KR20130115226A - Particles each containing aminocarboxylic acid(salt), and granular detergent composition - Google Patents

Abstract

Aminocarboxylic acid (salt) containing particle | grains containing zinc compound (a) and aminocarboxylic acid or its salt (b), and molar ratio represented by (a) / (b) is 0.5-6. .

Description

Aminocarboxylic acid (salt) -containing particles and granular detergent compositions {PARTICLES EACH CONTAINING AMINOCARBOXYLIC ACID (SALT), AND GRANULAR DETERGENT COMPOSITION}

 The present invention relates to aminocarboxylic acid (salt) -containing particles and granular detergent compositions.

This application claims priority based on patent application 2010-224126 for which it applied to Japan on October 1, 2010, and patent application 2011-049624 which was filed in Japan on March 7, 2011, and the content here. It is used for.

In recent years, it has been demanded that detergent compositions, such as medical use, also have a bactericidal effect in addition to the cleaning effect due to the increasing awareness of consumer's cleanliness.

As such a detergent composition, what mix | blended the oxidation catalyst containing the chelating agent of the coordination site of 5 or less, a metal compound, and surfactant is proposed. As said chelating agent, aminocarboxylates, such as methylglycine diacetate, imino disuccinate, and hydroxy imino disuccinate, are used (refer patent document 1).

However, since the aminocarboxylate itself has hygroscopicity, it is likely to form a lump form with other detergent raw materials when blended into the granular detergent composition. Therefore, in the granular detergent composition containing aminocarboxylate, there existed a problem that solidification generate | occur | produces easily (so-called caking is easy to occur). In order to improve this problem, at least one polyethyleneglycol or at least one nonionic surfactant or a mixture thereof with methylglycine diacetate (x) as an aminocarboxylate, or polyvinyl alcohol, polyvinylpyrrolidone The mixed powder or mixed granule which used the polymer (y) selected from the group which consists of polyalkylene glycol and its derivative (s) is proposed (refer patent document 2).

Moreover, the granulated material of the conventional oxidation catalyst is insufficient in solubility in water (especially solubility in water around 10 degreeC of low temperature).

International Publication No. 09/078459 Japanese Patent Publication No. 2008-505236

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 prevented sufficiently.

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.

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

(1) Aminocarboxylic acid (salt) containing zinc compound (a), aminocarboxylic acid or its salt (b), and molar ratio represented by (a) / (b) is 0.5-6 ) Containing particles.

(2) The aminocarboxylic acid (salt) -containing particles according to (1), wherein the zinc compound is sulfate.

(3) Aminocar according to (1) or (2), which further contains an organic binder (c), an anionic surfactant (d), and a nonionic surfactant (e) having a melting point of less than 45 ° C. Acid (salt) containing particles.

(4) In any one of (1)-(3), content of the said zinc compound (a) is 10-80 mass%, and content of the said aminocarboxylic acid or its salt (b) is 10-80 It is mass%, The aminocarboxylic acid (salt) containing particle | grains characterized by the above-mentioned.

(5) The granular detergent composition containing the aminocarboxylic acid (salt) containing particle | grains in any one of (1)-(4).

(Effects of the Invention)

According to this invention, the aminocarboxylic acid (salt) containing particle | grains which are hard to produce solidification, and a granular detergent composition can be provided.

In the present invention, "aminocarboxylic acid (salt) -containing particles" means particles containing one or both of aminocarboxylic acid or aminocarboxylate.

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

(Aminocarboxylic Acid (Salt) -Containing Particles)

The aminocarboxylic acid (salt) containing particle | grains of this invention contain a zinc compound (a) and aminocarboxylic acid or its salt (b).

Since the said aminocarboxylic acid (salt) containing particle | grains are low hygroscopicity, even if it mix | blends with a granular detergent composition etc., it is hard to produce solidification (it is hard to produce a cake). Therefore, the aminocarboxylic acid (salt) -containing particles are suitable for blending into powder-like compositions (cleaners, bleaches) for use in textile treatments or residential cleaning, and in particular, those having a granular detergent composition for medical use (bleaching performance). And the like).

The moisture absorption rate of aminocarboxylic acid (salt) containing particle | grains becomes like this. Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

If this moisture absorption rate is below an upper limit, when it mix | blends with a granular detergent composition etc., it will become hard to produce | solidify more.

In this invention, a "moisture absorption" means the value measured according to the following procedures. First, a sample is spread out to a glass chalet (85 mm inside diameter) so that it may become thickness 5mm, and it puts into the thermostat set to 45 degreeC of temperature and 80% of relative humidity.

Subsequently, the mass of the glass chalet in which the said sample was unfolded every elapsed time (every 60 minutes) is measured in the said thermostat, and the change with time is recorded.

And moisture absorption (mass%) is calculated | required by Formula (1) shown below. In formula (1), "a sample collection amount", a "sample input amount", and a "measured value" are as follows.

Measured value: Mass of the glass chalet with the sample unrolled after 48 hours in total.

Sample input: The mass of the glass chalet in which the sample measured after standing for 1 minute at a temperature of 25 ° C. before being placed in a thermostat.

Sampling amount of the sample: The value obtained by subtracting the mass of the glass chalet measured after standing for 1 minute at a temperature of 25 ° C. from the sample input amount.

The average particle diameter of aminocarboxylic acid (salt) containing particle | grains is 150-2000 micrometers normally, It is preferable that it is 200-1200 micrometers, It is more preferable that it is 50-500 micrometers, More preferably, 70-350 micrometers, 80 300 micrometers is especially preferable. When average particle diameter is more than a lower limit, particle aggregation is suppressed when mixing with another detergent raw material. On the other hand, solubility in water improves that it is below an upper limit.

In the present invention, the "average particle diameter" is a value measured as a median diameter on a volume basis by laser light scattering method using a particle size distribution measuring device (LDSA-3400A (17ch) manufactured by Tohnichi Computer Applications Corporation) (Measurement Method 1 ) Or the value obtained by the following method (measurement method 2).

(Measurement Method of Average Particle Diameter) (Measurement Method 2)

First, a classification operation is carried out on the measurement object (sample) using nine sieves and a support dish of mesh sizes 1680 µm, 1410 µm, 1190 µm, 1000 µm, 710 µm, 500 µm, 350 µm, 250 µm and 149 µm. Is done.

In the classification operation, first, the sieves of the above nine stages are piled up in order so that the mesh sizes increase in order, and 100 g / time sample is put on the top of the sieve having a mesh size of 1680 µm. The lid was then covered and attached to a low-tap sieve shaker (manufactured by iida-seisakusho Japan Corporation, tapping: 156 times / minute, rolling: 290 times / minute), vibrated for 10 minutes and left on each sieve and support dish. One sample is collected for each sieve mesh and the mass of the sample is measured.

When the mass frequency of the base plate and each sieve is integrated, the mesh size of the first sieve whose mass frequency is 50% or more is set to a μm, and the mesh size of the sieve one step larger than a μm to b μm, The average particle diameter (mass 50%) is calculated | required from the following formula using c% as the integration of the mass frequency from a support pan to the sieve of a micrometer, and d% as the mass frequency on a sieve of amicrometer.

Water content of aminocarboxylic acid (salt) containing particle | grains becomes like this. Preferably it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 0.3-4 mass%.

In this invention, a moisture content shows the value measured using the infrared moisture meter (Kett Electric Laboratory make, product name: Kett moisture meter).

<Zinc compound (a)>

As the zinc compound (a) (hereinafter also referred to as "(a) component"), a granular detergent composition or the like is usually used after being used in water, so that the zinc compound (a) is easily dissolved in water. Can be.

Examples of the water-soluble salts include nitrates, sulfates, chlorides, acetates, perchlorates, cyanide salts, ammonium chloride salts, tartarate salts, and gluconate salts, and hydrates thereof can also be used.

As the component (a), zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc stannate, zinc perchlorate, zinc gluconate, and the like are preferred. Zinc sulfate is more preferable, and anhydrous zinc sulfate, zinc sulfate monohydrate, and zinc sulfate heptahydrate are particularly preferable.

When the hydrous salt is used as the component (a), the dehydration and transition temperature of the component (a) is in the range of the temperature conditions at the time of kneading kneading or granulation when preparing the aminocarboxylic acid (salt) -containing particles. When present, the hardness of the aminocarboxylic acid (salt) -containing particles changes rapidly, making it difficult to obtain a uniform (homogeneous) granulated material. From this, as said (a) component, it is preferable that the dehydration / transition temperature is out of the range of the temperature conditions at the time of kneading kneading or granulation, It is more preferable that the low temperature side is 55 degrees C or less, and the high temperature side is 70 degrees C or more, It is still more preferable that the low temperature side is 43-50 degreeC, and the high temperature side is 73-280 degreeC.

"Dehydration and transition temperature of (a) component" shows the value observed by the transition point measurement by differential scanning calorimetry (DSC). This dehydration and transition temperature is determined by making it the temperature of the peak top of the endothermic peak obtained by DSC. As for the DSC measurement, any type of commercially available heat flux type or heat guaranteed type may be used. When an example of a measurement is shown, (alpha)-alumina is used for a reference, and the polyhydrate of a zinc compound (a) is arrange | positioned at the sample side. Measurement temperature range: 0-100 degreeC, temperature rising rate: It carries out on conditions of 2 degree-C / min. The dehydration and transition temperature is taken as the temperature of the peak top of the endothermic peak of 10 mJ / min or more observed at 20 degreeC or more. When there exists a plurality of endothermic peaks, the endothermic peak observed on the highest temperature side among 100 ° C. or less is regarded as the dehydration and transition temperature.

In addition, about the zinc compound (a) which does not have an endothermic peak below 100 degreeC, a dehydration and transition temperature is computed by changing similarly to a measurement temperature range from 0 to 300 degreeC, and measuring it.

(a) A component may be used individually by 1 type and may use 2 or more types together.

10-80 mass% is preferable in conversion of anhydride, and, as for content of (a) component in aminocarboxylic acid (salt) containing particle | grains, 20-55 mass% is more preferable.

If content of (a) component is more than a lower limit, the hygroscopicity of aminocarboxylic acid (salt) containing particle | grains will further reduce, and it will become hard to produce solidification. On the other hand, when it is below an upper limit, the compounding balance of the aminocarboxylic acid or its salt (b) mentioned later becomes easy, and the effect of this invention improves.

<Aminocarboxylic Acid or Salts thereof (b)>

As aminocarboxylic acid or its salt (b) (hereinafter also referred to as "(b) component"), ethylenediaminetetraacetic acid or its salt, β-alanine diacetic acid or its salt, the following general formula (b1) or general formula ( The compound etc. which are represented by b2) can be illustrated.

[In formula (b1), X <^11> -X <^14> respectively independently represents a hydrogen atom, an alkali metal, alkaline earth metal, or cationic ammonium, R represents a hydrogen atom or a hydroxyl group, n <_1> represents the integer of 0 or 1, Indicates. In 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 cationic ammonium, n ₂ represents an integer of 0 to 5]

In said formula (b1), sodium, potassium, etc. can be illustrated as alkali metal in X <^11> -X <^14> .

Calcium, magnesium, etc. can be illustrated as alkaline earth metal in X <^11> -X <^14> . In addition, when at least 1 of X <^11> -X <^14> is an alkaline earth metal, it corresponds to 1/2 atomic weight. For example, when X ¹¹ is calcium, -COOX ¹¹ is "-COO-1/2 (Ca)".

Examples of the cationic ammonium in X ^{11 to} X ¹⁴ include alkanolamines such as monoethanolamine and diethanolamine, and specifically, examples in which one to three hydrogen atoms of ammonium are substituted with alkanol groups Can be. As for carbon number of an alkanol group, 1-3 are preferable.

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 said formula (b1), R may be any of a hydrogen atom and a hydroxyl group.

In the formula (b1), n ₁ is preferably 1.

As a specific example of a compound represented by Formula (b1), imino disuccinic acid, 3-hydroxy-2,2'- imino disuccinic acid, or those salts etc. can be illustrated, for example, an imino disuccinic acid or its salt is mentioned. desirable.

Examples of the salts include alkali metal salts such as sodium salts and potassium salts, alkanolamine salts such as monoethanolamine salts and diethanolamine salts, and sodium salts and potassium salts are particularly preferred.

In said formula (b2), the alkyl group in A may be linear or branched.

1-30 are preferable and, as for carbon number of an alkyl group, 1-18 are more preferable. Some of the hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent may be exemplified by sulfo (-SO ₃ H), amino groups (-NH _2), hydroxyl group, a nitro group (-NO ₂₎ or the like.

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 among these, a hydrogen atom is particularly preferable.

As said alkali metal, alkaline-earth metal, and cationic ammonium in X <^21> -X <^23> , the same thing as the alkali metal, alkaline-earth metal, and cationic ammonium in said X <^11> -X <^14> is illustrated in said Formula (b2), respectively. can do.

Among these, it is preferable that X <^21> -X <^23> is an alkali metal.

X ^{21 to} X ²³ may be the same or different from each other.

In said formula (b2), it is preferable that n <_2> is an integer of 0-2, and 1 is especially preferable.

As a specific example of a compound represented by Formula (b2), a nitrilo triacetic acid, methylglycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-2 acetic acid, a serine diacetic acid, those salts, etc. are illustrated, for example. Among them, nitrilotriacetic acid, methylglycine diacetic acid or salts thereof are preferable, and methylglycine diacetic acid or salts thereof are particularly preferable.

Examples of the salts include alkali metal salts such as sodium salts and potassium salts, alkanolamine salts such as monoethanolamine salts and diethanolamine salts, and sodium salts and potassium salts are particularly preferred.

(b) A component may be used individually by 1 type and may use 2 or more types together.

Among the above-mentioned, since solidification hardly arises as (b) component, the compound represented by the said general formula (b1) or general formula (b2) is preferable, and the compound represented by general formula (b2) is more preferable.

10-80 mass% is preferable, and, as for content of (b) component in aminocarboxylic acid (salt) containing particle | grains, 35-75 mass% is more preferable. If content of (b) component is more than a lower limit, the compounding effect (effect of coordinating with a metal ion and making a chelate compound) of (b) component will become easier to be obtained. On the other hand, if it is below an upper limit, the compounding balance with the said (a) component will be easy to be taken, and the effect of this invention will improve.

When the compound represented by the above general formulas (b1) to (b2) is blended in the process of producing aminocarboxylic acid (salt) -containing particles, for example, part or all of the "-COOX" of the terminal group It becomes "-COO-", and it is thought that the said compound acts as a binder.

Moreover, as (b) component, since the hygroscopicity of aminocarboxylic acid (salt) containing particle | grains is suppressed lower, it is preferable to use that whose average neutralization degree is 80% or more, It is more preferable to use what is 90% or more, 100 Particular preference is given to using what is%.

"Neutralization degree" here means the mole fraction of neutralized carboxylic acid with respect to the total carboxylic acid in a molecule | numerator. When all carboxylic acids in a molecule are neutralized, it is 1.0, and when all is an acid form (-COOH), it is zero.

In this invention, "(a) / (b)" shows the content rate (molar ratio) of (a) component with respect to (b) component.

As for the mixing ratio of (a) component and (b) component in aminocarboxylic acid (salt) containing particle | grains, the molar ratio represented by (a) / (b) is 0.5-6, It is preferable that it is 0.5-5.8, It is 0.5- It is more preferable that it is 5.5.

If the molar ratio represented by (a) / (b) is more than a lower limit, the hygroscopicity of aminocarboxylic acid (salt) containing particle | grains will reduce and it will become hard to produce solidification. On the other hand, if the molar ratio represented by (a) / (b) is below an upper limit, the density | concentration of (b) component is fully ensured.

<Other ingredients>

Aminocarboxylic acid (salt) containing particle | grains may contain other components other than the said (a) component and (b) component as needed.

As other components, Bases, such as sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide; Coating components such as crystalline alumino silicate (A-type zeolite, P-type zeolite, X-type zeolite, etc.), amorphous aluminosilicate, clay minerals (such as talc and montmorillonite); Binders, such as polyethyleneglycol, polyvinylpyrrolidone, and polyvinyl alcohol, can be illustrated.

0.001-10 mass% is preferable, as for content of a base in aminocarboxylic acid (salt) containing particle | grains, 0.002-1 mass% is more preferable, 0.003-0.1 mass% is more preferable. When content of a base is more than a lower limit, when preparing aminocarboxylic acid (salt) containing particle | grains, (b) component will change to the structure which is hard to absorb moisture easily. On the other hand, if it is below an upper limit, it will become easy to balance with the other compounding component, and the density | concentration of (b) component is fully ensured.

0.5-5 mass% is preferable, and, as for content of the component for coating in aminocarboxylic acid (salt) containing particle | grains, 1-3 mass% is more preferable. When content of a coating component is more than a lower limit, aminocarboxylic acid (salt) containing particle | grains are hard to become a lump shape, and fluidity | liquidity improves. On the other hand, if it is below an upper limit, it will become easy to balance with the other compounding component, and the density | concentration of (b) component is fully ensured.

As said 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 a water-soluble organic compound which is melted by applying heat is preferable.

Especially, as (c) component, the organic compound of 25-100 degreeC of melting | fusing point is more preferable, The organic compound of 25-80 degreeC of melting | fusing point is more preferable, The organic compound of 40-80 degreeC of melting | fusing point is especially preferable, Melting | fusing point This 45-75 degreeC organic compound is the most preferable.

However, (c) component shall not contain (d) component, (e) component, (a) component, and (b) component in this 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. Especially, polyethyleneglycol is preferable, polyethyleneglycol of the average molecular weights 400-30000 is more preferable, polyethyleneglycol of the average molecular weights 1000-20000 is more preferable, polyethyleneglycol of the average molecular weights 4000-20000 is especially preferable.

"Average molecular weight" here shows the value of the polyethyleneglycol conversion standard 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.

3-30 mass% is preferable, as for content of a binder (c) in aminocarboxylic acid (salt) containing particle | grains, 5-25 mass% is more preferable, 8-20 mass% is especially preferable.

When content of a binder (c) is 3 mass% or more, the hygroscopicity of aminocarboxylic acid (salt) containing particle | grains is suppressed lower. Moreover, when it grind | pulverizes in manufacture of aminocarboxylic acid (salt) containing particle | grains, it becomes more difficult to produce fine powder. On the other hand, when content of a binder (c) is 30 mass% or less, especially the compounding balance of (a) component and (b) component is maintained favorable, and the solubility to water will improve.

Moreover, aminocarboxylic acid (salt) containing particle | grains may contain anionic surfactant (d) and the nonionic surfactant (e) whose melting | fusing point is less than 45 degreeC.

[Anionic Surfactant (d)]

As the anionic surfactant (d), for example, linear or branched alkyl (8 to 18 carbon atoms) benzenesulfonate, long-chain alkyl (10 to 20 carbon atoms) sulfonate, long chain olefin (average C10 to carbon atoms) Sulfonate, long-chain monoalkyl (10-20 carbon atoms) sulfate ester salt, polyoxyethylene (average degree of polymerization 1-10) long-chain alkyl (10-20 carbon atoms) ether sulfate ester salt, polyoxyethylene ( Average degree of polymerization 3-30) alkyl (average 6 to 12 carbon atoms) phenyl ether sulfate ester salt, α-sulfo fatty acid ester salt (average carbon atoms 12 to 20); Long chain monoalkyl, dialkyl or seskialkyl phosphates; Polyoxyethylene monoalkyl, dialkyl or seskialkyl phosphates and the like are used.

Among the above, (d) component is linear or branched alkyl (8-18 carbon atoms) benzene sulfonate, long-chain alkyl (10-20 carbon atoms) sulfonate, long-chain olefin (10-20 carbon atoms) sulfonate , Long-chain monoalkyl (10-20 carbon atoms) sulfate ester salt, α-sulfofatty acid ester salt (12-20 carbon atoms) is preferable, long-chain alkyl (10-20 carbon atoms) sulfonate, long-chain olefin ( Especially preferred is an average of 10 to 20 carbon atoms) sulfonate.

In addition, said "long chain" may be linear or branched, and may have a saturated or unsaturated bond.

The form of the salt in (d) component can illustrate alkali metal salts, such as sodium and potassium, an amine salt, ammonium salt, etc., and an alkali metal salt is preferable.

(d) A component may be used individually by 1 type and may be used in combination of 2 or more type.

1-20 mass% is preferable, as for content of (d) component in aminocarboxylic acid (salt) containing particle | grains, 3-18 mass% is more preferable, 5-15 mass% is especially preferable.

When content of (d) component is 1 mass% or more, the solubility with respect to the water of aminocarboxylic acid (salt) containing particle | grains improves. On the other hand, when content of (d) component is 20 mass% or less, the compounding balance of (a) component and (b) component is maintained favorably, and the bleaching effect improves.

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

When manufacturing the aminocarboxylic acid (salt) containing particle | grains of this invention, (e) component melts easily by heating, and it fully mixes with another raw material. Thereby, kneading kneading is performed favorably and the aminocarboxylic acid (salt) containing particle | grains which have moderate hardness are prepared.

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

As (e) component, a polyethyleneglycol addition type nonionic surfactant and a polyethyleneglycol polypropylene glycol addition type nonionic surfactant are mentioned, for example, Especially, a polyethyleneglycol addition type nonionic surfactant is preferable and C8-C8 is preferable. 3 to 80 moles of ethylene glycol or ethylene oxide (preferably 5 to 50 moles) are added to 1 mole of 20 (preferably 10 to 18) aliphatic alcohols, and more preferably less than 45 ° C of melting point. Do.

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

(e) A component may be used individually by 1 type and may be used in combination of 2 or more type.

1-9 mass% is preferable, as for content of (e) component in aminocarboxylic acid (salt) containing particle | grains, 2-9 mass% is more preferable, 3-8 mass% is more preferable.

When content of (e) component is 1 mass% or more, the solubility with respect to the water of aminocarboxylic acid (salt) containing particle | grains improves. On the other hand, when content of (e) component is 9 mass% or less, when manufacturing aminocarboxylic acid (salt) containing particle | grains, the extrusion pressure at the time of extrusion from an extruder does not become too low, for example, the shape retention of an extrudate is more It becomes good. And the obtained aminocarboxylic acid (salt) containing particle | grains are easy to suppress generation | occurrence | production of adhesion and solidification at the time of carrying and conveying the physical property which is hard to cause coalescence.

In the aminocarboxylic acid (salt) containing particle | grains of this invention, it is preferable to mix | blend polyhydric carboxylic acid especially as a solubility improving agent on the conditions which wash washing liquid shows alkali.

Examples of the polyvalent carboxylic acid include succinic acid and citric acid. In aminocarboxylic acid (salt) containing particle | grains, 5 mass% or less is preferable and, as for content of the said polyhydric carboxylic acid, 3 mass% or less is more preferable. If it is 5 mass% or less, it will become easy to take the compounding balance with (a) component especially. On the other hand, the lower limit is preferably 1% by mass or more because the effect of improving solubility is easily obtained.

Moreover, as another component, what is normally mix | blended with detergents and bleaches, such as medical use, can be illustrated. Specific examples include aluminosilicates such as cationic surfactants, amphoteric surfactants, and zeolites as grinding aids; Carbonates such as sodium carbonate and calcium carbonate, and amorphous silica; Bleach activators, such as silicate, such as calcium silicate and magnesium silicate, other inorganic salts (sodium sulfate, sodium chloride, etc.), the medium or long-chain fatty acid or its salt, and an organic peracid precursor, 1-hydroxyethane-1,1-depot Heavy metal chelating agents, clay minerals, fluorescent brighteners, ultraviolet absorbers, antioxidants, antibacterial agents, pigments, etc. other than (b) component, such as a sulfonic acid or its salt, can be illustrated.

Specific examples of the medium or long chain fatty acid include fatty acids having 8 to 10 carbon atoms in the acyl group, and fatty acids having 12 to 18 carbon atoms in the acyl group as the long chain fatty acids. In addition, "heavy chain or long chain" may be linear or branched chain, and may have a saturated or unsaturated bond. 0.1-5 mass% is preferable, and, as for content of a heavy chain or a long chain fatty acid in aminocarboxylic acid (salt) containing particle | grains, 0.5-4 mass% is more preferable.

The organic peracid precursor reacts with hydrogen peroxide (oxygen-based bleaching component) generated from a peroxide such as sodium percarbonate to generate an organic peracid with strong bleaching power, thereby exerting a bleaching effect on medical care and the like. However, the organic peracid precursor is an unstable component that tends to deteriorate over time, such as when the compound is blended with a granular detergent, bleach or the like, and the oxidation promoting effect is lowered due to interaction with other components. For this reason, since the effect as much as mix | blended is hard to be acquired, it is preferable that the aminocarboxylic acid (salt) containing particle | grains of this invention do not contain an organic peracid precursor.

In addition, as other components, a pigment | dye, a fragrance | flavor, etc. can also be mix | blended in the range which does not impair the effect of this invention.

As aminocarboxylic acid (salt) containing particle | grains, a zinc compound (a), an aminocarboxylic acid or its salt (b), an organic binder (c), an anionic surfactant (d), and nonionic with melting | fusing point less than 45 degreeC The aminocarboxylic acid (salt) containing particle | grains containing surfactant (e) are preferable, Especially, content of a zinc compound (a) is 10-80 mass%, and also of aminocarboxylic acid or its salt (b) It is more preferable that content is 10-80 mass%.

It is preferable that it is 0.05-0.44 in the mass ratio represented by (d) / (a), and, as for the compounding ratio of anionic surfactant (d) and zinc compound (a), it is more preferable that it is 0.10-0.40. If (d) / (a) is more than a lower limit, the effect of moisture absorption suppression will be easy to be acquired, and if (d) / (a) is below an upper limit, the solubility to water will be improved.

The mixing ratio of the nonionic surfactant (e) and the zinc compound (a) having a melting point of less than 45 ° C is preferably 0.05 to 0.36, more preferably 0.06 to 0.30 in the mass ratio represented by (e) / (a). . When (e) / (a) is more than a lower limit, the solubility to water is improved, and when (e) / (a) is below an upper limit, the extrusion pressure at the time of extrusion when manufacturing aminocarboxylic acid (salt) containing particle | grains is produced. Formability can be improved and solidification of a granulated material is easy to be suppressed, without becoming too low.

It is preferable that it is 0.44-2.0 in the mass ratio represented by (b) / (a), and, as for the compounding ratio of an aminocarboxylic acid or its salt (b) and zinc compound (a), it is more preferable that it is 0.48-1.9. When (b) / (a) is more than a lower limit, when manufacturing aminocarboxylic acid (salt) containing particle | grains, the extrusion pressure at the time of extrusion will not become high too much, and if (b) / (a) is below an upper limit or less, aminocarboxylic acid Hygroscopicity of (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 from 0.7 to a mass ratio represented by (c) / [(d) + (e)]. It is preferable that it is 2.0, and it is more preferable that it is 0.8-1.5. If (c) / [(d) + (e)] is in the said range, the shape retention of aminocarboxylic acid (salt) containing particle | grains will improve and it will be easy to suppress hygroscopicity, maintaining good solubility with respect to water.

"Mass ratio represented by (d) / (a)" shows the ratio of content (mass%) of (d) component to content (mass%) of (a) component in aminocarboxylic acid (salt) containing particle | grains. .

"Mass ratio represented by (e) / (a)" shows the ratio of content (mass%) of (e) component to content (mass%) of (a) component in aminocarboxylic acid (salt) containing particle | grains. .

"Mass ratio represented by (b) / (a)" shows the ratio of content (mass%) of (b) component to content (mass%) of (a) component in aminocarboxylic acid (salt) containing particle | grains. .

"Mass ratio represented by (c) / [(d) + (e)]" is ((%) relative to the content (mass%) of the sum of the (d) component and the (e) component in the aminocarboxylic acid (salt) -containing particles. The ratio of content (mass%) of c) component is shown.

<Method for producing aminocarboxylic acid (salt) -containing particles>

Specifically as a manufacturing method of aminocarboxylic acid (salt) containing particle | grains, the following methods (I)-(III) and (IV) can be illustrated.

Method (I): The method of adding and mixing (a) component (powder form), after adding water etc. by the method of spraying, mixing (b) component (powder form).

As water etc., the water and the aqueous solution of the said base can be illustrated. By (a) component by spraying, such as water, (b) component becomes easy to change into the structure which is hard to absorb moisture. When adding the aqueous solution of a base, 8-12 are preferable and, as for pH of this aqueous solution, 8-10 are more preferable. What is necessary is just to control suitably spray amount, such as water, so that it may become a suitable range of water content mentioned above, 0.2-5 mass parts is preferable with respect to a total of 100 mass parts of (a) component and (b) component, and 0.2-3 mass parts is more preferable. Do.

After adding and mixing (a) component (powder shape), you may add the said coating component further. By further adding the coating component, the aminocarboxylic acid (salt) -containing particles are less likely to have a lump shape, and the fluidity is improved.

As the mixer used in the method (I), a Loedig Mixer (type M20, manufactured by Matsubo Corporation), a high speed mixer, a proshare mixer, or the like can be used.

The mixing speed is preferably 100 to 350 rpm, more preferably 150 to 250 rpm, for example, at a rotational speed of the main shaft. The temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C.

Method (II): The method of mixing a (a) component, (b) component, and water, preparing a slurry, and spray-drying the said slurry.

The spray drying conditions are preferably 2 to 4 MPa, and more preferably 2.5 to 3 MPa.

As for temperature, it is preferable to make the gas temperature supplied from the lower part of a spray drying tower into 170-300 degreeC, It is more preferable to set it as 230-270 degreeC, The gas temperature discharged from the top of a spray drying tower is 70 It is preferable to set it as -125 degreeC, and it is more preferable to set it as 90-110 degreeC.

Method (III): After mixing (a) component and (b) component, the method of adding and mixing a liquid binder.

As the liquid binder, a binder exemplified above as other components can be used, and a water-soluble polymer that is solid at ordinary temperature and dissolved when heated is preferable. Especially, since polyethylene glycol is easy to handle, polyethyleneglycol is especially preferable. As polyethyleneglycol, the thing of average molecular weights 1000-20000 is preferable, and the thing of average molecular weights 4000-10000 is more preferable. If the said average molecular weight is more than a lower limit, fluidity will become more favorable, and if it is below an upper limit, solubility will become more favorable. The average molecular weight here shows the average molecular weight described in the cosmetic raw material reference | standard (2nd edition comment). By adding a liquid binder, sufficient shearing force is imparted upon stirring, and the hygroscopicity of aminocarboxylic acid (salt) -containing particles is further reduced, so that solidification hardly occurs.

As the mixer used in the method (III), a Rodige mixer (type M20, manufactured by Matsubo Corporation), a high speed mixer, a proshare mixer, or the like can be used.

The mixing speed is preferably 100 to 350 rpm, more preferably 150 to 250 rpm, for example, at a rotational speed of the main shaft. The temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C.

Since the mixing efficiency is increased when the binder is added and mixed, it is preferable to perform the grinding operation by rotating the chopper at 1000 to 5000 rpm while rotating the main shaft.

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

Method (IV): It has a kneading process of kneading and kneading the said (a)-(e) component, and the granulation process of extruding and granulating the kneaded material obtained by the said kneading process.

[Chemical process]

In the kneading step, kneading kneading of the components (a) to (e) is carried out.

The method for performing the kneading kneading is not particularly limited, and for example, a method of using a conventionally known batch or continuous kneader can be exemplified.

When using a batch kneader, for example, the (c) component, the (d) component, the (e) component, and the (b) component are introduced into a horizontal chamber having a stirring vane rotating therein in the longitudinal direction. Then, the batch kneader is heated to 40 to 80 ° C. and stirred and mixed. Subsequently, a kneaded product is obtained by introducing (a) component and kneading kneading in the said horizontal chamber.

It is preferable that the stirring blade rotates in the vertical direction with respect to the horizontal axis of a horizontal chamber, and the rotation speed is about 120-360 rpm. The stirring blade can use various things, and the ski-shaped shovel blade is especially preferable. Moreover, it is also preferable to use together the chopper blade which rotates at 3000-6000 rpm with a stirring blade.

As a kneader which has a horizontal chamber provided with such stirring blades, For example, Proshare mixer (made by Pacific Machinery & Engineering Co., Ltd.); Rödige mixers, ribbon mixers, turbulizers, pug mixers, spartan granulators (manufactured by Fuji Paudal Co., Ltd.); A desk kneader (Irie Shokai Co., Ltd. product) etc. can be illustrated.

When using a continuous kneader, for example, a closed compaction treatment apparatus (preferably heated to a temperature at which (e) component is melted (preferably 25 to 100 ° C, more preferably 40 to 80 ° C) (preferably Is a horizontal type continuous kneader), after mixing (c) component, (d) component, (e) component, and (b) component in advance, or mixing (a) component while mixing. Thereby, a powder mixture is prepared, and a kneaded material is obtained by applying a shearing force to the powder mixture at that temperature and kneading kneading.

Alternatively, the closed compaction treatment 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 in advance (a) to ( A kneaded product is obtained by continuously introducing the powder mixture of e) component and kneading kneading | mixing.

Such kneading kneading may be performed using a single screw or twin screw kneading extruder or the like in addition to the kneader. As a continuous kneader used here, Kurimoto, Ltd., for example. Products of KRC Kneader, Nara Machinery Co., Ltd. A product extruder etc. can be illustrated.

Among these methods, a method of using a continuous kneader is preferable because the hygroscopicity of the aminocarboxylic acid (salt) -containing particles finally obtained is suppressed low and hardening is more likely to occur.

In addition, since aminocarboxylic acid (salt) -containing particles that are unlikely to cause solidification and have excellent solubility in water are easily obtained, the components (c) to (e) and (b) are first mixed and then (a) The method of adding and kneading and kneading | mixing kneading is preferable.

It is preferable that the temperature at the time of kneading kneading in a kneading process is a temperature range which does not contain the dehydration and transition temperature of (a) component, It is more preferable that it is 3 degreeC or more high from melting | fusing point of (e) component, It is more preferable that it is 5-20 degreeC high temperature from melting | fusing point of (c) component.

By performing kneading and kneading in a temperature range that does not include the dehydration and transition temperature of the component (a), the extrusion pressure at the time of extruding from the extruder becomes constant (stable), and a homogeneous extrudate is easily obtained, and the shape retention is easy. It becomes good.

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

The storage stability of aminocarboxylic acid (salt) containing particle | grains becomes favorable by performing kneading kneading | mixing without adding water substantially.

When content of the aminocarboxylic acid (salt) containing particle finally obtained when kneading and kneading the said (a)-(e) component becomes 10-80 mass% of (a) component, and 10-80 mass% of (b) component Each component is mix | blended individually. In addition, it is preferable that each component uses the following, respectively.

Since both (d) component and (b) component improve the storage stability of aminocarboxylic acid (salt) containing particle | grains, it is preferable to use a powdery thing as it is.

The component (d) may be mixed with a small amount of inorganic salts (sodium chloride, sodium sulfate, aluminosilicate, calcium carbonate, etc.) from the fact that the powder of the component (d) itself can be easily formed.

(a) It is preferable to use the powder whose average particle diameter is 30-800 micrometers, It is more preferable to use 50-600 micrometers powder, It is further more preferable to use 60-550 micrometer powder. When the average particle diameter of (a) component is more than a lower limit, particle aggregation of (a) component itself is suppressed. On the other hand, if the average particle diameter of (a) component is below an upper limit, a uniform kneaded material will become easy to be obtained.

(b) It is preferable to use the powder whose average particle diameter is 30-1500 micrometers, It is more preferable to use the powder of 50-1300 micrometers, It is further more preferable to use the 60-1200 micrometer powder. If the average particle diameter of (b) component is more than a lower limit, the agglomeration of the particle | grains of (b) component itself will be suppressed, and the freezing prevention effect by hygroscopicity will improve. On the other hand, if the average particle diameter of (b) component is below an upper limit, a uniform kneaded material will become easy to be obtained.

It is preferable that it is 50-65 degreeC, and, as for the temperature of the kneaded material after kneading kneading | mixing, it is more preferable that it is 53-63 degreeC.

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

It is preferable that it is 50-900g, and, as for the hardness of the kneaded material after kneading kneading | mixing, it is more preferable that it is 200-700g.

If the hardness of the kneaded product is greater than or equal to the lower limit, the kneaded product will not be too soft, and the decrease in solubility due to coalescence after extrusion can be suppressed. The fall of solubility by this and deterioration of storage stability can be suppressed.

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

In order to control the hardness of the kneaded material in the above preferred range, for example, the temperature at the time of kneading kneading may be adjusted or the blending amount of (e) component may be adjusted.

[Assembling process]

In the granulation step, the kneaded material obtained in the kneading step is extruded and granulated.

Specifically, strands, such as a cylinder, a pillar, and a triangular column, are thrown into the single- or two-screw screw kneading extruder by extruding the kneaded material obtained by the said kneading process; Spherical, plate-shaped, or noodle-shaped granules are obtained.

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

It is preferable that it is 48-70 degreeC, and, as for the temperature of the extrudate after extrusion granulation, it is more preferable that it is 52-67 degreeC.

If the temperature of an extrudate is more than a lower limit, the pressure of extrusion will not become high too much and the burden (load) to an apparatus will be easy to be reduced. On the other hand, when the temperature of an extrudate is below an upper limit, unity of a granulated material is easy to be suppressed at the time of the sizing (grinding) operation mentioned later.

It is preferable that the extrusion power in the extruder at the time of extruding a kneaded material is 4-50 kwh / t, It is more preferable that it is 4.5-48 kwh / t, It is still more preferable that it is 5-45 kwh / t, 5.5-40 kwh / Particularly preferred is t.

When extrusion power is 4 kwh / t or more, the storage stability of the aminocarboxylic acid (salt) containing particle | grains obtained improves. On the other hand, when the extrusion power is 50 kwh / t or less, the extrudate does not become too hard and fine powder hardly occurs when pulverized. Moreover, the solubility with respect to the water of aminocarboxylic acid (salt) containing particle | grains improves.

Examples of the extruder include pelleta double (manufactured by Fuji Paudal Co., Ltd.), twin dome gran (manufactured by Fuji Paudal Co., Ltd.), multi-grain (manufactured by Dalton Co., Ltd.), and the like. have.

In addition, you may perform operation which obtains kneaded material by kneading kneading in a kneading process, and operation which performs extrusion granulation in a granulation process with one apparatus. As this method, the method of attaching a mesh board to the discharge port of the kneaded material in the apparatus for kneading kneading, for example, and passing this mesh board can be illustrated to obtain a granulated material.

As an apparatus applicable to this method, EXTRUD-O-MIX by Hosokawa Micron Corporation can be illustrated, for example.

In order to match the length of the obtained extrudate after performing extrusion granulation, it is preferable to carry out sizing by using a grinder (crushing granulator) equipped with a high speed rotary knife cutter or the like to impart the impact and shear force to the extrudate and pulverize it.

The rotational speed of the high speed rotary knife cutter is preferably about 30 to 100 m / s.

Examples of the mill include COMMINUTOR (manufactured by Fuji Paudal Co., Ltd.), FITZ MILL (manufactured by Hosokawa Micron Corporation), speed mill (manufactured by Okada Seiko Co., Ltd.), and the like. It can be illustrated.

It is preferable to make the said extrudate into the granulated material of 200-700 micrometers of average particle diameters by such a sizing, and it is more preferable to make the granulated material of 250-450 micrometers. If the particle diameter of a granulated material is more than a lower limit, the storage stability of aminocarboxylic acid (salt) containing particle | grains will improve. On the other hand, the solubility with respect to the water of an aminocarboxylic acid (salt) containing particle | grains improves that the particle diameter of a granulated material is below an upper limit.

Moreover, it is preferable to set the ratio of the granulated particle | grains whose particle diameter is less than 150 micrometers to 14 mass% or less with respect to the whole aminocarboxylic acid (salt) containing particle | grains, and it is more preferable to set it as 0.2-10 mass%. When it is below an upper limit, oscillation becomes less likely to generate | occur | produce, and the fluidity | liquidity of aminocarboxylic acid (salt) containing particle | grains improves.

The manufacturing method of the aminocarboxylic acid (salt) containing particle | grains of this invention may have other processes other than the kneading process and granulation process mentioned above.

As another process, the process of further covering the surface of the granulated material obtained by the granulation process, etc. can be illustrated.

Among the above, the method (I), the method (III), or the method (IV) is preferable from the point of energy efficiency related to manufacture.

(Granular detergent composition)

The granular detergent composition of this invention contains the aminocarboxylic acid (salt) containing particle | grains of the said this invention.

200-1500 micrometers is preferable, as for the average particle diameter of a granular detergent composition, 250-1000 micrometers is more preferable, 280-500 micrometers is more preferable. If the said average particle diameter is more than a lower limit, generation | occurrence | production of a fine powder will be suppressed, while if it is below an upper limit, the solubility to water will improve.

0.3-1.5 g / mL is preferable, as for the bulk density of a granular detergent composition, More preferably, 0.6-1.2 g / mL is more preferable, 0.7-0.9 g / mL is still more preferable. When the said bulk density is more than a lower limit, the space (storage place) required at the time of the storage of a granular detergent composition can be made smaller, and it is advantageous. On the other hand, the solubility to water of a granular detergent composition becomes it favorable that it is below an upper limit.

In this invention, a bulk density shows the value measured by the method according to JISK3362-1998.

Water content of a granular detergent composition becomes like this. Preferably it is 15 mass% or less, More preferably, it is 2-9 mass%, More preferably, it is 4-8 mass%. If the said moisture content is below an upper limit, the solidification of a granular detergent composition will become hard to produce more.

0.1-20 mass% is preferable, as for content of aminocarboxylic acid (salt) containing particle | grains in a granular detergent composition, 0.5-15 mass% is more preferable, 1-12 mass% is more preferable.

When content of aminocarboxylic acid (salt) containing particle | grains is more than a lower limit, it will act with detergent raw materials (surfactant, a peroxide, etc.), and a washing bleaching effect, an antibacterial effect, a bactericidal effect, etc. will become easy to be exhibited. On the other hand, if it is below an upper limit, it will become easy to take the compounding balance with another detergent raw material, and a sufficient washing | cleaning effect will become easy to be obtained.

As detergent raw materials other than the aminocarboxylic acid (salt) containing particle | grains in a granular detergent composition, what is normally mix | blended with detergent compositions, such as medical grade, can be used.

Detergent raw materials include, for example, surfactants (anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc.), inorganic builders, organic builders, alkali agents, sulfates such as sulfates, percarbonates, or granulations thereof. Bleach such as water, re-contamination (deposition) inhibitor, dye, pigment, flavoring agent, enzyme (e.g. protease, lipase, cellulase, amylase, etc.), bleach activator or granules thereof, reducing agents such as sulfite, thiosulfate, fluorescent Examples include brighteners, ultraviolet absorbers, softening agents (such as bentonite), foam control agents (such as silicone), surface modifiers, oil absorbers, antioxidants, antibacterial agents, and the like.

The manufacturing method of a granular detergent composition can be manufactured by a well-known manufacturing method.

For example, after dispersing and dissolving detergent raw materials, such as surfactant, an inorganic builder, an organic builder, and an alkaline agent, in water and preparing a slurry, the said slurry is spray-dried and spray dried particle | grains are obtained. Subsequently, the spray dried particles and other detergent raw materials are kneaded and kneaded, extruded or pulverized to obtain powder. Then, a granular detergent composition can be obtained by mixing the said powder, aminocarboxylic acid (salt) containing particle | grains, 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 said aminocarboxylic acid (salt) containing particle | grains contains the aminocarboxylic acid (salt) which has hygroscopicity, it is hard to produce solidification.

Although it is not certain as a reason why the granular detergent composition containing the said aminocarboxylic acid (salt) containing particle | grains is hard to produce solidification, it guesses as follows.

The aminocarboxylic acid (salt) containing particle | grains of this invention contain zinc compound (a) and aminocarboxylic acid or its salt (b) in predetermined molar ratio (a) / (b) = 0.5-6.

In the aminocarboxylic acid (salt) -containing particles of the present invention, by containing the (a) component and the (b) component in a predetermined molar ratio, the vicinity of the surface of the (b) component particle is hardly absorbed by the (a) component. Since it changes to a structure, compared with the case of only (b) component particle | grains, it is hard to be influenced by an environment, and it is thought that hygroscopicity is low. Thereby, it is thought that the granular detergent composition of this invention is hard to generate | occur | produce, and it is hard to produce what is called caking.

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

(Example)

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

<Measurement Method of Average Particle Diameter> (Measurement 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 determined using a laser light scattering method using a particle size distribution measuring device (LDSA-3400A (17ch) manufactured by Tohnichi Computer Applications Corporation). Was measured as the median diameter on a volume basis.

<Measurement of volume density>

In this Example, the bulk density was measured by the method according to JIS K3362-1998.

<Measurement method of water content>

In the present embodiment, the moisture content was measured using an infrared moisture meter (Kett Electric Laboratory product, product name: Kett moisture meter), 5 g of the sample, a sample surface temperature of 130 ° C. (when measuring the granular detergent composition) or 170 ° C. (spray dried particles). When measured), the measurement was performed under the conditions of 20 minutes.

<Calculation method of moisture absorption rate (measured)>

First, the sample was unfolded to a thickness of 5 mm in a glass chalet (inner diameter of 85 mm) and placed in a thermostat set at a temperature of 45 ° C. and a relative humidity of 80%. Subsequently, the mass of the glass chalet in which the said sample was unfolded every elapsed time (every 60 minutes) was measured in the said thermostat, and the change with time was recorded. And moisture absorption (measurement) (mass%) was calculated | required by Formula (1) mentioned above.

<Calculation method of moisture absorption calculated value>

The moisture absorption calculated value (mass%) was calculated | required by Formula (2) shown below.

In formula (2), "metal salt" means zinc sulfate monohydrate or anhydrous sodium sulfate.

"The compounding quantity of MGDA" and "the compounding quantity of a metal salt" are content of "(b) MGDA" and "(a) zinc sulfate monohydrate" or "sodium sulfate anhydride" shown to Table A1-A4, respectively.

"The moisture absorption of MGDA single body" is 83.4 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 the anhydrous sodium sulfate is used.

In addition, when aminocarboxylic acid (salt) is other than MGDA, it calculates by replacing "MGDA" in following formula (2) with each aminocarboxylic acid (salt).

 <Evaluation Method of Solidification of Granular Detergent Composition>

Coated cardboard (Basic weight: 350g / m²), Wax sandpaper (Basic weight: 30g / m2) and Kraft pulp paper (Basic weight: 70g / m²) The box of mm and height 85mm was produced.

500g of granular detergent compositions of each case were put into this box, and it put into the thermostat set to the temperature of 30 degreeC, and relative humidity 80% for 48 hours. Thereafter, the granular detergent composition was slowly spilled from the box onto a sieve having a mesh size 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 standard

A: The residual amount of the granular detergent composition remaining on the sieve was less than 25 g.

B: The residual 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.

<Raw material used>

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

Zinc compound (a)

Zinc sulfate monohydrate: The product of Shinyo Corporation, brand name "dry zinc sulfate", 70 micrometers of average particle diameters.

Comparative component (a ') of component (a)

Anhydrous sodium sulfate: The product made by Shikoku Chemicals Corporation, brand name "neutral anhydrous manganese A0", an average particle diameter of 89 micrometers.

Aminocarboxylic acids or salts thereof (b)

MGDA: Trisodium methylglycine diacetic acid, product of BASF, brand name "Trilon M Powder", coordination site 4, content rate (net content) 83 mass%, average particle diameter 63 micrometers.

NTA: Nitrilo triacetic acid trisodium, the BASF Corporation make, brand name "Trilon A92R", 92 mass% of pure parts, 63 micrometers of average particle diameters.

IDS: iminodisuccinic acid tetrasodium, LANXESS K.K. Product, brand name "Baypure CX100", 80 mass% of pure components, 100 micrometers of average particle diameters.

· Other ingredients

Sodium hydrogen carbonate: Junsei Chemical Co., Ltd. Products, express.

Zeolite: A-type zeolite, the product made from Tisilicate company, brand name "zeolite Na-4A", 80 mass% of pure parts, 3 micrometers of average particle diameters.

Polyethyleneglycol: Lion Corporation make, brand names "PEG'6000P", the average molecular weight 6000, melting | fusing point 56-61 degreeC.

Detergent Raw Materials

MES paste: α- sulfo fatty acid alkyl ester salt-containing paste [paste composition: 63 mass% of α- sulfo fatty acid alkyl ester salt (MES-Na), 16 mass% of nonionic surfactant (polyoxyethylene alkyl ether mentioned later), di salt And 8 mass% of impurities such as methyl sulfate, 13 mass% of water], and the fatty acid chain length of the α-sulfofatty acid alkyl ester salt is a mixture ratio of 16 and 18 carbon atoms, 16 carbon atoms and 18 carbon atoms C16 / C18 = 8/2 (Mass ratio).

LAS-K: Spray in <production example of granular detergent composition> which mentions linear alkyl (10-14 carbon atoms) benzenesulfonic acid [Lion Corporation make, Lipon LH-200 (LAS-H pure content 96 mass%)] mentioned later. The compound neutralized with 48 mass% potassium hydroxide aqueous solution at the time of preparing the slurry for dry particle preparation.

LAS-H: Linear alkyl (10-14 carbon atoms) benzenesulfonic acid [Lion Corporation make, Lipon LH-200 (96 mass% of pure parts)].

Polyoxyethylene alkyl ether: Ethylene oxide 15 mol adduct (melting point 40 degreeC) of ECOROL 26 (brand name, the product of ECOGREEN company; the alcohol which has a C12-C16 alkyl group). 90 mass% of pure parts, 10 mass% of moisture content.

Soap: carbon number (C) 12-18 fatty acid sodium [Lion Corporation make, 67 mass% of pure parts, Tita 40-45 degreeC; Fatty acid composition C12 0.7 mass%, C14 11.4 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: A-type zeolite, the product made from Tisilicate company, brand name "zeolite Na-4A", 80 mass% of pure parts, 3 micrometers of average particle diameters.

MA agent: Acrylic acid-maleic acid copolymer salt, Nippon Shokubai Co., Ltd. Product, brand name "ACUALIC TL-400", pure 40 mass%.

Potassium carbonate: potassium carbonate (powder) (manufactured by Asahi Glass Co., Ltd.) Average particle diameter 490 µm, bulk density 1.30 g / cm 3.

Sodium carbonate: granular material (Asahi Glass Co., Ltd.) Average particle diameter 320 mu m, bulk density 1.07 g / cm 3.

Anhydrous sodium sulfate: The product made by Shikoku Chemicals Corporation, brand name "neutral anhydrous forage A0."

Sodium percarbonate granulated product: Zhejiang JINKE CHEMICALS Co., Ltd., brand name "SPCC", 13.8 mass% of effective oxygen amount, average particle diameter 870 micrometers.

Carboxymethyl cellulose: Daicel Corporation make, brand name "CMC Daicel 1190", mass average molecular weight about 300,000, etherification degree 0.70.

Fluorescent agent: Shiva Japan Co., Ltd. make, a brand name "TINOPAL CBS-X."

Pigment: 20 mass% aqueous dispersion of Navy Blue (Dainichiseika Color & Chemicals Mfg. Co., Ltd.).

Fragrance: Fragrance composition A shown to Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.

Enzyme: Protease (Sabinase 12T) / Amylase (Stainzyme 12T) / Lipase (LIPEX100T) / Cellulase (Celline 4500T) (above, all Novozyme Japan Co., Ltd.) = 2/1/1/1 (mass ratio) Mixture.

Bleach activator granulated material: mass ratio of OBS12 (sodium 4-dodecane oil oxybenzenesulfonate), PEG6000, AOS (sodium 14-olefin sulfonate powder) and A-type zeolite powder 70/20/5 / 5, assembly.

<Production example of aminocarboxylic acid (salt) -containing particles>

The aminocarboxylic acid (salt) containing particle | grains of each case were prepared according to the composition shown to Tables A1-A4.

In a table | surface, content of a compounding component shows the pure part conversion amount.

(Example A1)

MGDA was charged at 40 ° C. in a Lodge mixer (type M20, manufactured by Matsubo Corporation) with a homogeneous shovel and a clearance between the shovel and the wall surface was 5 mm, and the water was rotated at 200 rpm while the main shaft was rotated at 200 rpm. 1.0 parts by mass) was sprayed on.

After completion of spraying, zinc sulfate monohydrate was added at 40 ° C, the main shaft was stirred while rotating at 200 rpm (the chopper was stopped), and MGDA-containing particles were obtained 5 minutes after the stirring was started.

(Examples A2 and A3)

Except having changed the compounding quantity of zinc sulfate monohydrate and MGDA according to the composition shown in Table A1, MGDA containing particle | grains were obtained like Example A1.

(Example A4)

MGDA-containing particles were obtained in the same manner as in Example A2, except that 1 mass% aqueous sodium hydrogen carbonate (heavy bath) solution (pH8.5 / 25 ° C) was used instead of water.

(Example A5)

Water (36 mass% in the spray drying slurry), MGDA and zinc sulfate monohydrate are charged into a mixing tank having a spray drying slurry preparation device, that is, a stirring blade composed of a stirring blade and a rotating shaft, and having a circulation line with a pump. did. Then, stirring was continued for 10 minutes, the temperature was adjusted to 75 degreeC, and the slurry for spray drying was prepared on the scale of compounding quantity 200 kg / batch.

The rotation speed of the stirring blade at this time was set to 60 rpm.

The obtained spray drying slurry was transferred to a spray drying tower, and sprayed at a spray pressure of 2.5 MPa (gauge pressure) from a pressure spray nozzle provided near the top of the spray drying tower to obtain MGDA-containing particles as spray dried particles. At that time, the gas of 230-270 degreeC was supplied to the lower part of the spray drying tower, and it became the temperature of 90-110 degreeC, and discharged from the tower top of the spray drying tower, and hot gas was supplied to the spray drying tower. In addition, the temperature of the hot gas supplied was adjusted suitably in order to obtain MGDA containing particle | grains of desired water content (3 mass%).

(Example A6)

MGDA was put at 40 degreeC in the Lodige mixer (M20 type | mold, Matsubo Corporation make) which has a homobular shovel, and the clearance between a shovel-wall surface was 5 mm, and water was sprayed, rotating a main shaft at 200 rpm.

After completion of spraying, zinc sulfate monohydrate was added at 40 ° C, the spindle was stirred while rotating at 200 rpm (chopper was stopped), zeolite was added at 40 ° C after 5 minutes after the stirring was started, and the spindle was rotated at 200 rpm. MGDA containing particle | grains were obtained by performing stirring (chopper is stopped) for 5 minutes, making it carry out.

(Example A7)

60 ° C MGDA and 60 ° C zinc sulfate monohydrate in a Rodige mixer (type M20, manufactured by Matsubo Corporation) with a clearance of 5 mm with a shovel-shaped shovel and a jacket-wall clearance controlled at 65 ° C. Was added while stirring (rotating the chopper) while rotating the main shaft at 200 rpm. Five minutes after the above stirring was started, the chopper was rotated at 4000 rpm (the rotation speed of the spindle was kept), and polyethylene glycol at 25 ° C. was added thereto, followed by stirring for 5 minutes to obtain MGDA-containing particles.

(Example A8)

NTA containing particle | grains were obtained like Example A1 except having changed the compounding quantity of zinc sulfate monohydrate according to the composition shown in Table A2, and changing MGDA to predetermined amount of NTA.

(Example A9)

According to the composition shown in Table A2, IDS containing particle | grains were obtained like Example A1 except having changed the compounding quantity of zinc sulfate monohydrate and changing MGDA to predetermined amount of IDS.

(Comparative Example A1)

The raw material MGDA (BASF Corporation make, a brand name "Trilon M Powder") was used as it is.

(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, A4)

MGDA containing particle | grains were obtained like Example A1 except having changed the compounding quantity of zinc sulfate monohydrate and MGDA according to the composition shown in Table A3.

(Reference Example A1)

Zinc sulfate monohydrate (manufactured by Shinyo Corporation, trade name "dry zinc sulfate") as a raw material was used as it was.

(Reference Example A2)

Anhydrous sodium sulfate (manufactured by Shikoku Chemicals Corporation, trade name "neutral anhydrous A0") was used as it is.

(Comparative Example A5)

NTA (made by BASF Corporation, brand name "Trilon A92R") of a raw material was used as it was.

(Comparative Example A6)

IDS (LANXESS K.K. product, brand name "Baypure CX100") of a raw material was used as it was.

The average particle diameter was measured by the method mentioned above about the particle | grains of each example, and the moisture absorption rate (actual measurement) and the moisture absorption rate calculated value were computed, respectively. The result was written together to Table A1-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 had a moisture absorption rate (compared to the aminocarboxylic acid (salt) alone of Comparative Examples A1, A5 and A6). ) 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 had a moisture absorption rate (actual) / hygroscopicity calculated value of 30 to 75%. It can be seen that the rate (actual measurement) is significantly lower than the moisture absorption rate calculated value.

Therefore, it was confirmed that the aminocarboxylic acid (salt) -containing particles of Examples A1 to A9 according to the present invention had low hygroscopicity.

<Production example of granular detergent composition>

The granular detergent composition of each case was prepared by the method shown below.

(Example A10)

According to the composition shown in Table A5, each compounding component was thrown in the reaction apparatus which has a stirrer and a jacket, it was made to melt | dissolve and disperse in water (75 degreeC of jacket temperature of stirrer), and the slurry for spray drying particle preparation of 60 mass% of solid content concentration was prepared.

Table A5

 Subsequently, this spray dried particle preparation slurry was spray-dried under the following conditions using a countercurrent drying tower, and zeolite (to 100 mass parts of obtained spray dried particles as a coating agent which coats spray dried particle from the lower part of a spray drying tower). 1 part by mass) was then introduced to obtain spray dried particles.

[Condition of spray drying]

Spray Dryer: counterflow, tower diameter 2.0m, effective length 5.0m

Atomization method: pressure nozzle method

Spray pressure: 30 kg / cm 2

Hot air inlet temperature: 250 ℃

Hot air outlet temperature: 100 ℃

The average particle diameter of the obtained spray-dried particle | grains was 300 micrometers, 0.30 g / mL and the water content were 5.0 mass% (measurement condition 170 degreeC of water content, 20 minutes) of water content.

Next, 52.05 mass% of the obtained spray-dried particles, 18.6 mass% of MES paste, 3.6 mass% of polyoxyethylene alkyl ether, 0.1 mass% of fluorescent agent, and 0.45 mass% of water were continuously kneader (Kurimoto, Ltd. product, KRC). -S4), and the dough (135 krp rotation speed of a kneader, jacket temperature: jacket inlet 5 degreeC, outlet 25 degreeC (passing through a jacket and cooling)) was prepared, and the dough shape was prepared. The temperature of the obtained dough shape was 55 +/- 15 degreeC.

The obtained dough shape is put into pelleter double (manufactured by Fuji Paudal Co., Ltd., product name: EXD-100 type), and is cut simultaneously with extrusion from a die having a hole diameter of about 10 mm and a thickness of 10 mm (the cutter circumferential speed of pelleter is 5 m / s) to obtain a pellet-shaped molded body (diameter about 10 mm, length 70 mm or less (substantially 5 mm or more)).

5.2 mass% of zeolite as a grinding aid was added to 74.8 mass% of the obtained pellet-formed compacts, and it grind | pulverized using the wheat flour (Hosokawa Micron Corporation make, DKA-6 type | mold) arrange | positioned in three steps in series under ventilation coexistence, and obtained powder. Grinding conditions are as follows. The temperature of the obtained powder was 30 +/- 10 degreeC.

[Crushing condition]

Blowing temperature: 15 ± 3 ° C.

Blowing amount (ratio of gas / solid): 2.8 ± 0.25 m 3 / kg.

Screen diameter: 6 mm of 1st stage, 4 mm of 2nd stage, 2 mm of 3rd stage.

Grinder rotation speed: 470 rpm (approx. 60 m / s).

Treatment speed: 230 g / hr.

Subsequently, the powder 80.0 was placed on a horizontal cylindrical electric drum (with a diameter of 0.70 m, a length of 1.40 m, an inclination angle of 3 °, a thickness of 1 mm x a height of 50 mm x a length of 15 obstruction plates of 15 mm) so that the processing speed was 240 kg / hr. A polyoxyethylene alkyl ether was mixed with a mass%, 1.8 mass% of zeolite, 5.0 mass% of sodium percarbonate granules, 1.0 mass% of carboxymethyl cellulose, and 10 mass% of MGDA-containing particles of Example A1. 0.5 mass% was sprayed at the spray pressure of 0.5-1.5 MPa using the pressure cone nozzle K series (made by H. IKEUCHI & Co., Ltd.).

Then, after spraying 0.1 mass% of pigment | dye (20 mass% aqueous dispersion) and 0.1 mass% of fragrance | flavor, 1.0 mass% of enzymes and 0.5 mass% of bleaching activator granulated materials are added and mixed, and a granular detergent composition (average particle diameter 360) Μm, bulk density 0.85 g / ml).

In addition, the water content of the obtained granular detergent composition was 7.0 mass% (measurement condition 130 degreeC, 20 minutes of water content).

(Examples A11 to A17 and Comparative Examples A7 to A8)

A granular detergent composition was prepared in the same manner as in Example A10 except that instead of the MGDA-containing particles of Example A1, each of the aminocarboxylic acid (salt) -containing particles of Examples A2, Examples A4 to A9, and Comparative Examples A1 to A2 was used. Got it.

(Reference Example A3)

When preparing the granular detergent composition of Example A10, the spray dried particle obtained in the meantime was used as it is.

(Reference Example A4)

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 in place of the MGDA-containing particles of Example A1 in Example A10.

About the granular detergent composition of each case, solidification property was evaluated by the method mentioned above, and the moisture absorption rate (measurement) was also computed. The results are shown in Tables A6 and A7.

Table A6

Table A7

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

The average particle diameter of Examples B1-B10 and Comparative Examples B1, B2 was measured by the measuring method 2 or the method according to this in the above-mentioned [Measurement method of average particle diameter]. Dehydration and transition temperature were measured similarly to the method mentioned above.

The composition of the aminocarboxylic acid (salt) containing particle | grains manufactured by the manufacturing method of each case was shown to Table B1-B3.

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

Organic binder (c)

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

PEG-4000: The Lion Corporation make, brand name "PEG # 4000", average molecular weight 4000, melting | fusing point 55 degreeC.

Anionic surfactants (d)

AOS-Na: C14-18 alpha-olefin sulfonic acid Na salt, the Lion Corporation make, brand name "Liporan PJ-400", an average particle diameter of 200 micrometers.

AS-Na: Alkyl sulfate sodium salt having 10 to 18 carbon atoms, New Japan Chemical Co., Ltd. Product, brand name "Sinoline 90TK-T", 150 micrometers in average particle diameter.

Nonionic surfactants having a melting point of less than 45 ° C. (e)

POE alkyl ether (EO = 15): 15 mol addition product of the C12-C16 natural alcohol EO (ethylene oxide), Lion Corporation make, brand name "LMAO-90", 90 mass% of pure parts, 40 degreeC of melting points.

POE alkyl ether (EO = 9): C12-16 natural alcohol EO9 mol addition product, Lion Corporation make, brand name "Leox CL-90", 100 mass% of pure parts, 28 degreeC of melting points.

Zinc compound (a)

Zinc sulfate monohydrate: Horiike Sangyo Co., Ltd. Product BR> A brand name "ZNS-13", an average particle diameter of 200 micrometers, dehydration, transition temperature of 270 degreeC.

Aminocarboxylic acids or salts thereof (b)

MGDA: methylglycine diacetic acid trisodium, BASF Japan Ltd. Product, a brand name "Trillon M powder", the average particle diameter 80 micrometers; Average neutralization 100%.

· Other ingredients

Citric Acid: Junsei Chemical Co., Ltd. Product, reagent express.

The granular detergent used in [evaluation of the solidification property of a detergent] mentioned later was prepared by the preparation method shown below so that it might become the following composition.

Composition (mixture component amount) of granular detergent: MES-Na 9.0 mass%, LAS-Na 1.0 mass%, polyoxyethylene alkyl ether 4.0 mass%, soap 5.0 mass%, sodium carbonate balance, potassium carbonate 4.0 mass%, sodium sulfate 13.0 mass%, zeolite 15.0 mass%, acrylic acid-maleic acid copolymer salt 2.0 mass%, fluorescent brightener 0.1 mass%, water 7.0 mass%, enzyme 1.0 mass%, sodium percarbonate granule 5.0 mass%, bleach activator granulation 1.0 mass% of water, 1.0 mass% of aminocarboxylic acid (salt) containing particles

Preparation method of granular detergent:

[Drying process]

Polyoxyethylene alkyl ether, MES-Na, a part of zeolite (for grinding preparation, for post-mixing process), enzyme, sodium percarbonate granulated product, bleach activator granulated product, aminocarboxylic acid (salt The aqueous slurry of 62 mass% of solid content was obtained by stirring the predetermined amount of all compounding components except for ()) containing particle | grains at the preparation temperature of 80 degreeC for 17 minutes.

In addition, a part of said zeolite (for milling aids and for post-mixing process) represents 30 mass% of zeolite whole quantity.

Subsequently, the aqueous slurry was spray dried to prepare spray dried particles having a water content of 5% by mass.

[Assembling process]

A part of the polyoxyethylene alkyl ether, MES-Na, and a small amount (1 part by mass relative to 100 parts by mass of the spray-dried particles) together with the spray-dried particles obtained in the drying step are mixed with tap water (Edogawa-ku, Tokyo). It injected | threw-in to the continuous kneader (Kurimoto, Ltd. make, KRC-S4 type), and kneaded and kneaded continuously at the temperature of 55-65 degreeC.

Subsequently, the pellet-shaped solid detergent was shape | molded by extruding, supplying the kneaded material obtained by the said kneading kneading to a pelletizer (The Fuji Paudal Co., Ltd. make, die hole diameter 10 mm diameter) continuously.

Then, Wheatsmil (formerly DKA-3, manufactured by Hosokawa Micron Corporation) was placed in series, and the solid detergent and a part of the zeolite (for grinding aid) were introduced therein with a cold air at 15 ° C to average particles. It was pulverized and granulated so that the diameter might be 300-500 micrometers, and the granulated material was obtained.

The manufacturing capacity at this time was set to 180 kg / hr.

In addition, a part of said polyoxyethylene alkyl ether is remove | excluded the thing used by a post-mixing process, and represents 70 mass% of the whole 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 the post-mixing step), the enzyme, the sodium percarbonate granulated product, and the bleach activator granulated product And the aminocarboxylic acid (salt) -containing particles in a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, clearance 20 mm with the inner wall surface on the drum inner wall surface of the container 131.7 L, 45 mm in height). Granules detergent of each case was prepared by mixing for 1 minute under conditions of a filling rate of 30 volume%, rotation speed 22 rpm, and 25 degreeC using 2 obstruction plates).

At that time, only polyoxyethylene alkyl ether (for 30 mass%) was added while spraying so that a droplet diameter might be 40-150 micrometers using a pressure nozzle.

The granular detergent of each obtained example was the thing of the range of 0.82-0.88 g / cm <3> in bulk density.

The raw material used for preparation of granular detergent is as follows.

MES-Na: α-sulfofatty acid alkyl ester salt-containing paste [paste composition: 63 mass% of α-sulfofatty acid alkyl ester salt (MES-Na), 16 mass% of nonionic surfactant (polyoxyethylene alkyl ether to be described later), 8 mass% of impurities such as di salt and methyl sulfate, and 13 mass% of water] were used. Fatty acid chain length of (alpha)-sulfo fatty acid alkyl ester salt (MES-Na) is C16 / C18 = 8/2 (mass ratio) of 16 and 18 carbon atoms, 16 carbon atoms, and 18 carbon atoms.

LAS-Na: linear alkyl (10-14 carbon atoms) benzenesulfonic acid (LAS-H, Lion Corporation product, Lipon LH-200, AV value (mg number of potassium hydroxide required to neutralize 1 g of LAS-H) = 180.0) Neutralized with 48 mass% sodium hydroxide aqueous solution.

Polyoxyethylene alkyl ether: Ethylene oxide 15 mol adduct (melting point 40 degreeC) of ECOROL26 (brand name, the product of ECOGREEN company; the alcohol which has a C12-C16 alkyl group). 90 mass% of pure parts, 10 mass% of moisture content.

Soap: C12-18 fatty acid sodium carbon [Lion Corporation make, 67 mass% of pure components, Taita 40-45 degreeC; Fatty acid composition C12 0.7 mass%, C14 11.4 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].

Sodium carbonate: granular material (Asahi Glass Co., Ltd.) Average particle diameter 320 mu m, bulk density 1.07 g / cm 3.

Potassium carbonate: potassium carbonate (powder) (manufactured by Asahi Glass Co., Ltd.) Average particle diameter 490 µm, bulk density 1.30 g / cm 3.

Sodium sulfate: The product made by Shikoku Chemicals Corporation, a brand name "neutral anhydrous forage A0."

Zeolite: A-type zeolite, the product made from Tisilicate company, brand name "zeolite Na-4A", 80 mass% of pure parts, 3 micrometers of average particle diameters.

Acrylic acid-maleic acid copolymer salt: The sodium salt of the copolymer of acrylic acid and maleic acid, a brand name "Socaran CP7", BASF Japan Ltd. product.

Fluorescent whitening agent: Shiva Specialty Chemicals Co., Ltd., brand name "Tinopal CBS-X".

water

Enzyme: Protease (Sabinase 12T) / Amylase (Stainzyme 12T) / Lipase (LIPEX100T) / Cellulase (Celline 4500T) (above, all Novozyme Japan Co., Ltd.) = 2/1/1/1 (mass ratio) Mixture.

Sodium percarbonate granulated product: Zhejiang JINKE CHEMICALS Co., Ltd., brand name "SPCC", 13.8 mass% of effective oxygen amount, average particle diameter 870 micrometers.

Bleach activator granulated material: mass ratio of OBS12 (sodium 4-dodecaneyloxybenzenesulfonate), PEG-6000, AOS (14-alpha sodium olefinsulfonate powder) and A-type zeolite powder 70/20 / 5/5 assemblies.

Aminocarboxylic acid (salt) containing particle | grains: The aminocarboxylic acid (salt) containing particle | grains of Examples B1-B10 and Comparative Examples B1 and B2 which are mentioned later.

<Production example of aminocarboxylic acid (salt) -containing particles>

Aminocarboxylic acid (salt) containing particle | grains were manufactured by the following manufacturing method according to the compounding component and content (mass%) of the composition shown to Table B1-B3, respectively.

In a table | surface, content of (a) component shows the quantity as a hydrous salt (presence form) containing a water molecule. The other component shows the pure amount conversion amount.

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

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

(Example B1)

[Chemical process]

Kurimoto, Ltd. The hot water was circulated in the jacket of the product S-1KRC kneader, the kneader main body was heated to 60 degreeC, and it maintained at that temperature.

Subsequently, all components except (a) component shown in Table B1 were powder-mixed at normal temperature, Then, (a) component was mixed and the powder mixture of 1.5 kg of whole quantity was prepared. The powder mixture was continuously introduced into the kneader for 15 minutes while the operation was continued, and kneaded material was obtained by performing a kneading and kneading operation after the addition.

[Assembling process]

The obtained kneaded material was continuously put into the extruder (Dalton Co., Ltd. make, Multi Gran MG-55 type | mold) with a die which has a hole of 1.0 mm (phi), and it granulated by extruding through the said die.

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

Thereafter, the noodle-shaped granulated product was put into a speed mill (manufactured by Okada Seiko Co., Ltd.) provided with a screen of 2.5 mm φ, and pulverized at a rotational speed of 3000 rpm to obtain aminocarboxylic acid (salt) -containing particles. Got it.

(Example B2)

[Chemical process]

Hot water was circulated in the jacket of the PNV-5 type desk kneader (manufactured by Irie Shokai Co., Ltd.), and the kneader body was warmed to 60 deg. C to maintain the temperature.

Next, in the composition shown in Table B1, components other than (a) component were introduce | transduced in the horizontal chamber which has the inside of the stirring blade which rotates in a vertical direction.

Subsequently, after kneading operation at 45 rpm of stirring blades, (a) component heated at 58 ° C is introduced into the horizontal chamber, and the kneaded product is kneaded by performing kneading kneading operation (45 rpm of stirring blade) for 50 minutes. Got it. At that time, 1.5 kg of the total amount of each component was added to the kneader.

[Assembling process]

The obtained kneaded material was subjected to the same operations as in the granulation step in Example B1 to obtain aminocarboxylic acid (salt) -containing particles.

(Examples B3 to B8 and B10 to B12)

Aminocarboxylic acid (salt) containing particle | grains were obtained by performing operation similar to Example B1 according to the composition and manufacturing conditions shown to Table B1, B2. The powder mixture was added in 15 to 30 minutes per 1.5 kg of the total amount of each component.

(Example B9)

[Chemical process]

Kurimoto, Ltd. The hot water was circulated in the jacket of the product S-1KRC kneader, the kneader main body was heated to 57 degreeC, and it maintained at that temperature.

Next, all the components of (a)-(e) component were powder-mixed together according to the composition and manufacturing conditions shown in Table B2, and the powder mixture of 1.5 kg of whole quantity was prepared. The powder mixture was continuously introduced into the kneader while the operation was continued, and a kneaded product was obtained by performing a kneading and kneading operation after the addition. The powder mixture was added in 15 to 30 minutes per 1.5 kg of the total amount of each component.

[Assembling process]

The obtained kneaded material was subjected to the same operations as in the granulation step in Example B1 to obtain aminocarboxylic acid (salt) -containing particles.

(Comparative Example B1)

Aminocarboxylic acid (salt) -containing by performing the same operations as in Example B9 (powder mixing, kneading kneading, extrusion granulation together) according to the composition and production conditions shown in Table B3. The particles were obtained. The powder mixture was added in 15 to 30 minutes per 1.5 kg of the total amount of each component.

(Comparative Example B2)

According to the composition and production conditions shown in Table B3, amino (amino acid) was carried out in the same manner as in Example B9 (powder mixing, kneading kneading, extrusion granulation of all components of (c) to (e), (b) and citric acid together). Carboxylic acid (salt) containing particle | grains were obtained. The powder mixture was added in 19 minutes per 1.5 kg of the total amount of each component.

<Evaluation of aminocarboxylic acid (salt) -containing particles>

The following evaluation was performed about the aminocarboxylic acid (salt) containing particle obtained by the manufacturing method of each case, respectively. The result was written together to Table B1-B3.

[Ratio of particles with a particle diameter of less than 150 μm]

When the aminocarboxylic acid (salt) containing particle obtained by each example was classified and operated by the method similar to the said "measurement method of average particle diameter", the granulated material collect | recovered on the support dish through the sieve of mesh size 149 micrometers. The mass frequency was measured and the ratio (mass%) of the particle | grains whose particle diameter is less than 150 micrometers was calculated | required.

The smaller the proportion of the particles having a particle diameter of less than 150 µm means that the granules are less likely to generate fine powder.

[Evaluation of Solubility of Water 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 at a water temperature of 10 ° C, and stirred and mixed with a magnetic steerer. (Stier piece: length 20mm, diameter 5mm, rotation speed: 200rpm), The change of the electrical conductivity of ion-exchange water was measured with the electrical conductivity meter over time.

And after confirming that there was no residual amount of aminocarboxylic acid (salt) containing particle | grains in ion-exchange water, 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 until the said dissolution rate (%) became 90% or more was calculated | required as dissolution time (second). Specifically, time (seconds) on the horizontal axis and electrical conductivity values are taken on the vertical axis, and the measurement is continued until the electrical conductivity becomes equilibrium with time, and when all of the aminocarboxylic acid (salt) -containing particles are dissolved. The time until reaching 90% of the electrical conductivity was calculated | required as the electrical conductivity of 100%.

And the solubility with respect to the water of aminocarboxylic acid (salt) containing particle | grains was evaluated according to the following evaluation criteria. The evaluation result was A and B as pass.

(Evaluation standard)

A: The dissolution time was less than 200 seconds.

B: The 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 more.

[Evaluation of Hygroscopicity of Aminocarboxylic Acid (Salt) -Containing Particles]

Hygroscopicity of aminocarboxylic acid (salt) containing particle | grains is a characteristic which becomes an index of the solidification of aminocarboxylic acid (salt) containing particle | grains itself, and the solidification property of the detergent when mix | blended with a detergent. As the hygroscopicity is higher, the aminocarboxylic acid (salt) -containing particles or the detergent tend to become agglomerates and easily solidify.

Evaluation of the hygroscopicity of aminocarboxylic acid (salt) containing particle | grains was performed as follows.

The aminocarboxylic acid (salt) containing particle | grains (sample) obtained by each example were spread | diffused to the glass chalet (85 mm of internal diameters) so that it might become thickness 5mm, and it put into the thermostat set to the temperature of 45 degreeC and 80% of the relative humidity.

Subsequently, the mass of the glass chalet with which the sample was unfolded every 60 minutes was measured in the said thermostat, and the change with time was recorded.

And moisture absorption (mass%) was calculated | required by following formula (1). In Formula (1), "measured value", "sample input amount", and "sample collection amount" are as follows.

Measured value: Mass of the glass chalet with the sample unrolled after 48 hours in total.

Sample input volume: The mass of the glass chalet in which the sample was measured after standing for one minute at a temperature of 25 ° C. before being placed in a thermostat.

Sampling amount of a sample: The value which subtracted the mass of the glass chalet which is measured after standing for 1 minute at the temperature of 25 degreeC from the said sample input amount.

Based on the moisture absorption rate (mass%) calculated | required from Formula (1), the hygroscopicity of aminocarboxylic acid (salt) containing particle | grains was evaluated according to the following evaluation criteria. The evaluation result set A, B, and C as the pass.

(Evaluation standard)

A: The moisture absorption was less than 5 mass%.

B: The moisture absorption was 5 mass% or more and less than 10 mass%.

C: The moisture absorption was 10 mass% or more and less than 20 mass%.

D: The moisture absorption was 20 mass% or more and less than 40 mass%.

E: The moisture absorption was 40 mass% or more.

[Evaluation of Higher Chemical Determination]

Using the aminocarboxylic acid (salt) -containing particles obtained in each example, the above-described granular detergents were prepared, respectively, and 1000 g of the granular detergents were filled into a sealed carton detergent container (155 mm x 95 mm x 135 mm in height). The sealed carton detergent container after this filling was preserve | saved for two weeks in the thermostat of 45 degreeC of temperature and 60% of a relative humidity.

Thereafter, the sealed carton detergent container was taken out of the thermostat, and after being opened, the solidified state of the contents was confirmed by the following method.

In the sealed carton detergent container, the granular detergent was slowly flowed out on a sieve having a mesh size 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 in accordance with the following evaluation criteria. The evaluation result was A and B as pass.

(Evaluation standard)

A: The residual amount of the granular detergent remaining on the sieve was less than 50 g.

B: The residual amount of the granular detergent remaining on the sieve was 50 g or more and less than 100 g.

C: The residual 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 of 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.

Moreover, the granular detergent which mix | blended the aminocarboxylic acid (salt) containing particle | grains of Examples B1-B10 also confirmed that it was hard to produce solidification.

(Industrial availability)

Since the aminocarboxylic acid (salt) containing particle | grains of this invention hardly generate | occur | produce solidification and are excellent in solubility to water, it can be used suitably as a detergent raw material.

Claims (5)

A zinc compound (a),
Aminocarboxylic acid or salt thereof (b);
The molar ratio represented by (a) / (b) is 0.5-6, The aminocarboxylic acid (salt) containing particle | grains characterized by the above-mentioned. The method of claim 1,
Aminocarboxylic acid (salt) containing particle | grains characterized by the above-mentioned zinc compound being sulfate. 3. The method according to claim 1 or 2,
The amino carboxylic acid (salt) containing particle | grains further containing an organic binder (c), anionic surfactant (d), and nonionic surfactant (e) whose melting | fusing point is less than 45 degreeC. The method according to any one of claims 1 to 3,
Content of the said zinc compound (a) is 10-80 mass%, and content of the said aminocarboxylic acid or its salt (b) is 10-80 mass%, The aminocarboxylic acid (salt) containing particle | grains characterized by the above-mentioned. . The granular detergent composition containing the aminocarboxylic acid (salt) containing particle | grains in any one of Claims 1-4.