per 1 mole of aliphatic alcohol having 8 to 20 carbon atoms (preferably 10 to 18 carbon atoms), and the melting point is less than 45 ° C. Are more preferred.
Specific examples of the component (e) include polyoxyethylene alkyl ethers (preferably having 5 to 15 moles of ethylene glycol or ethylene oxide added thereto and alkyl having 12 to 18 carbon atoms).

As the component (e), one type may be used alone, or two or more types may be used in combination.
In the aminocarboxylic acid (salt) -containing particles, the content of the component (e) 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 (e) is 1% by mass or more, the solubility of the aminocarboxylic acid (salt) -containing particles in water is improved. On the other hand, when the content of the component (e) is 9% by mass or less, when the aminocarboxylic acid (salt) -containing particles are produced, for example, the extrusion pressure at the time of extrusion from the extruder does not become too low, and the extrudate is maintained. The formability becomes better. And the aminocarboxylic acid (salt) containing particle | grains obtained have a physical property which is hard to raise | generate coalescence, and it is easy to suppress the generation | occurrence | production of adhesion | attachment and solidification in the case of transport.

In the aminocarboxylic acid (salt) -containing particles 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 aminocarboxylic acid (salt) -containing particles, 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 compounding balance with (a) 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 or long chain fatty acids or salts thereof, bleaching activators such as organic peracid precursors, 1-hydroxyethane-1,1-diphosphone Examples include heavy metal chelating agents other than the component (b) 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 aminocarboxylic acid (salt) -containing particles, 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 blending, it is preferable that the aminocarboxylic acid (salt) -containing particles of the present invention do not contain an organic peracid precursor.
Moreover, as other components, a pigment | dye, a fragrance | flavor, etc. can be mix | blended in the range which does not impair the effect of this invention.

As aminocarboxylic acid (salt) -containing particles, zinc compound (a), aminocarboxylic acid or salt thereof (b), organic binder (c), anionic surfactant (d), and melting point of less than 45 ° C. Aminocarboxylic acid (salt) -containing particles containing a nonionic surfactant (e) are preferable. Among them, the content of the zinc compound (a) is 10 to 80% by mass, and the aminocarboxylic acid or The content of the salt (b) is more preferably 10 to 80% by mass.

The mixing ratio of the anionic surfactant (d) and the zinc compound (a) is preferably 0.05 to 0.44 in terms of mass ratio represented by (d) / (a), and is 0.10. More preferably, it is ˜0.40. When (d) / (a) is equal to or higher than the lower limit, the effect of suppressing moisture absorption is easily obtained, and when (d) / (a) is equal to or lower than the upper limit, solubility in water is improved.

The blending ratio of the nonionic surfactant (e) having a melting point of less than 45 ° C. and the zinc compound (a) is 0.05 to 0.36 in mass ratio represented by (e) / (a). It is preferably 0.06 to 0.30. When (e) / (a) is at least the lower limit, solubility in water is improved, and when (e) / (a) is at most the upper limit, aminocarboxylic acid (salt) -containing particles are produced. In this case, the extrusion pressure at the time of extrusion does not become too low, the shape retention is improved, and the solidification of the granulated product is easily suppressed.

The mixing ratio of the aminocarboxylic acid or its salt (b) and the zinc compound (a) is preferably 0.44 to 2.0 in terms of mass ratio represented by (b) / (a). More preferably, it is 48 to 1.9. When (b) / (a) is at least the lower limit, when producing aminocarboxylic acid (salt) -containing particles, the extrusion pressure during extrusion does not become too high, and (b) / (a) is the upper limit. If it is less than the value, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is easily suppressed.

The blending ratio of the organic binder (c), the anionic surfactant (d) and the nonionic surfactant (e) having a melting point of less than 45 ° C. is (c) / [(d) + (e)] Is preferably 0.7 to 2.0, and more preferably 0.8 to 1.5. When (c) / [(d) + (e)] is within the above range, the shape retention of the aminocarboxylic acid (salt) -containing particles is improved while maintaining good solubility in water. Hygroscopicity is easily suppressed.

The “mass ratio represented by (d) / (a)” is the content (mass%) of the component (d) relative to the content (mass%) of the ingredient (a) in the aminocarboxylic acid (salt) -containing particles. ) Ratio.

The “mass ratio represented by (e) / (a)” is the content (mass%) of the component (e) relative to the content (mass%) of the ingredient (a) in the aminocarboxylic acid (salt) -containing particles. ) Ratio.

The “mass ratio represented by (b) / (a)” is the content (mass%) of the component (b) relative to the content (mass%) of the ingredient (a) in the aminocarboxylic acid (salt) -containing particles. ) Ratio.

“Mass ratio represented by (c) / [(d) + (e)]” is the total content (mass of component (d) and component (e) in the aminocarboxylic acid (salt) -containing particles. %) Of the content (mass%) of the component (c). *

<Method for producing aminocarboxylic acid (salt) -containing particles>
Specific methods for producing aminocarboxylic acid (salt) -containing particles include the following methods (I) to (III) and (IV).

Method (I): A method of adding (a) component (powder) and mixing after adding water or the like by spraying or the like while mixing component (b).
Examples of water include water and an aqueous solution of the above base. By spraying water or the like, the component (a) is likely to change to a structure in which the component (b) hardly absorbs moisture. When an aqueous solution of a base is added, the pH of the aqueous solution is preferably 8 to 12, and more preferably 8 to 10. The spray amount of water or the like may be appropriately controlled so as to be within the preferable range of the water content described above, and is 0.2 to 5 masses with respect to 100 mass parts in total of the components (a) and (b). Part is preferable, and 0.2 to 3 parts by mass is more preferable.
(A) After adding and mixing a component (powder form), the said coating | coated component can also be added further. By further adding the coating component, the aminocarboxylic acid (salt) -containing particles are less likely to be agglomerated and the fluidity is improved.
As the mixer used in the method (I), a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.), a high speed mixer, a pro-shear mixer, and the like can be used.
The mixing condition is such that the stirring speed is, for example, the rotational speed of the main shaft, preferably 100 to 350 rpm, more preferably 150 to 250 rpm. The temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C.

Method (II): A method in which component (a), component (b) and water are mixed to prepare a slurry, and the slurry is spray-dried.
The spray drying conditions are such that the spray pressure (gauge pressure) is preferably 2 to 4 MPa, more preferably 2.5 to 3 MPa.
As for the temperature, the gas temperature supplied from the lower part of the spray drying tower is preferably 170 to 300 ° C., more preferably 230 to 270 ° C., and the gas temperature discharged from the top of the spray drying tower is 70 ° C. It is preferably set to ˜125 ° C., more preferably 90 to 110 ° C.

Method (III): A method in which the component (a) and the component (b) are mixed and then a liquid binder is added and mixed.
As the liquid binder, the binders exemplified above as other components can be used, and a water-soluble polymer that is solid at room temperature and dissolves when heated is preferable. Among these, polyethylene glycol is particularly preferable because it is easy to handle. The polyethylene glycol preferably has an average molecular weight of 1,000 to 20,000, more preferably an average molecular weight of 4,000 to 10,000. When the average molecular weight is not less than the lower limit value, the fluidity becomes better, and when it is not more than the upper limit value, the solubility becomes better. An average molecular weight here shows the average molecular weight described in the cosmetics raw material reference | standard (2nd edition comment). By adding a liquid binder, sufficient shearing force is imparted during stirring, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is further reduced, and solidification hardly occurs.
As a mixer used in the method (III), a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.), a high speed mixer, a pro-shear mixer, or the like can be used.
The mixing condition is such that the stirring speed is, for example, the rotational speed of the main shaft, preferably 100 to 350 rpm, more preferably 150 to 250 rpm. The temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C.
When mixing by adding a binder, the mixing efficiency is increased. Therefore, it is preferable to perform the crushing operation by rotating the chopper at 1000 to 5000 rpm while rotating the main shaft.

In the methods (I) to (III), components (c), (d), and (e) may be added as appropriate.

Method (IV): A kneading step of kneading and kneading the components (a) to (e), and a granulating 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 (c), the component (d), the component (e), and the component (b) in the vertical direction. The mixture is introduced into a chamber, and a batch type kneader is heated to 40 to 80 ° C. to perform stirring and mixing. Next, a kneaded product is obtained by introducing the component (a) into the horizontal chamber and kneading and kneading.
The stirring blade rotates in a direction perpendicular 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 the kneading machine having a horizontal chamber equipped with such a stirring blade include, for example, a pro shear 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.

When a continuous kneader is used, for example, a closed consolidation apparatus (preferably a horizontal type) heated to a temperature at which the component (e) melts (preferably 25 to 100 ° C., more preferably 40 to 80 ° C.). In the continuous kneader), the above-mentioned component (c), component (d), component (e), and component (b) are mixed in advance after powder mixing or while mixing component (a). 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, the hermetic consolidation apparatus (preferably a horizontal continuous kneader) is continuously heated to a temperature at which the component (A) and the component (e) are melted, and powder mixed therein (a ) To (e) The powder mixture of the 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 using a continuous kneader is preferable because the hygroscopicity of the finally obtained aminocarboxylic acid (salt) -containing particles can be suppressed and solidification is less likely to occur.
In addition, since it is easy to obtain aminocarboxylic acid (salt) -containing particles that hardly cause solidification and have excellent solubility in water, the components (c) to (e) and (b) are first mixed with powder, A method in which the component (a) is added and kneaded gently is preferred.

In the kneading step, the temperature during kneading is preferably in a temperature range that does not include the dehydration / transition temperature of component (a), and is a temperature that is 3 ° C. higher than the melting point of component (e). More preferably, the temperature is 5 to 20 ° C. higher than the melting point of the component (c).
By performing kneading in a temperature range that does not include the dehydration / transition temperature of component (a), 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 aminocarboxylic acid (salt) -containing particles is improved.

When kneading the components (a) to (e), the final content of the aminocarboxylic acid (salt) -containing particles is (a) component 10 to 80% by mass, and (b) component 10 to Each component is blended so as to be 80% by mass. In addition, it is preferable to use the following for each component.
Both the component (d) and the component (b) are preferably used as they are because the storage stability of the aminocarboxylic acid (salt) -containing particles is improved.
The component (d) 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 (d) can be easily powdered. Also good.
As the component (a), a powder having an average particle size of 30 to 800 μm is preferably used, a powder of 50 to 600 μm is more preferable, and a powder of 60 to 550 μm is more preferable. (A) When the average particle diameter of a component is more than a lower limit, the powdering of (a) component itself is suppressed. On the other hand, when the average particle size of the component (a) is not more than the upper limit value, a uniform kneaded product is easily obtained.
As the component (b), a powder having an average particle size of 30 to 1500 μm is preferably used, a powder of 50 to 1300 μm is more preferable, and a powder of 60 to 1200 μm is more preferable. When the average particle size of the component (b) is equal to or greater than the lower limit, the dusting of the component (b) 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 (b) 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, 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-mentioned preferable range, for example, the temperature at the time of kneading and kneading may be adjusted, or the blending amount of the component (e) 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, 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, It is particularly preferably 5.5 to 40 kwh / t.
When the extrusion power is 4 kwh / t or more, the storage stability of the resulting aminocarboxylic acid (salt) -containing particles 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. In addition, the solubility of aminocarboxylic acid (salt) -containing particles in water is improved.
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 rotational 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 aminocarboxylic acid (salt) -containing particles is improved. On the other hand, when the particle size of the granulated product is not more than the upper limit, the solubility of the aminocarboxylic acid (salt) -containing particles in water is improved.
Further, the ratio of the granulated particles having a particle diameter of less than 150 μm is preferably 14% by mass or less, more preferably 0.2 to 10% by mass with respect to the total aminocarboxylic acid (salt) -containing particles. . When the amount is not more than the upper limit, dust generation is less likely to occur, and the fluidity of the aminocarboxylic acid (salt) -containing particles is improved.

The method for producing aminocarboxylic acid (salt) -containing particles of the present invention may have other steps other than the kneading step and the granulating step described above.
Examples of the other steps include a step of further covering the surface of the granulated product obtained in the granulation step.

Among these, the method (I), the method (III) or the (IV) is preferable from the viewpoint of energy efficiency related to production.

(Granular detergent composition)
The granular detergent composition of the present invention contains the aminocarboxylic acid (salt) -containing particles of the present invention.
The average particle size of the granular detergent composition is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and even more preferably 280 to 500 μm. Generation | occurrence | production of a fine powder is suppressed as this average particle diameter is more than a lower limit, and the solubility to water improves on the other hand when it is below an upper limit.

The bulk density of the granular detergent composition is preferably 0.3 to 1.5 g / mL, more preferably 0.6 to 1.2 g / mL, even more preferably 0.7 to 0.9 g / mL. If the bulk density is equal to or higher than the lower limit value, the space (storage location) required for storing the granular detergent composition can be reduced, which is advantageous. On the other hand, if it is below an upper limit, the solubility in water of a granular detergent composition will become favorable.
In the present invention, the bulk density is a value measured by a method according to JIS K3362-1998.

The water content of the granular detergent composition is preferably 15% by mass or less, more preferably 2 to 9% by mass, and further preferably 4 to 8% by mass. If this water content is below an upper limit, solidification of a granular detergent composition will become harder to arise.

In the granular detergent composition, the content of aminocarboxylic acid (salt) -containing particles is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 12% by mass.
When the content of the aminocarboxylic acid (salt) -containing particles is at least the lower limit, the detergent raw materials (surfactants, peroxides, etc.) act to exert a cleaning bleaching effect, a sterilizing effect, a bactericidal effect, etc. Become. On the other hand, when the amount is not more than the upper limit value, it becomes easy to achieve a blending balance with other detergent raw materials, and a sufficient cleaning effect and the like are easily obtained.

As the detergent raw material other than the aminocarboxylic acid (salt) -containing particles in the granular detergent composition, those usually blended in detergent compositions for clothing and the like can be used.
Detergent raw materials include, for example, surfactants (anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc.), inorganic builder, organic builder, alkaline agent, sulfate and other particle strength retaining agents, Bleaching agent such as percarbonate or granulated product thereof, recontamination (deposition) inhibitor, dye, pigment, fragrance, enzyme agent (for example, protease, lipase, cellulase, amylase, etc.), bleach activator or granulated product thereof , Reducing agents such as sulfites and thiosulfates, optical brighteners, ultraviolet absorbers, softeners (such as bentonite), foam control agents (such as silicone), surface modifiers, oil absorbers, antioxidants, Examples include antibacterial agents.

The manufacturing method of a granular detergent composition can be manufactured with a well-known manufacturing method.
For example, after preparing a slurry by dispersing and dissolving a detergent raw material such as a surfactant, an inorganic builder, an organic builder, or an alkali agent in water, the slurry is spray-dried to obtain spray-dried particles. Next, the spray-dried particles and other detergent raw materials are kneaded, extruded, granulated, or pulverized to obtain a powder. Thereafter, the granular detergent composition can be obtained by mixing the powder, aminocarboxylic acid (salt) -containing particles, and other detergent raw materials.

The aminocarboxylic acid (salt) -containing particles of the present invention have reduced hygroscopicity. Therefore, even if the granular detergent composition containing the aminocarboxylic acid (salt) -containing particles contains hygroscopic aminocarboxylic acid (salt), solidification hardly occurs.
The reason why the granular detergent composition containing the aminocarboxylic acid (salt) -containing particles hardly causes solidification is not clear, but is presumed as follows.
The aminocarboxylic acid (salt) -containing particles of the present invention contain a zinc compound (a) and an aminocarboxylic acid or salt (b) in a predetermined molar ratio (a) / (b) = 0.5-6. .
In the aminocarboxylic acid (salt) -containing particles of the present invention, by containing the component (a) and the component (b) in a predetermined molar ratio, the surface vicinity of the component particles (b) Therefore, it is considered that it is less affected by the environment and has a lower hygroscopicity than the case of only the component particles (b). Accordingly, it is considered that the granular detergent composition of the present invention hardly causes solidification and hardly causes so-called caking.

Furthermore, the granular detergent composition of the present invention has a sterilizing effect in addition to the cleaning effect. The reason for having such an effect is considered to be that the component (a) and the component (b) form a complex in water, and this complex exhibits a sterilizing effect or a bactericidal effect.

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

<Measuring method of average particle diameter> (Measuring method 1)
The average particle diameter of each particle of Examples A1 to A17, Comparative Examples A1 to A8, and Reference Examples A1 to A4 was measured using a particle size distribution analyzer (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.). The volume-based median diameter was measured by a laser light scattering method.

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

<Method for measuring water content>
In this example, the moisture content is 5 g of sample using an infrared moisture meter (product name: Kett moisture meter manufactured by Kett Science Laboratory Co., Ltd.), when the sample surface temperature is 130 ° C. (when measuring a granular detergent composition). ) Or 170 ° C. (when measuring spray-dried particles), measurement was performed under the conditions of a measurement time of 20 minutes.

<Calculation method of moisture absorption rate (actual measurement)>
First, the sample 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, at every elapsed time (every 60 minutes), the mass of the glass petri dish in which the sample was spread was measured in the thermostat and the change with time was recorded. And the moisture absorption rate (actual measurement) (mass%) was calculated | required by Formula (1) mentioned above.

<Calculation method of moisture absorption value>
The calculated moisture absorption value (% by mass) was determined by the following formula (2).
In the formula (2), “metal salt” means zinc sulfate monohydrate or anhydrous sodium sulfate.
“MGDA blending amount” and “metal salt blending amount” are “(b) MGDA” and “(a) zinc sulfate monohydrate” or “anhydrous sodium sulfate” shown in Tables A1 to A4, respectively. Content.
The “moisture absorption rate of MGDA alone” is 83.4% by mass (Comparative Example A1).
The “moisture absorption rate of the metal salt alone” is 4.7% by mass (reference example A1) when the metal salt is zinc sulfate monohydrate, and 0.5% by mass (reference example A2) when it is anhydrous sodium sulfate. is there.
When the aminocarboxylic acid (salt) is other than MGDA, the calculation is performed by replacing “MGDA” in the following formula (2) with each aminocarboxylic acid (salt).

<Evaluation method of solidification property of granular detergent composition>
A three-layer paper in which coated cardboard (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ) and kraft pulp paper (basis weight: 70 g / m ² ) are laminated in this order. Using this, a box having a bottom surface of 150 mm × 90 mm and a height of 85 mm was produced.
500 g of the granular detergent composition of each example was placed in this box and placed in a thermostatic bath set at a temperature of 30 ° C. and a relative humidity of 80% for 48 hours. Thereafter, the granular detergent composition was slowly poured out of the box onto a sieve having an opening of 5 mm. And the residual amount of the granular detergent composition which remained on the sieve was measured, and the solidification property of the granular detergent composition was evaluated by the following evaluation criteria.
Evaluation criteria A: The remaining amount of the granular detergent composition remaining on the sieve was less than 25 g.
B: The remaining amount of the granular detergent composition remaining on the sieve was 25 g or more and less than 50 g.
C: The residual amount of the granular detergent composition remaining on the sieve was 50 g or more.

<Used raw materials>
The raw materials used in this example are as follows.

・ Zinc compounds (a)
Zinc sulfate monohydrate: manufactured by Shinyo Co., Ltd., trade name “dry zinc sulfate”, average particle size 70 μm.

(A) Component comparison component (a ′)
Anhydrous sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”, average particle size 89 μm.

Aminocarboxylic acid or salt thereof (b)
MGDA: trisodium methylglycine diacetate, manufactured by BASF, trade name “Trilon M Powder”, coordination position 4, content (pure content) 83% by mass, average particle size 63 μm.
NTA: nitrilotriacetic acid trisodium, manufactured by BASF, trade name “Trilon A92R”, pure content 92% by mass, average particle size 63 μm.
IDS: tetrasodium iminodisuccinate, manufactured by LANXESS, trade name “Baypure CX100”, pure content 80% by mass, average particle size 100 μm.

・ Other ingredients Sodium bicarbonate: Made by Junsei Chemical Co., Ltd., special grade.
Zeolite: Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 μm.
Polyethylene glycol: manufactured by Lion Corporation, trade name “PEG # 6000P”, average molecular weight 6000, melting point 56-61 ° C.

・ Detergent raw material MES paste: 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 methylsulfate 8% by mass, moisture 13% by mass], α-sulfo fatty acid alkyl ester salt fatty acid chain lengths of 16 and 18, carbon numbers of 16 and carbon numbers of 18 Mixing ratio C16 / C18 = 8/2 (mass ratio).
LAS-K: linear alkyl (10 to 14 carbon atoms) benzene sulfonic acid [manufactured by Lion Corporation, Rypon LH-200 (LAS-H pure content 96 mass%)] > The compound neutralized with 48 mass% potassium hydroxide aqueous solution at the time of slurry preparation for spray-drying particle preparation.
LAS-H: linear alkyl (carbon number 10 to 14) benzenesulfonic acid [manufactured by Lion Corporation, Rypon LH-200 (pure content 96% by mass)].
Polyoxyethylene alkyl ether: ECOROL 26 (trade name, manufactured by ECOGREN; alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (melting point: 40 ° C.). Pure content 90% by mass, moisture content 10% by mass.
Soap: fatty acid sodium having 12 to 18 carbon atoms (C) [manufactured by Lion Corporation, pure content 67% by mass, titer 40 to 45 ° C .; fatty acid composition C12 0.7% by mass, C14 11.4% by mass, C16 29. 2 mass%, C18F0 (stearic acid) 0.7 mass%, C18F1 (oleic acid) 56.8 mass%, C18F2 (linoleic acid) 1.2 mass%; molecular weight 289].

Zeolite: Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 μm.
MA agent: acrylic acid-maleic acid copolymer salt, manufactured by Nippon Shokubai Co., Ltd., trade name “AQUALIC TL-400”, pure content 40% by mass.
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.) average particle size 490 μm, bulk density 1.30 g / cm ³ .
Sodium carbonate: granular ash (manufactured by Asahi Glass Co., Ltd.) Average particle size 320 μm, bulk density 1.07 g / cm ³ .
Anhydrous sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”.

Sodium percarbonate granulated product: manufactured by Zhejiang JINKE CHEMICALS, trade name “SPCC”, effective oxygen amount 13.8% by mass, average particle size 870 μm.
Carboxymethyl cellulose: manufactured by Daicel Chemical Industries, Ltd., trade name “CMC Daicel 1190”, mass average molecular weight of about 300,000, and degree of etherification of 0.70.
Fluorescent agent: Ciba Japan Co., Ltd., trade name “Chino Pearl CBS-X”.
Dye: 20% by mass aqueous dispersion of ultramarine (made by Dainichi Seika Kogyo Co., Ltd.).
Perfume: Perfume composition A shown in Tables 11 to 18 described in JP-A-2002-146399.
Enzyme: Protease (sabinase 12T) / Amylase (Stainzyme 12T) / Lipase (LIPEX100T) / Cellulase (CellClean 4500T) (all manufactured by Novozymes Japan Ltd.) = 2/1/1/1 (mass ratio) blend.
Granulated product of bleach activator: mass ratio of OBS12 (sodium 4-dodecanoyloxybenzenesulfonate), PEG6000, AOS (sodium α-olefinsulfonate having 14 carbon atoms) and A-type zeolite powder 70/20/5/5 granulated product.

<Production example of aminocarboxylic acid (salt) -containing particles>
The aminocarboxylic acid (salt) -containing particles of each example were prepared according to the compositions shown in Tables A1 to A4.
In the table, the content of the compounding component indicates a pure equivalent amount.

(Example A1)
A MGDA is introduced at 40 ° C. into a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.) with a scissors blade-shaped excavator and a clearance between the shovel and the wall surface of 5 mm, and water (MGDA 100 mass) while rotating the spindle at 200 rpm. 1.0 parts by mass) was sprayed.
After spraying was completed, zinc sulfate monohydrate was added at 40 ° C., and stirring was performed while the main shaft was rotated at 200 rpm (the chopper was stopped). After 5 minutes from the start of stirring, MGDA-containing particles were obtained.

(Examples A2, A3)
According to the composition shown in Table A1, MGDA-containing particles were obtained in the same manner as in Example A1, except that the blending amounts of zinc sulfate monohydrate and MGDA were changed.

(Example A4)
MGDA-containing particles were obtained in the same manner as in Example A2, except that 1% by mass aqueous sodium hydrogen carbonate (bicarbonate) solution (pH 8.5 / 25 ° C.) was sprayed instead of water.

(Example A5)
A spray drying slurry preparation device, that is, a mixing tank having a stirring blade including a stirring blade and a rotating shaft and having a circulation line with a pump, water (36% by mass in the slurry for spray drying), MGDA and zinc sulfate monohydrate A Japanese product was introduced. Thereafter, stirring was continued for 10 minutes, the temperature was adjusted to 75 ° C., and a slurry for spray drying was prepared at a scale of a blending amount of 200 kg / batch.
The rotation speed of the stirring blade at this time was set to 60 rpm.
The obtained slurry for spray drying is transferred to a spray drying tower, sprayed at a spray pressure of 2.5 MPa (gauge pressure) from a pressure spray nozzle installed near the top of the spray drying tower, and spray-dried particles As a result, MGDA-containing particles were obtained. At that time, a gas at a temperature of 230 to 270 ° C. is supplied from the lower part of the spray drying tower, and a high temperature gas is supplied to the spray drying tower by discharging from the top of the spray drying tower at a temperature of 90 to 110 ° C. did. In addition, the temperature of the supplied high-temperature gas was appropriately adjusted in order to obtain MGDA-containing particles having a desired water content (3% by mass).

(Example A6)
A MGDA was introduced at 40 ° C. into a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a scissors blade-shaped excavator and the clearance between the shovel and the wall surface was 5 mm, and water was sprayed while rotating the main shaft at 200 rpm. .
After spraying is completed, zinc sulfate monohydrate is charged at 40 ° C., stirring is performed while the main shaft is rotated at 200 rpm (the chopper is stopped), and after 5 minutes from the start of stirring, zeolite is charged at 40 ° C. Then, MGDA-containing particles were obtained by stirring (chopper stopped) for 5 minutes while rotating the main shaft at 200 rpm.

(Example A7)
A Rougege mixer (M20 type, manufactured by Matsubo Co., Ltd.) with a scissors blade-shaped excavator and a jacket temperature controlled to 65 ° C. and a clearance between the shovel and the wall surface of 5 mm, MGDA at 60 ° C., and zinc sulfate at 60 ° C. Monohydrate was added and stirred (chopper stopped) while rotating the main shaft at 200 rpm. Five minutes after the start of the stirring, the chopper was rotated at 4000 rpm (the rotational speed of the main shaft was unchanged), and polyethylene glycol at 25 ° C. was added and stirred for 5 minutes to obtain MGDA-containing particles.

(Example A8)
According to the composition shown in Table A2, NTA-containing particles were obtained in the same manner as in Example A1, except that the amount of zinc sulfate monohydrate was changed and MGDA was changed to a predetermined amount of NTA.

(Example A9)
According to the composition shown in Table A2, IDS-containing particles were obtained in the same manner as in Example A1, except that the blending amount of zinc sulfate monohydrate was changed and MGDA was changed to a predetermined amount of IDS.

(Comparative Example A1)
The raw material MGDA (manufactured by BASF, trade name “Trilon M Powder”) was used as it was.

(Comparative Example A2)
MGDA-containing particles were obtained in the same manner as in Example A1, except that anhydrous sodium sulfate was used instead of zinc sulfate monohydrate.

(Comparative Examples A3 and A4)
According to the composition shown in Table A3, MGDA-containing particles were obtained in the same manner as in Example A1, except that the blending amounts of zinc sulfate monohydrate and MGDA were changed.

(Reference Example A1)
The raw material zinc sulfate monohydrate (manufactured by Shinyo Co., Ltd., trade name “dry zinc sulfate”) was used as it was.

(Reference Example A2)
The raw material anhydrous sodium sulfate (manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”) was used as it was.

(Comparative Example A5)
The raw material NTA (trade name “Trilon A92R” manufactured by BASF Corporation) was used as it was.

(Comparative Example A6)
The raw material IDS (trade name “Baypure CX100” manufactured by LANXESS) was used as it was.

For the particles of each example, the average particle diameter was measured by the method described above, and the moisture absorption rate (actual measurement) and the calculated moisture absorption rate were calculated. The results are also shown in Tables A1 to A4.

(Table A1)

(Table A2)

(Table A3)

(Table A4)

From the results of Tables A1 to A4, the aminocarboxylic acid (salt) -containing particles of Examples A1 to A9 according to the present invention have a moisture absorption rate (compared with the aminocarboxylic acid (salt) alone of Comparative Examples A1, A5, and A6). It can be seen that the actual measurement is very low.
Further, from the comparison between Examples A1 to A9 and Comparative Examples A2 to A4, the aminocarboxylic acid (salt) -containing particles of Examples A1 to A9 have a moisture absorption rate (actual measurement) / calculated moisture absorption rate of 30 to 75%. It can be seen that the moisture absorption rate (actual measurement) is significantly lower than the calculated value of moisture absorption rate.
Therefore, it was confirmed that the aminocarboxylic acid (salt) -containing particles of Examples A1 to A9 according to the present invention have low hygroscopicity.

<Production example of granular detergent composition>
The granular detergent composition of each example was prepared by the method shown below.

(Example A10)
In accordance with the composition shown in Table A5, each compounding component was put into a reactor having a stirrer and a jacket, dissolved and dispersed in water (jacket temperature of the stirrer 75 ° C.), and spray-dried particles having a solid content concentration of 60% by mass. A slurry for preparation was prepared.

(Table A5)

Next, this slurry for preparing spray-dried particles is spray-dried using a countercurrent drying tower under the following conditions, and zeolite (obtained spray-dried particles obtained) as a coating for coating the spray-dried particles from the bottom of the spray-drying tower. The spray dried particles were obtained by introducing 1 part by mass to 100 parts by mass.
[Spray drying conditions]
・ Spray dryer: counter-current type, tower diameter 2.0m, effective length 5.0m
・ Atomization method: Pressurized nozzle method ・ Spraying pressure: 30 kg / cm ²
・ Hot air inlet temperature: 250 ℃
-Hot air outlet temperature: 100 ° C
The obtained spray-dried particles had an average particle size of 300 μm, a bulk density of 0.30 g / mL, and a water content of 5.0% by mass (moisture content measurement conditions: 170 ° C., 20 minutes).

Next, 52.05% by mass of the obtained spray-dried particles, 18.6% by mass of MES paste, 3.6% by mass of polyoxyethylene alkyl ether, 0.1% by mass of the fluorescent agent, and 0.45% by mass of water % Into a continuous kneader (manufactured by Kurimoto Steel Works, KRC-S4 type), and Kazuwa (kneader rotation speed 135 rpm, jacket temperature: jacket inlet 5 ° C., outlet 25 ° C. (water passed through the jacket) The dough-like material was prepared by cooling)). The temperature of the resulting dough was 55 ± 15 ° C.
The obtained dough-like material is put into a pelleter double (product name: EXD-100 type, manufactured by Fuji Paudal Co., Ltd.) and extruded from a die having a hole diameter of about 10 mm and a thickness of 10 mm and simultaneously cut (perimeter of the cutter of the pelleter). The speed was 5 m / s) to obtain a pellet-shaped formed body (diameter: about 10 mm, length: 70 mm or less (substantially 5 mm or more)).
Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKA-) was added to 74.8% by mass of the obtained pellet-shaped molded body by adding 5.2% by mass of zeolite as a grinding aid and arranged in three stages in the presence of air blowing. 6 type) to obtain a powder. The grinding conditions were as follows. The temperature of the obtained powder was 30 ± 10 ° C.
[Crushing conditions]
-Air temperature: 15 ± 3 degreeC.
・ Blowing rate (ratio of gas / solid): 2.8 ± 0.25 m ³ / kg.
-Screen diameter: 6 mm for the first stage, 4 mm for the second stage, and 2 mm for the third stage.
-Crusher rotation speed: 470 rpm (circumferential speed about 60 m / s).
Processing speed: 230 g / hr.

Next, a horizontal cylindrical rolling drum (diameter 0.70 m, length 1.40 m, inclination angle 3 °, thickness 1 mm × height 50 mm × length 350 mm baffle 15 so that the processing speed is 240 kg / hr. 80.0% by mass of the powder, 1.8% by mass of zeolite, 5.0% by mass of sodium percarbonate granule, 1.0% by mass of carboxymethylcellulose, and MGDA of Example A1 At the same time, 10 mass% of the contained particles are added and mixed, and at the same time, 0.5 mass% of polyoxyethylene alkyl ether is sprayed at a spray pressure of 0.5 to 1.5 MPa using a pressure cone nozzle K series (manufactured by Ikeuchi Co., Ltd.). Sprayed.
Then, after spraying 0.1% by weight of pigment (20% by weight aqueous dispersion) and 0.1% by weight of fragrance, 1.0% by weight of enzyme and 0.5% by weight of bleach activator granules By adding and mixing, a granular detergent composition (average particle diameter of 360 μm, bulk density of 0.85 g / mL) was obtained.
In addition, the moisture content of the obtained granular detergent composition was 7.0 mass% (measuring conditions of moisture content 130 ° C., 20 minutes).

(Examples A11 to A17, Comparative Examples A7 to A8)
A granular detergent in the same manner as in Example A10 except that the aminocarboxylic acid (salt) -containing particles of Examples A2, A4 to A9 and Comparative Examples A1 to A2 were used instead of the MGDA-containing particles of Example A1. A composition was obtained.

(Reference Example A3)
When preparing the granular detergent composition of Example A10, the spray-dried particles obtained in the middle were used as they were.

(Reference Example A4)
In Example A10, a granular detergent composition was obtained in the same manner as in Example A10, except that the zinc sulfate monohydrate of Reference Example A1 was used instead of the MGDA-containing particles of Example A1.

For the granular detergent composition of each example, the solidification property was evaluated by the method described above, and the moisture absorption rate (actual measurement) was calculated. The results are shown in Tables A6 and A7.

(Table A6)

(Table A7)

From the results of Tables A6 and A7, the granular detergent compositions of Examples A10 to A17 according to the present invention are less likely to cause solidification (so-called caking is less likely) than the granular detergent compositions of Comparative Examples A7 to A8. Was confirmed.

The average particle diameters of Examples B1 to B10 and Comparative Examples B1 and B2 were measured by the measuring method 2 or a method according to the same among the above-mentioned [Measuring method of average particle diameter]. The dehydration / transition temperature was measured in the same manner as described above.
The compositions of the aminocarboxylic acid (salt) -containing particles produced by the production methods of each example are shown in Tables B1 to B3.
The raw materials used in this example are as follows.

・ Organic binder (c)
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 (d)
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 (e) 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 Corporation, 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 Co., Ltd., trade name “Leox CL-90”, pure content 100 mass%, melting point 28 ° C.

・ Zinc compounds (a)
Zinc sulfate monohydrate: manufactured by Horiike Sangyo Co., Ltd. BR> A trade name “ZNS-13”, average particle size 200 μm, dehydration and transition temperature 270 ° C.

Aminocarboxylic acid or salt thereof (b)
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 mass, sodium sulfate 13.0% by mass, zeolite 15.0% by mass, acrylic acid-maleic acid copolymer salt 2.0% by mass, fluorescent brightener 0.1% by mass, 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, aminocarboxylic acid (salt) -containing particles 1.0% by mass

Preparation method of granular detergent:
[Drying process]
Polyoxyethylene alkyl ether, MES-Na, part of zeolite (for grinding aid, post-mixing step), enzyme, sodium percarbonate granule, bleach activator granule, amino An aqueous slurry having a solid content of 62% by mass was obtained by stirring a predetermined amount of all the components except the carboxylic acid (salt) -containing particles 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 added to a continuous kneader (KRC-S4 type, manufactured by Kurimoto Seiko Co., Ltd.) 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 (made 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 aminocarboxylic acid (salt) -containing particles are mixed with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, drum inner wall surface of vessel 131.7 L and inner wall surface). Using a baffle plate having a clearance of 20 mm and a height of 45 mm), the mixture was mixed for 1 minute under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. to produce granular detergents of each example.
At that time, only 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% by mass, nonionic surfactant (polyoxyethylene alkyl ether described later) 16% by mass, Impurities such as di-salt and methyl sulfate, 8% by mass, moisture 13% by mass] were used. The fatty acid chain length of α-sulfo fatty acid alkyl ester salt (MES-Na) is 16 and 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 (carbon number 10-14) benzenesulfonic acid (LAS-H, manufactured by Lion Corporation, Lipon LH-200, AV value (potassium hydroxide required to neutralize 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 mass 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.
Optical 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) 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 bleach activator: OBS12 (sodium 4-dodecanoyloxybenzene sulfonate), PEG-6000, AOS (sodium α-olefin sulfonate having 14 carbon atoms), and A-type zeolite powder Granulated product having a mass ratio of 70/20/5/5.
Aminocarboxylic acid (salt) -containing particles: Aminocarboxylic acid (salt) -containing particles of Examples B1 to B10 and Comparative Examples B1 and B2 described later.

<Production example of aminocarboxylic acid (salt) -containing particles>
Aminocarboxylic acid (salt) -containing particles were produced by the following production methods in accordance with the blending components and contents (mass%) of the compositions shown in Tables B1 to B3.
In the table, the content of the component (a) 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 B1)
[Kazuwa process]
Warm water was circulated in the jacket of an S-1KRC kneader manufactured by Kurimoto Steel Corporation, and the kneader body was heated to 60 ° C. and maintained at that temperature.
Subsequently, all components except the component (a) shown in Table B1 were powder-mixed at room temperature, and then the component (a) 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 product is continuously put into an extruder (manufactured by Dalton Co., Ltd., Multigran 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.) equipped with a 2.5 mmφ screen, and pulverized at a rotation speed of 3000 rpm to obtain aminocarboxylic acid (salt) -containing particles. .

(Example B2)
[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.
Subsequently, components other than the component (a) in the composition shown in Table B1 were introduced into a horizontal chamber having a stirring blade rotating in the vertical direction.
Next, after performing the kneading operation at a rotating speed of the stirring blade of 45 rpm, the component (a) 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 B1 to obtain aminocarboxylic acid (salt) -containing particles.

(Examples B3 to B8, B10 to B12)
Aminocarboxylic acid (salt) -containing particles were obtained by performing the same operations as in Example B1 according to the compositions and production conditions shown in Tables B1 and B2. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components.

(Example B9)
[Kazuwa process]
Warm water was circulated in the jacket of the S-1KRC kneader manufactured by Kurimoto Steel Corporation, and the kneader body was heated to 57 ° C. and maintained at that temperature.
Next, according to the composition and production conditions shown in Table B2, all the components (a) to (e) were powdered together to prepare a powder mixture of 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 B1 to obtain aminocarboxylic acid (salt) -containing particles.

(Comparative Example B1)
According to the composition and production conditions shown in Table B3, the same operations as in Example B9 (powder mixing, kneading kneading, extrusion granulation of all the components (a) to (e) together) Aminocarboxylic acid (salt) -containing particles were obtained. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components.

(Comparative Example B2)
According to the composition and production conditions shown in Table B3, the same operations as in Example B9 (components (c) to (e), (b) and all components of citric acid were mixed together, kneaded and extruded. By performing granulation, aminocarboxylic acid (salt) -containing particles were obtained. The powder mixture was charged for 19 minutes per 1.5 kg of the total amount of the components.

<Evaluation of aminocarboxylic acid (salt) -containing particles>
The following evaluation was performed about the aminocarboxylic acid (salt) containing particle | grains obtained by the manufacturing method of each example, respectively. The results are also shown in Tables B1 to B3.

[Proportion of particles having a particle diameter of less than 150 μm]
When the aminocarboxylic acid (salt) -containing particles obtained in each example were classified by the same method as the above-mentioned “Method for Measuring Average Particle Diameter”, the particles were collected on a tray through a sieve having a mesh size of 149 μm. The mass frequency of the granulated material 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 aminocarboxylic acid (salt) -containing particles in water]
1 g of aminocarboxylic acid (salt) -containing particles obtained in each example were 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 ( A stirrer piece: 20 mm in length, 5 mm in diameter, and rotation speed: 200 rpm), and the change in the electric conductivity of ion-exchanged water was measured over time with an electric conductivity meter.
And after confirming that the aminocarboxylic acid (salt) containing particle | grains in ion-exchange water did not melt | dissolve, the dissolution rate (%) was calculated | required 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 electric conductivity value on the vertical axis, the measurement is continued until the electric conductivity is balanced over time, and all the aminocarboxylic acid (salt) -containing particles are dissolved. Assuming that the electric conductivity was 100%, the time required to reach 90% of the electric conductivity was obtained.
And according to the following evaluation criteria, the solubility with respect to the water of aminocarboxylic acid (salt) containing particle | grains was evaluated. Those whose evaluation results were A and B were regarded as acceptable.
(Evaluation criteria)
A: The dissolution time was less than 200 seconds.
B: Dissolution time was 200 seconds or more and less than 300 seconds.
C: The dissolution time was 300 seconds or more and less than 500 seconds.
D: The dissolution time was 500 seconds or longer.

[Evaluation of hygroscopicity of aminocarboxylic acid (salt) -containing particles]
The hygroscopicity of the aminocarboxylic acid (salt) -containing particles is a characteristic that serves as an indicator of the solidification properties of the aminocarboxylic acid (salt) -containing particles themselves and the solidification properties of the detergent when blended in a detergent. The higher the hygroscopicity, the more easily the aminocarboxylic acid (salt) -containing particles or detergents are agglomerated and solidified.
The hygroscopic evaluation of the aminocarboxylic acid (salt) -containing particles was performed as follows.
The aminocarboxylic acid (salt) -containing particles (samples) obtained in each example were spread on a glass petri dish (inner diameter 85 mm) to a thickness of 5 mm and placed in a thermostatic chamber set at a temperature of 45 ° C. and a relative humidity of 80%. I put it in.
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 hygroscopicity of the aminocarboxylic acid (salt) -containing particles was evaluated according to the following evaluation criteria. Those whose evaluation results were A, B, and C were regarded as acceptable.
(Evaluation criteria)
A: The moisture absorption rate was less than 5% by mass.
B: The moisture absorption was 5% by mass or more and less than 10% by mass.
C: The moisture absorption was 10% by mass or more and less than 20% by mass.
D: The moisture absorption was 20% by mass or more and less than 40% by mass.
E: The moisture absorption was 40% by mass or more.

[Evaluation of solidification of detergent]
Using the aminocarboxylic acid (salt) -containing particles obtained in each example, the above granular detergent was prepared, and 1000 g of the granular detergent was filled in a seal carton detergent container (length 155 mm × width 95 mm × height 135 mm), The sealed carton detergent container after filling was stored in a thermostatic bath at a temperature of 45 ° C. and a relative humidity of 60% for 2 weeks.
Thereafter, the sealed carton detergent container was taken out 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. Those whose evaluation results were A and B were regarded as acceptable.
(Evaluation criteria)
A: The remaining amount of the granular detergent remaining on the sieve was less than 50 g.
B: The remaining amount of the granular detergent remaining on the sieve was 50 g or more and less than 100 g.
C: The remaining amount of the granular detergent remaining on the sieve was 100 g or more and less than 300 g.
D: The residual amount of the granular detergent remaining on the sieve was 300 g or more.

(Table B1)

(Table B2)

(Table B3)

From the results in Tables B1 to B3, it was confirmed that the aminocarboxylic acid (salt) -containing particles of Examples B1 to B10 according to the present invention were excellent in solubility in water.
It was also confirmed that the granular detergents containing the aminocarboxylic acid (salt) -containing particles of Examples B1 to B10 hardly cause solidification.

Since the aminocarboxylic acid (salt) -containing particles of the present invention are less likely to solidify and have excellent solubility in water, they can be suitably used as a raw material for detergents.

Claims (5)

1. A zinc compound (a);
   An aminocarboxylic acid or a salt thereof (b),
   Aminocarboxylic acid (salt) -containing particles, wherein the molar ratio represented by (a) / (b) is 0.5-6.
2. The aminocarboxylic acid (salt) -containing particles according to claim 1, wherein the zinc compound is a sulfate.
3. Furthermore, organic binder (c), anionic surfactant (d), and nonionic surfactant (e) whose melting | fusing point is less than 45 degreeC are contained, The 1 or 2 characterized by the above-mentioned. Of aminocarboxylic acid (salt) -containing particles.
4. The content of the zinc compound (a) is 10 to 80% by mass, and the content of the aminocarboxylic acid or a salt (b) thereof is 10 to 80% by mass. The aminocarboxylic acid (salt) -containing particles according to claim 1.
5. A granular detergent composition comprising the aminocarboxylic acid (salt) -containing particles according to any one of claims 1 to 4.