JP2010215814A - High bulk density granular detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high bulk density granular detergent composition which contains sodium percarbonate and has excellent solubility into a washing liquid, and in which sodium percarbonate is highly stable. <P>SOLUTION: The high bulk density granular detergent composition includes: surfactant-containing particles of the average particle diameter of at most 400 μm; and sodium percarbonate particles of the particle strength of at least 2.1×10<SP>6</SP>N/m<SP>2</SP>. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to high bulk density granular detergent compositions.

As for the detergent marketed for household use, a compact type high bulk density granular detergent composition which is not bulky and convenient to carry is the mainstream.
In recent years, washing with a low bath ratio with a reduced amount of washing liquid has become common due to the widespread use of drum-type washing machines and increased environmental awareness. When washing is performed at a low bath ratio, the detergent tends to be insufficiently dissolved, and there may be a problem that the detergent particles left undissolved adhere to the cloth, and a problem that the cleaning performance is deteriorated due to a delay in dissolution of the detergent.

Further, in a granular detergent composition having a high bulk density and a bleaching agent, sodium percarbonate is generally blended as a bleaching agent. In such a detergent composition with a bleaching agent, when a large amount of zeolite is blended in order to improve manufacturability and performance, or when the moisture content of the detergent particles is high, the storage stability of sodium percarbonate is improved. Ensuring is an issue.
On the other hand, Patent Document 1 discloses that sodium percarbonate is sprayed on a mixture of sodium percarbonate particles, a granulated product containing a bleach activator, and detergent particles with a nonionic surfactant or polyethylene glycol. A method has been proposed for improving the storage stability of.

Japanese Patent Laid-Open No. 9-87693

However, in order to improve the storage stability of sodium percarbonate by the method described in Patent Document 1, a coating step of spraying a nonionic surfactant or polyethylene glycol is required, which increases the number of steps and decreases the productivity.
Also, in terms of improving the solubility of the high bulk density granular detergent composition, it is preferable that the particle size of the detergent particles is small, but if the particle size of the detergent particles is small, the contact area between sodium percarbonate and the detergent particles is large. Therefore, there is a problem that the storage stability of sodium percarbonate tends to be lowered, and it has been difficult to achieve good solubility and good storage stability at the same time.
The present invention has been made in view of the above circumstances, and without adding a manufacturing process for improving the stability of sodium percarbonate particles, the solubility in washing liquid is good, and sodium percarbonate An object is to obtain a high bulk density granular detergent composition having excellent storage stability.

In order to solve the above problems, the high bulk density granular detergent composition of the present invention comprises a surfactant-containing particle having an average particle diameter of 400 μm or less, and a particle strength of 2.1 × 10 ⁶ N / m ² or more. It contains sodium carbonate particles.

  According to the present invention, the bulkiness of the sodium percarbonate is excellent in the storage stability of the sodium percarbonate as well as the solubility in the washing liquid without adding a production process for improving the stability of the sodium percarbonate particles. A density granular detergent composition is obtained.

[Method for measuring bulk density]
In the present invention, the high bulk density granular detergent composition refers to a granular detergent composition having a bulk density of 0.5 kg / L or more. The value of the bulk density is a value obtained by a measurement method according to JIS K3362.

[Measurement method of average particle size]
The average particle diameter in this specification is an average particle diameter (weight 50%) measured by the following method.
That is, the sample to be measured is classified using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked on a tray in the order of a sieve with a large opening, and a sample of 100 g / time is put on the top of the top 1680 μm sieve, and a lid is put on a low-tap sieve shaker (( (Made by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), and vibrated for 10 minutes under an atmospheric condition of a temperature of 25 ° C. and a relative humidity of 40%. The sample remaining in the sample is collected for each sieve, and the mass of each sample is measured.
The mass frequency of the tray and each sieve is integrated, the initial sieve opening with an integrated mass frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, The average particle diameter (weight 50%) was calculated by the following equation, where c% was the integration of the mass frequency up to the a μm sieve and d% was the mass frequency on the a μm sieve.

[Measurement method of particle strength]
The particle strength of sodium percarbonate particles in the present specification is a value measured by the following method. Using a particle hardness measuring device “GRANO (trade name)” manufactured by Okada Seiko Co., Ltd., under an atmospheric condition of a temperature of 25 ° C. and a relative humidity of 40%, a measuring load of 2000 grams, a measuring speed of 100 μm / sec, and a tip diameter of 3 mmφ The particle hardness (compression fracture strength) was measured under the conditions. The particle hardness was measured for 20 particles near the average particle diameter, and the average value was taken as the particle strength.

The granular detergent composition of the present invention contains surfactant-containing particles and sodium percarbonate particles as essential components.
<Sodium percarbonate particles>
The sodium percarbonate particles are particulate sodium percarbonate, and the surface may be coated with a known coating agent. Examples of the coating agent include silicate and magnesium sulfate.
By blending sodium percarbonate particles with the granular detergent composition, an effect of improving bleaching, sterilization and detergency can be obtained.

The particle strength of the sodium percarbonate particles in the present invention is 2.1 × 10 ⁶ N / m ² or more, preferably 3.0 × 10 ⁶ N / m ² or more. As the particle strength of the sodium percarbonate particles increases, the decomposition of sodium percarbonate when the granular detergent composition is stored over time is suppressed, and the storage stability of sodium percarbonate is improved.
Further, since the sodium percarbonate particles have a high particle strength, they are excellent in stability against physical external forces. For example, sodium percarbonate particles as a detergent raw material, or a granular detergent composition containing the same, external force when pumped or transferred in the manufacturing process of the detergent composition, and the final product is air transport or long distance Even when an external force is applied during transportation, the particles are hardly broken. When the particles are broken, the surface area of the sodium percarbonate particles is increased, so that the storage stability of sodium percarbonate is likely to be lowered. The present invention is excellent in the effect of improving the storage stability of sodium percarbonate in such an environment where the particles are subjected to a physical external force.

  The manufacturing method of the sodium percarbonate particle | grains of this invention is not specifically limited, For example, it can manufacture by the well-known wet crystal precipitation method. The wet crystal precipitation method is a method in which a suspension of sodium carbonate hydrate is prepared, reacted with an aqueous hydrogen peroxide solution, and sodium percarbonate as a reaction product is crystallized from the solution.

  As the reaction conditions in the wet crystal precipitation method, the concentration of sodium carbonate, the concentration of hydrogen peroxide, the reaction temperature, the reaction time, the type and content of the auxiliary agent contained in the sodium carbonate aqueous solution or the hydrogen peroxide aqueous solution can be adjusted. The particle strength of the sodium percarbonate particles can be changed by appropriately changing these.

For example, although sodium percarbonate particles can be produced by a production method including the following steps A, B, and C, the production method is not limited in the present invention.
(Step A) Anhydrous sodium carbonate is added to water or circulating mother liquor, and a suspension of sodium carbonate hydrate is obtained by an emulsion hydration reaction. When emulsifying and hydrating, sodium chloride is preferably added as a salting-out agent.
(Step B) A sodium carbonate hydrate suspension and an aqueous hydrogen peroxide solution are charged into a reaction kettle and reacted to crystallize sodium percarbonate crystals. When crystallizing, it is preferable to add a seed crystal.
(Step C) Sodium percarbonate crystals are solid-liquid separated and the filtrate is circulated and used to work up the crystals to obtain sodium percarbonate particles.
In order to increase the particle strength of the sodium percarbonate particles, in step A, it is preferable to reduce the amount of sodium chloride as a salting-out agent. The temperature of the suspension is preferably around 32 to 35 ° C. where heptahydrate is easily generated. In step B, it is preferable to reduce the amount of seed crystals in the reaction kettle and lengthen the reaction time. Further, it is desirable that the concentration of the aqueous hydrogen peroxide solution is high, the addition amount of the aqueous hydrogen peroxide solution is small, and the addition rate is low.

The active oxygen content of the sodium percarbonate particles is preferably 10 to 15.3% by mass, and more preferably 13 to 15.3% by mass. When the amount of active oxygen is at least the lower limit of the above range, the stability of the particles is easily improved and the efficiency of the bleaching effect is good. The upper limit of the theoretical value is 15.3% by mass.
The amount of active oxygen in the sodium percarbonate particles increases as the reaction molar ratio of hydrogen peroxide increases, and decreases as it decreases.
The amount of active oxygen is a value determined by the following method.

[Measurement method of active oxygen content]
10 mg of a sample was precisely weighed and placed in a tall beaker, 100 mL of 33% by mass acetic acid aqueous solution was added, and the mixture was dissolved by stirring with a magnetic stirrer. Subsequently, the solution obtained by adding 20 mL of 10 mass% potassium iodine aqueous solution was titrated with the 1 mol / L sodium thiosulfate solution. On the way, when the solution became colorless, 2 to 3 drops of saturated ammonium molybdate was added, and when the solution became pale yellow, the titration was continued. When the solution became colorless, the titration was terminated. From the titration amount p (mL) of a 1 mol / L sodium thiosulfate solution dropped from the start of titration to the end of titration, the amount of active oxygen was determined by the following formula.
[Formula for determining the amount of active oxygen]
Active oxygen amount (%) = {f × p × (1/2) × (1/1000) × 16} / g × 100
[Wherein, f is a factor of a 1 mol / L sodium thiosulfate solution, p is a titration amount (unit: mL), and g is a mass of the sample (unit: g). In this example, the sample material is 0.01 g. ]

The average particle size of the sodium percarbonate particles is preferably 100 to 1000 μm, and more preferably 400 to 800 μm. When the average particle size is at least the lower limit of the above range, the stability of the sodium percarbonate particles tends to be good, and when the average particle size is at most the upper limit, classification with other particles in the detergent tends to be suppressed.
The average particle diameter of the sodium percarbonate particles tends to increase, for example, when the seed crystal addition amount is reduced and decrease as the seed crystal addition amount increases.

<Surfactant-containing particles>
The surfactant-containing particle in the present invention refers to a particle containing 10% by mass or more of a surfactant in the particle.
The content of the surfactant in the surfactant-containing particles is more preferably 10% by mass or more and further preferably 15% by mass or more in order to obtain a good cleaning effect. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less in terms of balance with other components.
The surfactant-containing particles preferably contain a detergency builder in addition to the surfactant. Moreover, the arbitrary component mix | blended with a granular detergent composition can also be contained in surfactant-containing particle | grains in the range which does not impair the stability of surfactant-containing particle | grains.
As the surfactant, the detergency builder, and other optional components, publicly known components can be appropriately used as the constituent components of the granular detergent composition. Examples are given below.

<Surfactant>
One surfactant can be used alone, or two or more surfactants can be used in appropriate combination.
<Anionic surfactant>
Examples of the anionic surfactant include the following (1) to (12).
(1) α-sulfo fatty acid alkyl ester salt The type of α-sulfo fatty acid alkyl ester salt is not particularly limited, and any α-sulfo fatty acid alkyl ester salt used in general granular detergent compositions is preferably used. Can do. Suitable examples are given below.

In the formula (A-1), R ¹¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, preferably 14 to 16 carbon atoms, or linear or branched chain having 8 to 20 carbon atoms. Of the alkenyl group. R ¹² is an alkyl group having 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group, an ethyl group, and a propyl group are preferable because the detergency is further improved, and a methyl group is particularly preferable.
M represents a counter ion, and examples thereof include alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like. Of these, alkali metal salts are preferred.
As the α-sulfo fatty acid alkyl ester salt, for example, α-sulfo fatty acid methyl ester sodium salt (MES) is preferable.
When the α-sulfo fatty acid alkyl ester salt is contained in the granular detergent composition of the present invention, the content is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the entire composition. More preferably, it is 5 to 15% by mass. Within the above range, good detergency and recontamination preventing effect can be easily obtained.

(2) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(3) Alkane sulfonate having 10 to 20 carbon atoms.
(4) C-C20 α-olefin sulfonate (AOS).
(5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(6) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms to which an average of 0.5 to 10 mol is added.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(10) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(12) Soap. The kind of soap in particular is not restrict | limited, The soap used for a general granular detergent composition can be used conveniently. A higher fatty acid salt having 10 to 20 carbon atoms is preferable, and a higher fatty acid salt having 11 to 17 carbon atoms is more preferable.

  These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants may be used as a mixture.

<Nonionic surfactant>
Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms ether.
Among these, polyoxyethylene alkyl (or alkenyl) ether (AE) and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. In addition, the alkyl group or alkenyl group may be linear or branched.
(2) Polyoxyethylene alkyl phenyl ether or polyoxyethylene alkenyl phenyl ether.
(3) A fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (II) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ¹ CO (OA) _n OR ² (II)
(In the formula, R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents an alkylene having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. Represents an addition unit of oxide, and n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R ² may have a substituent of 1 to 3 carbon atoms. A good lower (C1-C4) alkyl group is shown.)
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

Among the nonionic surfactants described above, the nonionic surfactant of the above (1) is preferable, and in particular, a polysiloxane obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms. Oxyalkylene alkyl (or alkenyl) ether is preferred.
Further, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and 9 to 16 HLB, fatty acid methyl ester in which ethylene oxide is added to fatty acid methyl ester An ethoxylate, a fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester, and the like are preferably used.
These nonionic surfactants can be used singly or in appropriate combination of two or more.
In addition, HLB of nonionic surfactant in this specification is a value calculated | required by the method of Griffin (Yoshida, Shindo, Ogaki, Yamanaka co-edit, "New edition surfactant handbook", Kogyoshosho, 1991). Year, page 234).
Further, the melting point in the present specification is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical product”.

<Cationic surfactant>
Examples of the cationic surfactant include the following.
(1) Dilong chain alkyl dishort chain alkyl type quaternary ammonium salt.
(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.
However, the above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.
The “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyalkyl having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Oxyalkylene groups are preferred.

<Amphoteric surfactant>
Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

<Detergency Builder>
[Zeolite]
Zeolite is preferably used as the detergency builder. Zeolite contributes to the improvement of detergency. Zeolite is a general term for aluminosilicates, and both a crystalline and amorphous (amorphous) can be used as the aluminosilicate. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred.
As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like are suitable, and the average primary particle diameter is preferably 0.1 to 10 μm.
When the surfactant-containing particles contain zeolite, the content is preferably 10% by mass or more in order to obtain an effect of addition such as sufficient detergency, assuming that the total amount of the surfactant-containing particles is 100% by mass. The mass% or more is more preferable. The upper limit is preferably 40% by mass or less and more preferably 30% by mass or less from the viewpoint of the storage stability of sodium percarbonate.

As shown in the examples described later, the storage stability of sodium percarbonate is further improved when the surfactant-containing particles have a lower zeolite content. This indicates that zeolite has an adverse effect on the storage stability of sodium percarbonate. The reason is not clear, but the contact area with the sodium percarbonate particles is large because the zeolite is fine particles, and the zeolite contains free water and metals that adversely affect the stability of the sodium percarbonate particles Presumed to be.
According to the present invention, for example, even when the zeolite content of the surfactant-containing particles is 15% by mass or more, good storage stability of the sodium percarbonate particles can be obtained.

[Other detergency builders]
Examples of detergency builders other than zeolite include inorganic builders other than zeolite and organic builders.
Examples of inorganic builders include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite; crystalline layered sodium silicate [eg, manufactured by Clariant Japan Ltd. Crystalline alkali metal silicates such as “Na-SKS-6” (δ-Na ₂ O · 2SiO ₂ )], amorphous alkali metal silicates; sulfates such as sodium sulfate and potassium sulfate; sodium chloride Alkali metal chlorides such as potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; sodium carbonate and amorphous alkali metal silicate Complexes (for example, the trade name “NABION15” of Rhodia) It is.

Among the inorganic builders, sodium carbonate, or potassium salts (potassium carbonate, potassium sulfate, etc.) or alkali metal chlorides (potassium chloride, sodium chloride, etc.) are preferred as those having the effect of improving solubility.
When mix | blending potassium carbonate, the content is from a point of the effect of a solubility improvement, Preferably it is 1-15 mass% in a granular detergent composition, More preferably, it is 2-12 mass%, More preferably, it is 5-5. 12% by mass.
When blending an alkali metal chloride, the content thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably, in the granular detergent composition in terms of the effect of improving solubility. It is 3-7 mass%.
Moreover, when mix | blending crystalline alkali metal silicate, the content is from a point of washing | cleaning performance, Preferably it is 0.5-40 mass% in a granular detergent composition, More preferably, 1-25 mass%, More preferably, it is 3-20 mass%, Most preferably, it is 5-15 mass%.

  Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates, cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; Reacrylate, salt of acrylic acid-allyl alcohol copolymer, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, And polysaccharide derivatives such as polysaccharide oxides such as cellulose, amylose and pectin.

Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A-54-52196) are preferred.
As for content of an organic builder, 1-20 mass% is preferable in a granular detergent composition, More preferably, it is 1-10 mass%, Most preferably, it is 2-5 mass%.
The said detergency builder can be used individually by 1 type or in combination of 2 or more types as appropriate.

Among the above detergency builders, the detergency and stain dispersibility in the washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid It is preferable to use an organic builder such as a polymer salt or a polyacetal carboxylic acid salt in combination with an inorganic builder such as zeolite.
The total content of the detergency builder in the granular detergent composition is preferably 10 to 80% by mass and more preferably 20 to 75% by mass from the viewpoint of imparting sufficient cleaning performance.

<Other optional components>
<Carboxymethylcellulose>
Carboxymethylcellulose (hereinafter sometimes abbreviated as CMC) in the present specification is a concept including salts thereof. Examples of the salt of carboxymethyl cellulose include alkali metal salts such as sodium and potassium, ammonium salts, and the like, and a mixture of these salts may be used. Of the above-mentioned salts, sodium salts are preferably used. CMC contributes to the effect of preventing recontamination.

Examples of CMC include anionic water-soluble cellulose ether or water-insoluble cellulose ether obtained by reacting monochloroacetic acid after treating pulp with caustic soda as a raw material.
Specifically, a polymer compound having a repeating unit represented by the following formula (I) is exemplified.

[In formula (I), n represents the number of repeating units, and R ^{1 to} R ³ each independently represents a hydroxyl group or a carboxymethyl group (—CH ₂ COO ⁻ Z ⁺ ; Z ⁺ is a counter ion). Indicates. ]

  The weight average molecular weight of CMC is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 800,000 or more. As an upper limit, 1.2 million or less is preferable, for example, 1 million or less is more preferable. When the weight average molecular weight of CMC is within the above range, the recontamination preventing effect can be remarkably improved. Further, when the weight average molecular weight of CMC is 1,200,000 or less, the solubility becomes good.

The degree of etherification of CMC is preferably 0.2 to 1.3, more preferably 0.2 to 1.0, and still more preferably 0.2 to 0.7.
In the present specification, the degree of etherification of CMC means the average number of hydroxyl groups substituted with a carboxymethyl group or a salt thereof per glucose ring unit (of the three hydroxyl groups of the glucose ring, how many are carboxymethyl groups or their It indicates whether or not it has been replaced by a salt, and is a maximum of 3). For example, in the above formula (I), the average number of ethers in which R ^{1 to} R ³ are substituted with a carboxymethyl group or a salt thereof among —OR ¹ , —OR ² , and —OR ³ is the degree of etherification. .

CMC can use a commercial item suitably. For example, 1110, 1120, 1130, 1140, 1160, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380, 2200, 2260 sold under the trade name “CMC Daicel” from Daicel Chemical Industries, Ltd. , 2280, 2450, 2340, etc .; Sunrose F series such as F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, F1400MG sold by Nippon Paper Chemical Co., Ltd .; A02SH Sunrose A series such as A20SH, A200SH; SLD-F1 (trade name). Among these, CMC Daicel 1130, 1180, 1190, Sunrose F1400LC, F1400MC, and Sunrose SLD-F1 are particularly preferable.
CMC can be used alone or in combination of two or more. When using CMC, the content is preferably 0.6 to 5% by mass, more preferably 1 to 5% by mass, and even more preferably 3 to 5% by mass when the entire granular detergent composition is 100% by mass. Within the above range, excellent anti-contamination property can be obtained.

<Bleaching activator, bleach activation catalyst>
As the bleach activator, a known compound can be used, but an organic peracid precursor is preferably used.
Examples of the organic peracid precursor include tetraacetylethylenediamine, alkanoyloxybenzenesulfonic acid having 8 to 12 carbon atoms, alkanoyloxybenzoic acid having 8 to 12 carbon atoms, and salts thereof, among which 4-decanoyloxy Benzoic acid, sodium 4-dodecanoyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are preferred. These may be used alone or in combination of two or more.
Particles containing the bleach activator can be produced by a known production method. For example, it can be produced by an extrusion granulation method or a granulation method by a tablet shape using a briquetting machine.
Specifically, the organic peracid precursor particles are obtained by heating and melting a solid binder material at room temperature, such as polyethylene glycol of PEG # 3000 to # 20000, preferably PEG # 4000 to # 6000. After separating the body and surfactant powder such as olefin sulfonate, alkylbenzene sulfonate, alkyl sulfate ester salt, etc., extruded to produce a noodle-shaped organic peracid precursor granule having a diameter of about 1 mm, It is preferable to blend by lightly grinding to a length of about 0.5 to 3 mm. As the surfactant powder, an α-olefin sulfonate having an alkyl chain length of 14 is preferred.

A known compound can be used as the bleach activating catalyst. Specific examples include transition metal atoms and ligands such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, and molybdenum via nitrogen atoms, oxygen atoms, etc. As the transition metal contained, cobalt, manganese, etc. are preferable, and manganese is particularly preferable. In particular, the bleach activating catalyst described in JP-A No. 2004-189893 is preferable.
Particles containing the bleach activating catalyst can be produced by a known granulation method. For example, it can be produced by an extrusion granulation method or a granulation method by a tablet shape using a briquette machine.

<Fluorescent brightener>
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, and 2- (styryl). Phenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) disulfonic acid derivatives, and the like. Fluorescent whitening agents can be used alone or in combination of two or more.
The content of the fluorescent brightening agent in the granular detergent composition is preferably 0.001 to 1% by mass.

  Specific examples of commercially available products include Whiteex SA, Whitetex SKC (above, product; manufactured by Sumitomo Chemical Co., Ltd.); Specialty Chemicals); Lemonite CBUS-3B (above, trade name: manufactured by Khyati Chemicals) and the like are preferable. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are more preferable.

<Enzyme>
Enzymes that can be blended in the granular detergent composition of the present invention include hydrolases, oxidoreductases, lyases, transferases, and isomerases when classified from the reactivity of the enzyme. Either can be applied.
Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.

Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like.
As commercial products, sabinase, alcalase, cannase, everase, deozyme (above, trade name: manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); Maxacar, Maxapem (above, trade name: manufactured by Genencor) ); Protease K-14 or K-16 (protease described in JP-A-5-25492) and the like.

Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Specific examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name; manufactured by Novozymes), and liposum (trade name, manufactured by Showa Denko KK).
Examples of cellulases include commercially available cellzymes (trade names, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, alkaline cellulase K- 425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, and alkaline cellulase E -III (cellulase described in JP-A-63-264699) and the like.
Examples of amylases include commercially available stainzymes, termamyls, duramils (manufactured by Novozymes) and the like.
The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).

<Enzyme stabilizer>
As the enzyme stabilizer, for example, calcium salt, magnesium salt, polyol, formic acid, boron compound and the like can be blended. Of these, sodium tetraborate, calcium chloride and the like are preferable. An enzyme stabilizer can be used individually by 1 type or in combination of 2 or more types as appropriate.
As for content of the enzyme stabilizer in a granular detergent composition, 0.05-2 mass% is preferable.

<Polymers>
In the granular detergent composition of the present invention, as a binder or a powder physical property modifier used when densifying the granular detergent composition particles, or for imparting a recontamination preventing effect on hydrophobic fine particles (dirt). Polyethylene glycol having an average molecular weight of 200 to 200,000, salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, cellulose derivatives such as polyvinyl alcohol, hydroxypropyl methylcellulose (HPMC), cationized cellulose, powdered cellulose, etc. Cellulose or the like can be blended.
In addition, a copolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol, a terpolymer, or the like can be blended as a soil release agent.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Such polymers can be used singly or in appropriate combination of two or more.
As for content of the said polymers in a granular detergent composition, 0.05-5 mass% is preferable.

<Anti-caking agent>
As the anti-caking agent, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.

<Antifoaming agent>
Examples of the antifoaming agent include conventionally known ones such as silicone / silica-based ones. Moreover, you may use this antifoamer as an antifoamer granulated material obtained by the following manufacturing method.
First, 100 g of maltodextrin (trade name, manufactured by Nissho Chemical Co., Ltd .; enzyme-modified dextrin) is added with 20 g of silicone (compound type, product name: PS Antifoam, manufactured by Dow Corning) as an antifoam component and mixed. To obtain a homogeneous mixture. Next, after mixing 50 mass% of the obtained homogeneous mixture, polyethylene glycol (PEG-6000, melting point 58 ° C.) 25 mass%, and neutral anhydrous sodium sulfate 25 mass% at 70-80 ° C., an extrusion granulator ( Granulate by model EXKS-1, manufactured by Fuji Paudal Co., Ltd. to obtain a defoamer granulated product (see JP-A-3-186307).

<Metal ion scavenger>
The metal ion scavenger captures trace metal ions and the like in tap water and has an effect of suppressing the adsorption of metal ions to the fiber (object to be washed).
As metal ion scavengers that can be incorporated into the granular detergent composition of the present invention, in addition to those included in the detergency builder, aminopolyacetic acids such as glycol ethylenediamine hexaacetic acid; 1-hydroxyethane-1,1 -Diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy- 1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriamine Organic phospho such as penta (methylenephosphonic acid) Acid derivative or a salt thereof; diglycolic acid, organic acids or salts thereof such as oxalic acid.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the metal ion scavenger in the granular detergent composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass. If it is 0.1 mass% or more, the effect which capture | acquires the metal ion in tap water will improve. On the other hand, if it is 5 mass% or less, the effect of capturing metal ions is sufficiently obtained.

<PH adjuster>
The pH of the granular detergent composition of the present invention is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by mass aqueous solution of the granular detergent composition is preferably 8 or more, and the 1 mass It is more preferable that pH in a 9% aqueous solution is 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
As a technique for controlling the pH of the granular detergent composition, the pH is usually adjusted with an alkaline agent. In addition to the alkaline agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, etc. Examples include alkanolamine, sodium hydroxide, potassium hydroxide and the like.
Specifically, for example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, Rhodia Co., Ltd.), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio). Are preferably used.
Moreover, in order to prevent that the pH of a granular detergent composition becomes high too much, it can also adjust to the said pH range using an acid etc.
Examples of such acids include the metal ion scavenger, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, sodium hydrogen carbonate, sulfuric acid, Hydrochloric acid or the like can be used.
Further, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.
The said pH adjuster can be used individually by 1 type or in combination of 2 or more types as appropriate.

<Fragrance>
The fragrance in the present invention is not particularly limited, and any fragrance generally used in detergents may be used and comprises a fragrance component, a solvent, a fragrance stabilizer, and the like.
As such a fragrance, for example, those described in JP-A Nos. 2002-146399 and 2003-89800 can be used.
0.001-2 mass% is preferable and, as for content of the fragrance | flavor in a granular detergent composition, 0.01-1 mass% is more preferable.

<Dye>
In the present invention, various dyes such as dyes and pigments can be used to improve the appearance of the granular detergent composition. Of these, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance are particularly preferable.
Examples of such a dye include oxides, and preferable examples include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green.

<Method for producing surfactant-containing particles>
The method for producing the surfactant-containing particles is not particularly limited, and can be produced by a commonly used production method. For example, the surfactant and other raw materials are dispersed / dissolved in water and spray-dried, and are used for kneading / extrusion, stirring granulation, tumbling granulation, etc. Etc., and can be produced by a method such as pulverization if necessary.

  The average particle diameter of the surfactant-containing particles contained in the granular detergent composition of the present invention is 400 μm or less. When it is 400 μm or less, good solubility of the granular detergent composition is easily obtained. The average particle size of the surfactant-containing particles is preferably 300 μm or less. The lower limit of the average particle diameter is preferably 100 μm or more, more preferably 150 μm or more in terms of suppressing dust generation and solidification.

<Moisture content>
When water is used in the production process of the surfactant-containing particles, the finally obtained surfactant-containing particles contain moisture. If the surfactant-containing particles contain a large amount of water, the storage stability of sodium percarbonate in the granular detergent composition tends to decrease, but reducing the water content in the surfactant-containing particles to 5% by mass or less In production, productivity deteriorates and energy loss increases, which is disadvantageous.
As shown in Examples described later, according to the present invention, good storage stability of sodium percarbonate particles can be obtained even if the water content of the surfactant-containing particles is 6% by mass or more.

[Method for measuring water content]
The method for measuring the amount of water in the surfactant-containing particles in the present specification is as follows.
First, 5 g of the surfactant-containing particles are weighed on a pre-weighed sample pan, and the sample is heated and dried for 3 minutes with an infrared moisture meter. After drying, weigh the dried sample and the sample pan, divide the difference between the weight of the sample before and after the drying and the weight of the container by the weight of the first sample, and multiply by 100 to obtain the amount of water in the surfactant-containing particles. Is calculated. As the infrared moisture meter, an infrared moisture meter “FD-600 (trade name)” manufactured by Kett Science Laboratory Co., Ltd. was used.

<Method for producing granular detergent composition>
The manufacturing method of the granular detergent composition of this invention is not restrict | limited in particular, It can manufacture by the method of mixing each component by a well-known method. For example, by adding surfactant-containing particles, sodium percarbonate particles and other components to a horizontal cylindrical rolling mixer or V-type mixer and stirring and mixing, and by mixing spraying flavoring and other liquid components it can. Further, a method of feeding a powder component quantitatively on a belt conveyor can be used.

The content of the surfactant-containing particles in the granular detergent composition of the present invention is preferably 50 to 99% by mass, and the content of sodium percarbonate particles is more preferably 1 to 20% by mass.
The mass ratio of the surfactant-containing particles to the sodium percarbonate particles [surfactant-containing particles / sodium percarbonate particles] contained in the granular detergent composition is preferably 99/1 to 1/1. If the ratio of the sodium percarbonate particles is too large, the surfactant content is relatively lowered, so that a sufficient detergency cannot be obtained. If the ratio is too small, the bleaching effect cannot be sufficiently obtained.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, “%” representing the content is “mass%” and “part” representing the blending amount is “part by mass”.
<Surfactant-containing particles>
<Raw materials>
The raw materials shown in Table 1 are as follows.
-MES mixed concentrate: manufactured in the following [Production Example 1].
LAS salt: LAS-H (linear alkyl (carbon number 10 to 14) benzenesulfonic acid [manufactured by Lion Corporation, product name: Lipon LH-200 (pure content: 96% by mass)]), concentration of 48% by mass A mixture of a compound neutralized with an aqueous sodium hydroxide solution and a compound neutralized with an aqueous 48% by weight potassium hydroxide solution instead of the aqueous sodium hydroxide solution in a mass ratio of 1: 2. The blending amount in the table indicates the value as a mixture.
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67% by mass, titer: 40 to 45 ° C .; fatty acid composition: C12 11.7% by mass, C14 0.4% by mass, C16 29.2% by mass, C18F0 (stearic acid) 0.7% by mass, C18F1 (oleic acid) 56.8% by mass, C18F2 (linoleic acid) 1.2% by mass; molecular weight: 289).
AE15: ECOROL26 (product name, manufactured by ECOGREEN, alcohol having an alkyl group having 12 to 16 carbon atoms) an ethylene oxide average 15 mol adduct (pure content 90%, moisture 10%).
* AE7: Ethanol oxide average 7 mol adduct of ECOOLL26 (product name, manufactured by ECOGREEN, alcohol having 12 to 16 carbon atoms) (pure content 90%, moisture 10%).

MA agent: acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by mass aqueous solution).
Sodium polyacrylate: Socaran PA30 (product name, manufactured by BASF, weight average molecular weight 8,000, solid content 50%).
Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
Sodium carbonate: granular ash (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ ).
-Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd., average particle size 490 μm, bulk density 1.30 g / cm ³ ).
Sodium chloride: Nissei Yaki salt C (product name, manufactured by Nippon Salt Corporation).
Zeolite: A-type zeolite (product name: Shilton B, manufactured by Mizusawa Chemical Co., Ltd .; pure content: 80% by mass).

[Production Example 1: Production of MES mixed concentrate]
(Sulfonation process)
First, methyl palmitate (product name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (product name: Pastel M-180, manufactured by Lion Corporation) are 80:20 (mass ratio). Then, the mixture was further hydrogenated by a conventional method to reduce the iodine value to 0.2 to obtain a purified fatty acid methyl ester. Using this flow-through type thin film reactor, this purified fatty acid methyl ester was reacted with SO ₃ gas diluted to 7% with dehumidified air at a reaction molar ratio (SO ₃ / saturated fatty acid ester) = 1.18 and a reaction temperature of 80 ° C. Sulfonation under conditions gave a sulfonated product.
(Aging process)
The resulting sulfonated product was then introduced into a loop ripening tube with a double tube jacket having an average residence time of 20 minutes. Three loop type ripening tubes were connected in succession, and the average residence time was 60 minutes. In order to maintain sufficient stirring and a constant temperature, the sulfonated product is allowed to flow through the loop aging tube at a linear speed of 0.16 m / s, and the aging reaction is performed at 78 to 82 ° C. to complete the sulfonation. -Sulfo fatty acid methyl ester was obtained.
(Esterification / bleaching process)
Subsequently, 20 parts by mass of methanol (manufactured by Sumitomo Chemical Co., Ltd., methanol: industrial grade, moisture 500 ppm or less) was introduced into 100 parts by mass of the obtained α-sulfo fatty acid methyl ester, and then this mixture and 35% hydrogen peroxide. (Mitsubishi Gas Chemical Co., Ltd., 35% hydrogen peroxide for industrial use: industrial grade) 5.7 parts by mass are introduced into a continuous loop reactor equipped with a mixing mixer and a heat exchanger for bleaching, and α-sulfo fatty acid A methyl ester bleached product was obtained.

(Neutralization process)
Next, with respect to 125 parts by mass of the obtained α-sulfo fatty acid methyl ester bleached product, 28 parts by mass of 48% NaOH aqueous solution (manufactured by Daiso Corporation, caustic soda: industrial grade), nonionic surfactant (AE15: ECOROL 26 (product name) ), 25 parts by mass of ECOGREEN), 69 parts by mass of water, 24 parts by mass of methanol (manufactured by Sumitomo Chemical Co., Ltd .: methanol: industrial grade), and 5 parts by mass of linear alkylbenzene sulfonic acid (said LIPON LH-200 (product name)) Part was continuously fed to the neutralization line.
The neutralization method employs the neutralization method described in JP-A-2001-64248, and a 48% by mass aqueous solution of sodium hydroxide is quantitatively fed between the premixer and the neutralization mixer. I was able to neutralize. And after neutralizing the neutralized product of the α-sulfo fatty acid methyl ester bleached product previously neutralized and the α-sulfo fatty acid methyl ester bleached product with a premixer, an aqueous sodium hydroxide solution and A neutralized product was obtained by mixing.
(Concentration process)
Furthermore, using the above neutralized product as a raw material surfactant aqueous solution, recycle flash evaporation described in Japanese Patent Application Laid-Open No. 2004-210807 is performed, and lower alcohol is removed and concentrated to concentrate MES with a moisture content of 10.8%. A mixture (62% by mass of MES, 3.5% by mass of LAS-Na, 16.8% by mass of nonionic surfactant) was obtained.

[Production Example 2: Production of surfactant-containing particles (a1)]
According to the mixing ratio shown in Table 1, surfactant-containing particles (a1) were produced. In addition, the compounding quantity of the LAS salt shown in Table 1 does not include the linear alkylbenzene sulfonate contained in the MES mixed concentrate.
(Slurry preparation process and spray drying process)
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. To this, LAS salt and soap were added and stirred for 10 minutes.
Subsequently, the MA agent was added. After further stirring for 10 minutes, a part of the zeolite (2.0% for the addition during the kneading, 5.0% for the grinding aid, 1.5% for the surface coating from the addition amount described in Table 1) Amount removed), sodium carbonate, potassium carbonate, sodium sulfate, sodium sulfite were added. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%.
The slurry was spray-dried using a counter-current spray drying tower at a hot air temperature of 280 ° C. to obtain spray-dried particles having an average particle diameter of 320 μm, a bulk density of 0.30 g / cm ³ and a water content of 5%.
(Kneading process)
Obtained spray-dried particles, MES mixed concentrate, zeolite (for kneading addition, 2.0%), remaining nonionic surfactant excluding 0.3% nonionic surfactant for spray addition, fluorescent whitening Agent and water were put into a continuous kneader (KRC-S4, KRC-S4 type), kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C., and containing 6% of water containing a surfactant. A mixture of was obtained.

(Crushing process)
The mixture obtained in the kneading process was cut with a cutter while extruding it using a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm (the cutter peripheral speed was 5 m / s) and about 5 to 30 mm long pellets were obtained.
Subsequently, zeolite (for grinding aid, 5.0%) was added to the obtained pellets, and Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) arranged in series in the presence of cold air (10 ° C., 15 m / s), DKA-3) (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / 3rd stage are all 4700 rpm) .
(Surface modification treatment)
The powder obtained in the pulverization step was mixed with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, volume: 131.7 L, 2 mm baffle plate with inner wall clearance of 20 mm and height of 45 mm on the drum inner wall surface) Zeolite (with a sheet) is added, zeolite (for surface coating, 1.5%) is added, nonionic surfactant (for spray addition, 0.3%) under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. %)) And surface-modified surfactant-containing particles (a1) obtained by rolling for 1 minute. The content of zeolite in the surfactant-containing particles (a1) is 20% by mass, and the water content is 6% by mass.
(Adjustment of particle size)
The particle size of the obtained surfactant-containing particles (a1) is adjusted according to the mesh size of the screen mesh at the time of pulverization, and contains four types of surfactants having an average particle size of 300 μm, 350 μm, 400 μm, and 500 μm. Particles (a1) (hereinafter referred to as a1-300 μm, a1-350 μm, a1-400 μm, and a1-500 μm (comparative example), respectively) were obtained. All the surfactant particles had a bulk density of 0.8 kg / L.

[Production Example 3: Production of surfactant-containing particles (a2)]
In this example, surfactant-containing particles (a2) with a small amount of zeolite added were produced. That is, in Production Example 2, a surfactant containing an average particle diameter of 400 μm and a bulk density of 0.8 kg / L was produced in the same manner as in Production Example 2 except that the amount of each component was changed as shown in Table 1. Particles (a2) (hereinafter referred to as a2-400 μm) were obtained.
The breakdown of the amount of zeolite added is 8.0% for the slurry preparation step, 0.5% for the kneading addition, 5.0% for the grinding aid, and 1. for the surface coating. 5%.

[Production Example 4: Production of surfactant-containing particles (a3)]
In this example, surfactant-containing particles (a3) with a small amount of added water were produced. That is, in Production Example 2, the average particle size was 400 μm and the bulk density was 0 as in Production Example 2, except that the water content was changed as shown in Table 1 depending on the conditions in the spray drying process and the kneading process. .8 kg / L of surfactant-containing particles (a3) (hereinafter referred to as a3-400 μm) were obtained.
The breakdown of the amount of zeolite added is 11.5% for the slurry preparation step, 0.5% for the addition during kneading, 5.0% for the grinding aid, and 3. 0%.

[Production Example 5: Production of surfactant-containing particles (a4)]
According to the blending ratio shown in Table 1, surfactant-containing particles (a4) were produced by the following method.
First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 50 ° C. Sodium sulfate and fluorescent brightening agent were added thereto, and after stirring for 10 minutes, sodium carbonate was added and then sodium polyacrylate was added. After further stirring for 10 minutes, a part of sodium chloride and zeolite (amount shown in the table) The amount excluding 10% by mass for surface coating was added. The mixture was further stirred for 30 minutes to prepare a slurry for spray drying. The temperature of the obtained slurry for spray drying was 60 ° C. This slurry was spray-dried with a counter-current spray dryer equipped with a pressure spray nozzle to obtain spray-dried particles having a bulk density of 0.50 g / cm ³ and an average particle size of 400 μm.
Next, a nonionic surfactant, LAS salt, and soap were added under mixing at 80 ° C. to prepare a surfactant composition. Next, spray-dried particles were put into a Redige mixer M20 type (manufactured by Matsuzaka Giken Co., Ltd.), and stirring of the main shaft (150 rpm) and chopper (4000 rpm) was started. Warm water at 80 ° C. was passed through the jacket at a flow rate of 10 L / min. The above-mentioned surfactant composition was charged therein for 2 minutes, and after stirring for 5 minutes, a part of zeolite (10% by mass) was added to perform surface coating treatment for 2 minutes. (A4) was obtained. The obtained surfactant-containing particles (a4) (hereinafter referred to as a4-400 μm) had an average particle size of 400 μm, a bulk density of 0.8 kg / L, and a water content of 6% by mass.

<Sodium percarbonate particles>
<Raw materials>
The raw materials used in the production examples of sodium percarbonate particles are as follows.
Sodium carbonate: granular ash (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ ).
-Light anhydrous sodium carbonate: manufactured by Tokuyama Corporation.
Sodium chloride: Nissei Yaki salt C (product name, manufactured by Nippon Salt Corporation).
-Sodium silicate: manufactured by Osaka Silicate Soda Co., Ltd.
-Aqueous hydrogen peroxide solution having a concentration of 60%: manufactured by Nippon Peroxide.
Aminotrimethylene phosphonic acid (ATMP): Dequest 2000 (trade name, manufactured by Monsanto).

[Production Example 11: Production of sodium percarbonate particles (b1)]
(Process A)
As a mother liquor, an aqueous sodium carbonate solution having a sodium carbonate content of 12.3% was placed in a slurry preparation container and circulated by starting a shear emulsifier. 26 parts by weight of light anhydrous sodium carbonate, 1.0 part by weight of sodium chloride and 0.3 part by weight of sodium silicate were added to 100 parts by weight of this sodium carbonate aqueous solution to cause an emulsification reaction. The emulsification reaction time was 20 minutes, the emulsification reaction temperature was 32 to 35 ° C., and a suspension was produced.

(Process B)
On the other hand, in a hydrogen peroxide tank, 20 parts by mass of 60% aqueous hydrogen peroxide, 0.4 parts by mass of aminotrimethylenephosphonic acid (ATMP), 0.1 parts by mass of disodium ethylenediaminetetraacetate, magnesium sulfate Was introduced and stirred uniformly to obtain an aqueous hydrogen peroxide solution.
The obtained aqueous hydrogen peroxide solution was added to the suspension prepared in Step A at an addition rate of 210 ml / h, and at the same time, 0.05 parts by mass of sodium percarbonate having an average particle size of 100 μm was added as a seed crystal. The reaction was carried out at a reaction temperature of 22 to 23 ° C. and a reaction time of 90 minutes to produce sodium percarbonate crystals.

(Process C)
The produced crystal was subjected to solid-liquid separation using a centrifugal separator, and the obtained crystal was dried in a fluidized bed at about 90 ° C. for 30 minutes. In this way, sodium percarbonate particles (b1) were obtained.
Table 2 shows the main production conditions in this example, the amount of active oxygen of the obtained sodium percarbonate particles (b1), the average particle diameter (unit: μm), and the particle strength (unit: N / m ² ).

[Production Examples 12 to 16: Production of sodium percarbonate particles (b2) to (b6)]
Sodium percarbonate particles (b2) to (b6) were produced in the same manner as in Production Example 11 except that the production conditions were changed as shown in Table 2.
Table 2 shows the amount of active oxygen, average particle diameter, and particle strength of the obtained sodium percarbonate particles (b2) to (b6).
Sodium percarbonate particles (b5) and (b6) are comparative examples having a small particle strength.

[Sodium Percarbonate Particles of Comparative Example (b7)]
As sodium percarbonate particles (b7) of Comparative Example, sodium percarbonate particles manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: SPC-G, average particle size 751 μm, particle strength 1.5 × 10 ⁶ N / m ² were used. .

[Examples and Comparative Examples]
According to the blending ratio shown in Table 3, a granular detergent composition was produced by the following method. In Table 3, Examples 1 to 12 are examples, and Examples 13 to 16 are comparative examples. The raw materials shown in Table 3 are as follows.
Surfactant-containing particles (a): surfactant particles obtained in the above production example.
-Sodium percarbonate particle | grains (b): Sodium percarbonate particle | grains obtained by the said manufacture example, and the sodium percarbonate particle | grains (b7) of a comparative example.
Enzyme: Sabinase 12T (manufactured by Novozymes), particulate.
Fragrance: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18].
-Dye: Ultramarine (Daiichi Seika Kogyo, Ultramarine Blue).
-Brightening agent: Chinopearl CBS-X (Ciba Specialty Chemicals) / Chinopearl AMS-GX (Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture.

Filling rate 30 in a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a drum inner wall surface of a container 131.7 L and two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Surfactant-containing particles (a) and sodium percarbonate particles (b) were charged under the conditions of volume%, rotation speed 22 rpm, and 25 ° C., and rolled for 1 minute while spraying the fragrance.
In order to color a part of the obtained particles, the particles are transferred on the belt conveyor at a speed of 0.5 m / s (the particle layer on the belt conveyor is 30 mm high and the layer width is 300 mm). A 20% aqueous dispersion of 0.1% by mass was sprayed.
After the coloring step, the obtained particles and enzyme are put into the same horizontal cylindrical rolling mixer as above, under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., and mixed for 5 minutes to form granules. A detergent composition was obtained.

[Evaluation methods]
Table 3 shows the bulk density of the granular detergent compositions obtained in Examples 1 to 16.
In addition, the dissolution rate was measured by the following method, and the active oxygen residual rate of sodium percarbonate (hereinafter sometimes referred to as PC residual rate) was measured by the following method. The results are shown in Table 3. The faster the dissolution rate, the better the solubility. The higher the PC residual rate, the higher the storage stability of sodium percarbonate.
<Method for evaluating dissolution rate>
The electrical conductivity was measured by the following method to calculate the dissolution time, and the dissolution rate of the sample (granular detergent composition) was evaluated. An evaluation standard of ○ or higher is considered acceptable.
That is, 1 L of water adjusted to 5 ° C. and 3 ° DH hard water (calcium chloride was added to ion-exchanged water) was filled in a cylindrical 1 L beaker having an inner diameter of 105 mm. Set the beaker on the electric conductivity meter “TOA PH / EC METER WM-50EG (trade name)” manufactured by Toa Denpa Kogyo Co., Ltd., and stir the blade with a constant speed motor (length 40 mm, width 22 mm) The water in the beaker was stirred at a rotational speed of 250 rpm using the one attached to one side of the tip of the stirring shaft. The stirring shaft is at the center of the beaker and is perpendicular to the bottom surface of the beaker, and the position of the lower end of the stirring blade is 5 mm from the bottom of the beaker. The electrical conductivity a before the sample was measured in advance, and 0.67 g of the sample was charged all at once into the central portion of the stirring blade. The electric conductivity was measured at intervals of 5 seconds with the time point of charging being 0 seconds, and the electric conductivity b after t seconds was measured. The value of electrical conductivity when the value of electrical conductivity did not continue to rise for 2 minutes or more was taken as the electrical conductivity c at the dissolution completion point. Then, the dissolution rate after t seconds was calculated by the following formula, and the time (t) when the dissolution rate reached 90% or more was defined as the dissolution time (second).

[formula]
Dissolution rate (%) after t seconds = (Electrical conductivity b after t seconds−Electrical conductivity a before sample introduction) / (Electrical conductivity c at the completion of dissolution c−Electric conductivity a before sample introduction) × 100
〔Evaluation criteria〕
A: The dissolution time is less than 150 seconds.
A: Dissolution time is 150 seconds or more and less than 170 seconds.
○: Dissolution time is 170 seconds or more and less than 190 seconds.
Δ: Dissolution time is 190 seconds or more and less than 210 seconds.
X: Dissolution time is 210 seconds or more.

<Method for evaluating active oxygen residual rate (PC residual rate) of sodium percarbonate>
500 g of a sample (granular detergent composition) is placed in a low hygroscopic paper detergent container (11 cm × 15 cm × 9 cm), held at 25 ° C. and 65% RH for 8 hours, and then at 45 ° C. and 85% RH for 16 hours. After that, the sample was again placed in a constant temperature and humidity test chamber where the operation of holding at 25 ° C. and 65% RH for 8 hours was repeated, and left for 21 days.
The amount of active oxygen before storage and the amount of active oxygen after storage for 21 days are measured by the above method, and the active oxygen residual rate (PC residual rate) is obtained by the following formula to evaluate the storage stability of sodium percarbonate. did. An evaluation standard of ○ or higher is considered acceptable.

[Formula for calculating PC residual ratio]
PC residual ratio (%) = (active oxygen amount after storage / active oxygen amount before storage) × 100
〔Evaluation criteria〕
A: PC residual ratio is 80% or more.
A: PC residual ratio is 70% or more and less than 80%.
○: PC residual ratio is 60% or more and less than 70%.
Δ: PC residual ratio is 50% or more and less than 60%.
X: PC residual ratio is less than 50%.

As shown in the results of Table 3, Example 1 in which the average particle size of the surfactant-containing particles is 400 μm or less and the particle strength of the sodium percarbonate particles is 1.8 × 10 ⁻¹⁰ N / m ² or more. The granular detergent composition of -12 has good dissolution rate and PC residual ratio, and is excellent in both the solubility of the detergent composition and the storage stability of sodium percarbonate.
In particular, Example 6 in which the average particle size of the surfactant-containing particles is as small as 300 μm has high solubility.
Moreover, when Example 3 and Example 10 are compared, the storage stability of sodium percarbonate is higher in Example 10 having a lower zeolite content in the surfactant-containing particles. When Example 1 is compared with Example 11, the storage stability of sodium percarbonate is higher in Example 1 where the amount of water in the surfactant-containing particles is smaller.
In contrast, Example 13 in which the average particle size of the surfactant-containing particles is 500 μm or less has poor solubility, and Examples 14 to 16 in which the sodium percarbonate particles have low particle strength have poor storage stability of sodium percarbonate. .
As described above, generally, when the particle size of the detergent particles is small, the contact area between the sodium percarbonate and the detergent particles is large, so that the stability of sodium percarbonate is lowered. By increasing the particle strength of the sodium particles, it is possible to reduce the particle size of the detergent particles to obtain good solubility, and at the same time improve the storage stability of sodium percarbonate.
In addition, by controlling the production conditions of sodium percarbonate particles and controlling the crystal state so that the particle strength is in a specific range, this effect can be obtained, so the stability of sodium percarbonate particles is improved. It is not necessary to add a manufacturing process to make it happen.

Claims (1)

A high bulk density granular detergent composition comprising surfactant-containing particles having an average particle size of 400 μm or less and sodium percarbonate particles having a particle strength of 2.1 × 10 ⁶ N / m ² or more.