JP6991035B2 - Granular detergent - Google Patents

Description

The present invention relates to a granular detergent.

Concentration of surfactants and high bulk density of powders have become the mainstream in granular detergents from the viewpoints of reducing transportation costs, space required for storage and display, and eliminating the labor of weighing in ordinary households.
As a method for concentrating the surfactant and increasing the bulk density of the powder, a method of dry-blending granules containing a high concentration of the surfactant is known.
In Patent Document 1, fine particles are suppressed and good fluidity is maintained by using surfactant particles containing a highly crystalline anionic surfactant at a high concentration in combination with particles containing a nonionic surfactant as a main component. How to do it is proposed.

Japanese Unexamined Patent Publication No. 10-095997

Depending on the storage location and usage location of the detergent, it may be stored under high temperature conditions, and even granular detergents are required to be able to withstand storage under high temperature conditions.
According to the findings of the present inventors, in the method of Patent Document 1, when the granular detergent is stored at a high temperature, the fluidity is lowered and it may be difficult to scoop with a spoon.
An object of the present invention is a granular detergent having a small decrease in fluidity even when stored under high temperature conditions.

The present invention has the following aspects.
[1] A granular detergent containing the following particle group (A), the following particle group (B), the following particle group (C), and the following particle group (D).
Particle group (A): A particle group of anionic surfactant-containing particles (a) containing 40% by mass or more of an anionic surfactant and having an anionic surfactant content higher than that of other surfactants.
Particle group (B): Nonion interface containing 30% by mass or more of a nonionic surfactant and 25% by mass or more of a water-swellable clay mineral, and the content of the nonionic surfactant is higher than the content of other surfactants. A group of particles of the activator-containing particle (b).
Particle group (C): A group of water-soluble inorganic salt-containing particles (c) that do not contain percarbonate and contain 70% by mass or more of water-soluble inorganic salt, and have an average particle diameter of 500 μm or more.
Particle group (D): A particle group of percarbonate-containing particles (d) containing 80% by mass or more of percarbonate.
[2] Further, the granular detergent of [1] containing the following particle group (E).
Particle group (E): A group of water-soluble inorganic salt-containing particles (e) containing neither a surfactant nor a percarbonate and containing 80% by mass or more of a water-soluble inorganic salt, and having an average particle diameter of less than 500 μm. A group of particles that are.
[3] The granular detergent according to [1] or [2], which has a water content of 3% by mass or less.
[4] The granular detergent according to any one of [1] to [3], wherein the zeolite content is 10% by mass or less with respect to the total mass of the granular detergent.
[5] The average particle size of the particle group (D) is 500 μm or more, and the absolute value of the difference between the average particle size of the particle group (C) and the average particle size of the particle group (D) is 300 μm or less. The granular detergent according to any one of [1] to [4].

According to the present invention, a granular detergent having a small decrease in fluidity even when stored under high temperature conditions can be obtained.

[Measurement method of water content]
In the present specification, the water content of the particle group and the water content of the granular detergent are values measured as evaporative volatilization after heating at 130 ° C. for 20 minutes by an infrared moisture meter (for example, Kett Moisture Meter manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.). Is.
[Measuring method of bulk density]
In the present specification, the bulk density of the particle group is a value measured according to JIS K3362 (2008).

[Measurement method of average particle size]
In the present specification, the average particle size of the particle group is a value measured by the following sieving method.
The average particle size is measured by a classification operation using a 10-stage sieve having a mesh size of 1400 μm, 1180 μm, 1000 μm, 710 μm, 500 μm, 425 μm, 355 μm, 250 μm, 150 μm and 75 μm, and a saucer.
For the classification operation, stack the sieves with small meshes to the sieves with large meshes in this order on the saucer, put a sample of 100 g / time from the top of the 1400 μm sieve, cover it, and use a low-tap sieve shaker (stock). Manufactured by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), and after shaking for 10 minutes, the sample (classified sample) remaining on each sieve and saucer is collected for each sieve. do. The mass of the classified sample of each particle size is measured, and the mass frequency (%) is calculated.
When determining the average particle size, the opening of the first sieve whose cumulative mass frequency is 50% or more is set to "aμm", the opening of the sieve one step larger than aμm is set to "bμm", and the sieve of aμm from the saucer. The integrated value of the mass frequencies up to is "c%", and the mass frequency on the sieve of aμm is "d%", and the average particle size (50% by mass particle size) is obtained by the following formula (1). The average particle size.

(Granular detergent)
The granular detergent of the present invention is a granular composition containing a particle group (A), a particle group (B), a particle group (C), and a particle group (D).
In the granular detergent, the anionic surfactant-containing particles (a) constituting the particle group (A), the nonionic surfactant-containing particles (b) constituting the particle group (B), and the particle group (C) are formed. The water-soluble inorganic salt-containing particles (c) and the percarbonate-containing particles (d) constituting the particle group (D) exist as independent particles.

<Particle group (A)>
The particle group (A) contains 40% by mass or more of an anionic surfactant, and the content of the anionic surfactant is higher than the content of other surfactants. It is also a group of "particles (a)").
The particle group (A) contained in the granular detergent may be one kind or two or more kinds having different compositions. It is assumed that the composition of the particles (a) constituting one kind of particle group (A) is uniform.

The anionic surfactant is not particularly limited as long as it is used for a granular detergent, and examples thereof include the following.
(1-1) α-sulfofatty acid alkyl ester salt.
The type of α-sulfofatty acid alkyl ester salt (hereinafter, also referred to as α-SF salt) is not particularly limited. Those represented by the following formula (1) are preferable.
R ¹ -CH (SO ₃ M) -COOR ² ... (1)
In formula (1), R ¹ is a straight-chain or branched-chain alkyl group having 8 to 20 carbon atoms, preferably 14 to 16 carbon atoms, or a straight-chain or branched-chain alkenyl group having 8 to 20 carbon atoms. Is. ^R2 is an alkyl group having 1 to 6 carbon atoms, and preferably has 1 to 3 carbon atoms. A methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is particularly preferable, because the detergency is further improved.
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; and ammonium salts. Of these, alkali metal salts are preferable.

(1-2) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(1-3) Alkane sulfonate having 10 to 20 carbon atoms.
(1-4) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(1-5) An alkyl sulfate or an alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(1-6) Any of the 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) are mixed with an average of 0. An alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 5 to 10 molar additions of 10 to 20 carbon atoms.
(1-7) Any 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 3 to An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with 30 mol.
(1-8) Any of the 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) are mixed with an average of 0. An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 5 to 10 molar additions of 10 to 20 carbon atoms.
(1-9) An alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(1-10) A monoalkyl, dialkyl or sesquialkyl phosphate having an alkyl group having 10 to 20 carbon atoms.
(1-11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(1-12) Higher fatty acid salt (soap) having 10 to 20 carbon atoms.
These anionic surfactants can be used as alkali metal salts such as sodium salts and potassium salts, amine salts, ammonium salts and the like.
The anionic surfactant may be one kind or two or more kinds.
As the anionic surfactant, α-SF salt is preferable, and α-sulfofatty acid methyl ester sodium salt (MES) is more preferable.

The particle (a) may contain a surfactant other than the anionic surfactant. For example, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant and the like can be mentioned.
Examples of the nonionic surfactant include (2-1) to (2-8) described later.
The nonionic surfactant may be one kind or two or more kinds.

Examples of the cationic surfactant include the following.
(3-1) Di-long-chain alkyl Di-short-chain alkyl type quaternary ammonium salt.
(3-2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(3-3) Tri-long chain alkyl mono-short chain alkyl type quaternary ammonium salt.
However, the above-mentioned "long-chain alkyl" indicates 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 poly having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. An oxyalkylene group is preferred.
The cationic surfactant may be one kind or two or more kinds.

Examples of the amphoteric tenside include an imidazoline-based amphoteric tenside, an amidobetaine-based amphoteric tenside, and an amine oxide-based amphoteric tenside. Specific examples thereof include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauric acid amide propyl betaine, and alkylamine oxide.
The amphoteric tenside may be one kind or two or more kinds.

The total content of the surfactant with respect to the total mass of the particles (a) is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more. The upper limit may be 100% by mass. When it is at least the lower limit of the above range, the amount of the particles (a) required for exhibiting the cleaning performance can be further reduced, and dust generation can be suppressed, which is preferable.
The total amount of the anionic surfactant contained in the particle (a) is the total amount of each of the other surfactants (for example, the total amount of the nonionic surfactant, the total amount of the cationic surfactant, or the amphoteric surfactant). More than the total amount of).
The total content of the anionic surfactant with respect to the total mass of the particles (a) is 40% by mass or more, preferably 50% by mass or more. The upper limit may be 100% by mass. When it is at least the lower limit of the above range, the amount of the particles (a) required for exhibiting the cleaning performance can be further reduced, and dust generation can be suppressed, which is preferable.
The total content of the anionic surfactant is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total content of the surfactant in the particles (a). % Is more preferable.

[Other optional ingredients]
The particle (a) may further contain an optional component other than the surfactant, if necessary. As other optional components, known components to be blended in granular detergents can be used, for example, organic builders, water-soluble inorganic salts, water-insoluble inorganic salts, fluorescent agents, polymers, enzyme stabilizers, anti-scavengers, and the like. Examples thereof include a reducing agent, a metal ion scavenger, and a pH adjuster.

Examples of the organic builder include citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylic acid salt, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid and the like.

Examples of the water-soluble inorganic salt include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and sodium sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite. Salts; crystalline layered sodium silicate, amorphous alkali metal silicate; sulfates such as sodium sulfate and potassium sulfate; alkali metal chlorides such as sodium chloride and potassium chloride; pyrophosphates, tripolyphosphates, orthoric acid Phosphates such as salts, metaphosphates, hexametaphosphates and phytates; complex of sodium carbonate and amorphous alkali metal silicates and the like can be mentioned.
Anhydrous is preferably used as sodium carbonate and sodium sulfate. The description of "sodium carbonate" and "sodium sulfate" in the present specification refers to anhydrate.

Examples of the water-insoluble inorganic salt include aluminosilicates and clay minerals. Examples of the clay mineral include the water-swellable clay mineral described later.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used. Crystalline aluminosilicate is preferable from the viewpoint of cation exchange ability. As the crystalline aluminosilicate, zeolites such as A-type, X-type, Y-type, and P-type zeolites are suitable.

The content of zeolite is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total mass of the particles (a). It may be zero. When it is not more than the upper limit of the above range, the storage stability of the percarbonate is more excellent.

The water content of the particle group (A) is preferably 7% by mass or less, more preferably 6% by mass or less. The lower limit is not particularly limited. Substantially, 0.5% by mass or more is preferable. When it is not more than the upper limit of the above range, the storage stability of the percarbonate is more excellent.
When the granular detergent contains two or more kinds of particle groups (A) having different compositions, the preferable range of the water content of the particle group (A) means the preferable range of the water content of each particle group (particles). The same applies to the groups (B) to (E).)

The average particle size of the particle group (A) is preferably 250 to 550 μm, more preferably 350 to 450 μm. When the average particle size of the particle group (A) is at least the lower limit of the above range, there is little dusting and it is easy to handle, and when it is at least the upper limit, the solubility in water is good.
When the granular detergent contains two or more kinds of particle groups (A) having different compositions, the preferable range of the average particle size of the particle group (A) means the preferable range for the average particle size of each particle group. (The same applies to the particle groups (B) to (E)).

The bulk density of the particle group (A) is preferably 0.6 to 1.0 g / cm ³ , more preferably 0.6 to 0.7 g / cm ³ . When the bulk density of the particle group (A) is at least the lower limit of the above range, classification can be suppressed, and when it is at least the upper limit, the difference from the bulk density of the particle group (B) becomes small and the mixing property becomes good. Dust generation can be suppressed.
When the granular detergent contains two or more kinds of particle groups (A) having different compositions, the preferable range of the bulk density of the particle group (A) means the preferable range of the bulk density of each particle group (particles). The same applies to the groups (B) to (E).)

The total content of the particle group (A) with respect to the total mass of the granular detergent is preferably 4 to 15% by mass, more preferably 7 to 15% by mass, still more preferably 9 to 12% by mass. When the content of the particle group (A) is at least the above lower limit value, the adhesiveness of the particle group (B) can be suppressed, and when it is at least the above upper limit value, the dust generation property of the granular detergent and the granular detergent after storage are obtained. It is preferable in terms of fluidity.

The method for producing the particle group (A) may be any method as long as the content of the anionic surfactant in the particles (a) can be 40% by mass or more, and a known method can be used. A commercially available product may be used as the particle group (A).
For example, as a method for producing particles (a) in which the anionic surfactant in the particles is an α-SF salt, a step of preparing a paste containing the α-SF salt (pasting step) and preparing flakes from the paste. Step (flake formation step), preparation of noodles from the flakes (noodle formation step), step of adjusting pellets from the noodles (pelletization step), step of crushing the flakes, noodles or pellets to obtain particles. Examples thereof include a method having (grinding step).
The above (noodle formation step) and (pelletization step) are arbitrary steps and may be omitted. Further, after the above (grinding step), a step of classifying the particle group (classification step) may be provided. Further, after the above (flaking step), (noodle making step) or (pelling step), and before the crushing step, a step (aging step) for aging the flakes, noodles or pellets may be provided.

<Particle group (B)>
The particle group (B) contains 30% by mass or more of a nonionic surfactant and 25% by mass or more of a water-swellable clay mineral, and the content of the nonionic surfactant is higher than that of other surfactants. It is a group of surfactant-containing particles (b) (hereinafter, also simply referred to as “particles (b)”).
The particle group (B) contained in the granular detergent may be one kind or two or more kinds having different compositions. It is assumed that the composition of the particles (b) constituting one kind of particle group (B) is uniform.

The nonionic surfactant is not particularly limited as long as it is conventionally used for granular detergents, and examples thereof include the following.
(2-1) An average of 3 to 30 mol, preferably 3 to 20 mol, more preferably 5 to 20 mol of an alkylene oxide having 2 to 4 carbon atoms in an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. The added polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. Further, the alkyl group may have a branched chain. As the aliphatic alcohol, primary alcohol is preferable.
(2-2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(2-3) Fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between the ester bonds of a long-chain fatty acid alkyl ester.
(2-4) Polyoxyethylene sorbitan fatty acid ester.
(2-5) Polyoxyethylene sorbitol fatty acid ester.
(2-6) Polyoxyethylene fatty acid ester.
(2-7) Polyoxyethylene cured castor oil.
(2-8) Glycerin fatty acid ester.
The nonionic surfactant may be one kind or two or more kinds.

The particles (b) may contain a surfactant other than the nonionic surfactant. For example, anionic surfactants, cationic surfactants, amphoteric surfactants and the like can be mentioned. These include the same as the anionic surfactant, the cationic surfactant and the amphoteric surfactant in the particle (a).

The total content of the surfactant with respect to the total mass of the particles (b) is more preferably 30% by mass or more, further preferably 40% by mass or more. The upper limit is 75% by mass, preferably 60% by mass or less. It is preferable that it is at least the lower limit of the above range in terms of cleaning performance. When it is not more than the upper limit, the fluidity of the particles (b) becomes good.
The total amount of the nonionic surfactant contained in the particle (b) is the total amount of each of the other surfactants (for example, the total amount of the anionic surfactant, the total amount of the cationic surfactant, or the amphoteric surfactant). More than the total amount of).
The total content of the nonionic surfactant is 30% by mass or more, preferably 50% by mass or more, based on the total mass of the particles (b). The upper limit is 75% by mass, preferably 70% by mass or less, and more preferably 65% by mass or less. When it is at least the lower limit of the above range, dust generation of other particle groups can be satisfactorily suppressed, and when it is at least the upper limit, the balance with other components is good.
The total content of the nonionic surfactant is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total content of the surfactant in the particles (b). % Is more preferable.

The "water-swellable clay mineral" means a clay mineral having a swelling power of 20 mL / 2 g or more. Here, "swelling power" is expressed by the swelling volume (mL) of 2 g of water-swellable clay mineral, applying the test method of bentonite specified in the 15th revised Japanese Pharmacopoeia mutatis mutandis.
Water-swellable clay minerals include smectite clays such as bentonite, montmorillonite, saponite, byderite, hectorite, stebunsite, soconite, and nontronite, natural clays such as vermiculite, halloysite, and swellable mica, and synthetic clays thereof. And mixtures thereof.
The water-swellable clay mineral may be one kind or two or more kinds.

The total content of the water-swellable clay mineral is 25% by mass or more, preferably 30% by mass or more, and more preferably 35% by mass or more with respect to the total mass of the particles (b). The upper limit is 70% by mass, preferably 60% by mass or less, and more preferably 50% by mass or less. When it is at least the lower limit of the above range, the oil absorption capacity of the nonionic surfactant becomes good, and when it is at least the upper limit, the balance with other components is good.

If necessary, the particles (b) may further contain other optional components that do not fall under either a surfactant or a water-swellable clay mineral. Other optional components include those similar to other optional components in the particle (a) (excluding water-swellable clay minerals).

The water content of the particle group (B) is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is not particularly limited. Substantially, 1% by mass or more is preferable. When it is not more than the upper limit of the above range, the storage stability of the percarbonate is more excellent.
The average particle size of the particle group (B) is preferably 300 to 600 μm, more preferably 400 to 500 μm. When the average particle size of the particle group (B) is at least the lower limit of the above range, there is little dusting and it is easy to handle, and when it is at least the upper limit, the solubility in water is good.
The bulk density of the particle group (B) is preferably 0.5 to 0.9 g / cm ³ , more preferably 0.6 to 0.8 g / cm ³ . When it is at least the lower limit value in the above range, classification can be suppressed, and when it is at least the upper limit value, the difference from the bulk density of the particle group (A) becomes small, the mixing property becomes good, and dust generation can be suppressed.
The total content of the particle group (B) with respect to the total mass of the granular detergent is preferably 2 to 15% by mass, more preferably 4 to 10% by mass. When the content of the particle group (B) is at least the above lower limit value, dust generation of other particle groups can be suppressed, and when it is at least the above upper limit value, it is preferable in terms of fluidity after storage of the granular detergent.

As a method for producing the particle group (B), a known method can be used. A commercially available product may be used as the particle group (B).
For example, it can be produced by a method of stirring and mixing a water-swellable clay mineral and other optional components as required, adding a nonionic surfactant to the mixture, and stirring and granulating the mixture.

<Particle group (C)>
The particle group (C) is a water-soluble inorganic salt-containing particle (c) that does not contain a percarbonate and contains 70% by mass or more of a water-soluble inorganic salt (hereinafter, also simply referred to as “particle (c)”). It is a group of particles having an average particle size of 500 μm or more.
The particle group (C) contained in the granular detergent may be one kind or two or more kinds having different compositions. It is assumed that the composition of the particles (c) constituting one kind of particle group (C) is uniform.

Examples of the water-soluble inorganic salt include the same water-soluble inorganic salts mentioned as other optional components in the particles (a).
The particles (c) are preferably granulated products containing a water-soluble inorganic salt and a binder. The granulated product facilitates control of the average particle size and bulk density.
As the binder, an organic water-soluble polymer compound or an inorganic water-soluble polymer compound is used. The organic water-soluble polymer compound and the inorganic water-soluble polymer compound may be used in combination.

[Organic water-soluble polymer compound]
The organic water-soluble polymer compound is a polymer compound that is uniformly mixed with water at a concentration of 0.1 g or more, preferably 0.2 g or more, more preferably 2 g or more with respect to 100 g of water at 40 ° C. The organic water-soluble polymer compound may be one kind or two or more kinds.
Examples of the organic water-soluble polymer compound include natural polymer compounds, semi-synthetic polymer compounds and synthetic polymer compounds. Specific examples thereof include vinyl-based polymer compounds, polysaccharides, polyether-based polymer compounds, polyester-based polymer compounds, peptide-based polymer compounds, polyurethanes, and derivatives thereof.

Examples of the vinyl-based polymer compound include vinyl-based polycarboxylic acid salts (acrylic acid-based polymer compounds), vinyl-based polysulfonates, polyvinylpyridine salts, polyvinylimidazolium salts and the like. Examples of the polysaccharide include various natural or synthetic polysaccharides.
Examples of the polyester-based polymer compound include a copolymer of terephthalic acid and ethylene glycol and / or a propylene glycol unit, or a terpolymer.
Examples of the peptide-based polymer compound or its derivative include gelatin, casein, albumin, collagen, polyglutamic acid salt, polyaspartic acid salt, polylysine, polyarginine and derivatives thereof.
Examples of polyurethane include water-soluble polyurethane and the like.
Further, other water-soluble polymer compounds such as polyethylene glycol can also be used.

In particular, when a water-soluble organic polymer compound having hydrophilic functional groups such as anionic, amphoteric, and nonionic is used as a binder and a water-soluble inorganic salt is granulated in the presence of water, the water-soluble inorganic salt is hydrated. It is preferable because it is easy to do.
Examples of the water-soluble organic polymer compound having an anionic group include a carboxyl group, a polymer compound having a sulfo group, and a water-soluble polysaccharide having an anionic group. Examples of the water-soluble organic polymer compound having a carboxyl group include polymers obtained by polymerizing monomers such as acrylic acid, maleic acid, itaconic acid, aconitic acid, methacrylic acid, fumaric acid, 2-hydroxyacrylic acid, and citraconic acid. And its salts, and polymers of these monomers with other vinyl-based monomers and vinyl-based polycarboxylic acids (salts) such as salts thereof. Examples of the water-soluble polymer compound having a sulfo group include a monomer obtained by polymerizing a monomer such as acrylamide propane sulfonic acid, methacrylamide propane sulfonic acid, and styrene sulfonic acid and a salt thereof, and these polymers and other vinyl-based compounds. Examples thereof include a copolymer with a polymer and a vinyl-based polysulfonic acid (salt) such as a salt thereof. Examples of the water-soluble polysaccharide having an anionic group include polyuranate, alginate, polyaspartic acid, carrageenan, hyaluronate, chondroitin sulfate, carboxymethyl cellulose and the like.

Examples of the amphoteric water-soluble polymer compound include a copolymer of a vinyl-based monomer having an anionic group and a vinyl-based monomer having a cationic group, and a vinyl-based monomer having a carboxybetaine group or a sulfobetaine group. Examples thereof include an amphoteric polymer, and specific examples thereof include an acrylic acid / dimethylaminoethyl methacrylate copolymer and an acrylic acid / diethylaminoethyl methacrylate copolymer.
Examples of the nonionic water-soluble polymer compound include synthetic polymer compounds such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylethyl ether and polyethylene glycol, and polysaccharides such as hydroxyethyl cellulose, guar gum, dextran and pullulan.

[Inorganic water-soluble polymer compound]
The inorganic water-soluble polymer compound is a compound that is uniformly mixed with water at a concentration of 0.1 g or more, preferably 0.2 g or more, more preferably 2 g or more with respect to 100 g of water at 40 ° C.
As long as it is such an inorganic water-soluble polymer compound, it is not particularly limited, and one kind alone or two or more kinds can be used in combination as appropriate. As the inorganic water-soluble polymer compound, those obtained by hydrolyzing and depolymerizing a solution containing a precursor compound of a metal alkoxide are preferable, silicate is more preferable, and sodium silicate is particularly preferable.

The granulated product containing the water-soluble inorganic salt and the binder can be produced by adding the binder and water to the particles of the water-soluble inorganic salt and granulating by using a known granulation method.
The organic water-soluble polymer compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total mass of the particles (c).
The inorganic water-soluble polymer compound is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total mass of the particles (c).

The content of the water-soluble inorganic salt is 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more with respect to the total mass of the particles (c). It may be 100% by mass.
The water content of the particle group (C) is preferably 2% by mass or less, more preferably 1% by mass or less. It may be zero. When it is not more than the upper limit of the above range, the storage stability of the percarbonate is more excellent.
The average particle size of the particle group (C) is 500 μm or more, preferably 700 to 1100 μm, and more preferably 800 to 1000 μm. When the average particle size of the particle group (C) is at least the lower limit of the above range, the effect of improving the fluidity of the granular detergent is excellent, and when it is at least the upper limit, the solubility in water is excellent.
The bulk density of the particle group (C) is preferably 0.9 to 1.3 g / cm ³ , more preferably 1.0 to 1.2 g / cm ³ . When it is at least the lower limit of the above range, the fluidity becomes good, and when it is at least the upper limit, classification can be suppressed.
The total content of the particle group (C) with respect to the total mass of the granular detergent is preferably 10 to 30% by mass, more preferably 15 to 25% by mass. When the content of the particle group (C) is at least the above lower limit value, it is preferable in terms of fluidity after storage of the granular detergent, and when it is at least the above upper limit value, the balance with other particle groups is good.

<Particle group (D)>
The particle group (D) is a group of percarbonate-containing particles (d) containing 80% by mass or more of percarbonate (hereinafter, also simply referred to as “particles (d)”).
Percarbonates generate hydrogen peroxide when dissolved in water and contribute to the bleaching effect. When moisture or other detergent components come into contact with the surface of the percarbonate, the percarbonate may be decomposed. Therefore, it is preferable to perform a coating or the like in order to prevent this. As the particles in the coated form, oxygen-based bleach particles already proposed can be used. For example, bleach particles described in Japanese Patent No. 2918991 can be mentioned. The bleaching agent particles are granulated products obtained by separately spraying a boric acid aqueous solution and a silicic acid alkali metal salt aqueous solution onto sodium percarbonate particles that have been kept in a fluid state and drying them. A stabilizer such as a conventionally known chelating agent may be used in combination with the coating agent.

The content of percarbonate is 80% by mass or more, preferably 85% by mass or more, and more preferably 90% by mass or more, based on the total mass of the particles (d). The upper limit may be 100% by mass, but 95% by mass or less is preferable from the viewpoint of storage stability of the percarbonate.
The water content of the particle group (D) is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less, from the viewpoint of the stability of the particles (d). It may be zero.

The average particle size of the particle group (D) is 500 μm or more, preferably 500 to 900 μm, and more preferably 600 to 800 μm. When the average particle size of the particle group (D) is at least the lower limit of the above range, the stability of the particles (d) is excellent, and when it is at least the upper limit, the solubility in water is excellent.
The absolute value of the difference between the average particle size of the particle group (C) and the average particle size of the particle group (D) coexisting in the granular detergent is preferably 300 μm or less, more preferably 200 μm or less. It may be zero. Within this range, the effect of improving the fluidity by using the particle group (C) is excellent. When the granular detergent contains at least two kinds of the particle group (C) or the particle group (D), the difference between the average particle size of the particle group (C) and the average particle size of the particle group (D) is the largest. A large value may be within the above range.
The bulk density of the particle group (D) is preferably 0.7 to 1.1 g / cm ³ , more preferably 0.8 to 1.0 g / cm ³ . When it is equal to or more than the lower limit value and less than or equal to the upper limit value in the above range, the difference from the bulk density of other particle groups is small and classification is unlikely to occur.
The total content of the particle group (D) with respect to the total mass of the granular detergent is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. When the content of the particle group (D) is at least the above lower limit value, it is preferable in terms of cleaning performance, and when it is at least the above upper limit value, the balance with other particle groups is good.

<Particle group (E)>
The particle group (E) is a water-soluble inorganic salt-containing particle (e) containing 70% by mass or more of a water-soluble inorganic salt without containing a surfactant and a percarbonate (hereinafter, also simply referred to as “particle (e)”). It is a group of particles having an average particle diameter of less than 500 μm.
The particle group (E) contained in the granular detergent may be one kind or two or more kinds having different compositions. It is assumed that the composition of the particles (e) constituting one kind of particle group (E) is uniform.

Examples of the water-soluble inorganic salt include the same water-soluble inorganic salts mentioned as other optional components in the particles (a).
The particles (e) may be granulated products containing the same binder as the particles (c), but particles composed of crystals of a water-soluble inorganic salt are preferable.
The content of the water-soluble inorganic salt is 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more with respect to the total mass of the particles (e). It may be 100% by mass.
The water content of the particle group (E) is preferably 2% by mass or less, more preferably 1% by mass or less. It may be zero. When it is not more than the upper limit of the above range, the storage stability of the percarbonate is more excellent.

The average particle size of the particle group (E) is less than 500 μm, preferably 150 to 400 μm, and more preferably 200 to 350 μm. When the average particle size of the particle group (E) is at least the lower limit of the above range, it is preferable in terms of the fluidity of the granular detergent, and when it is at least the upper limit, the solubility in water is excellent.
The bulk density of the particle group (E) is preferably 0.8 to 1.3 g / cm ³ , more preferably 0.9 to 1.2 g / cm ³ . When it is equal to or more than the lower limit value and less than or equal to the upper limit value in the above range, the difference from the bulk density of other particle groups is small and classification is unlikely to occur.
The total content of the particle group (E) with respect to the total mass of the granular detergent is preferably 15 to 55% by mass, more preferably 25 to 45% by mass. When the content of the particle group (E) is at least the above lower limit value and at least the above upper limit value, the balance with other particle groups is good.

<Arbitrary ingredient>
If necessary, the granular detergent may contain an optional component that does not fall under any of the particle groups (A) to (E) as long as the effect of the present invention is not impaired. Examples thereof include bleach activators, bleach activation catalysts, enzymes, defoamers, surface coating agents (zeolites, etc.), fragrances, pigments and the like.
These optional components may be powder-mixed with the particle groups (A) to (E) as other particle groups, or may be attached to the particle groups (A) to (E) by, for example, spraying.
The total content of the optional components with respect to the total mass of the granular detergent is 0 to 10% by mass, preferably 0 to 8% by mass, more preferably 0 to 6% by mass, and particularly preferably 0 to 4% by mass.

The water content of the granular detergent is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1.5% by mass or less. When it is not more than the upper limit of the above range, the storage stability of percarbonate is excellent. The lower limit is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, still more preferably 1.0% by mass or more from the viewpoint of solubility of the granular detergent.
The content of zeolite is preferably 10% by mass or less, more preferably 7.5% by mass or less, still more preferably 5% by mass or less, based on the total mass of the granular detergent. When it is not more than the upper limit of the above range, the storage stability of percarbonate is excellent. The lower limit is preferably 1.5% by mass or more, more preferably 3% by mass or more, and further preferably 4.5% by mass or more from the viewpoint of cleaning performance.

<Manufacturing method of granular detergent>
In the granular detergent, the particle group (A), the particle group (B), the particle group (C), the particle group (D), and other particle groups are mixed in a predetermined ratio as needed. Can be manufactured by.
As a method for mixing the particle group, a known powder mixing method can be used. For example, the entire particle group is charged into a conventionally known powder mixing device (for example, a horizontal cylindrical rolling mixer or a V-type mixer). And a method of mixing. As for the charging of each particle group, two or more kinds may be thrown at the same time, one kind may be thrown at a time, or these may be thrown in combination. After mixing the whole grain group, a liquid component such as a fragrance may be added by spraying or the like and mixed.

<How to use granular detergent>
The granular detergent can be used for washing the object to be washed. As a method for washing the object to be washed using the granular detergent, for example, a washing solution diluted with 50 to 5000 times water so that the concentration of the granular detergent is 0.02 to 2% by mass (200 to 20000 ppm) is used. Examples thereof include conventionally known washing methods such as washing the washing object with a washing machine in which the washing object is put so that the bath ratio becomes 3 to 50 times, or immersing the washing object in the washing liquid.
Examples of the object to be washed include textile products such as clothing, cloth, curtains, and sheets.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

(Raw materials used)
<Particle group (A)>
Particle group (A-1): A group of anionic surfactant-containing particles produced in Production Example 1. The content of the anionic surfactant is 83% by mass, the water content is 5% by mass, the average particle size is 370 μm, and the bulk density is 0.68 g / cm ³ .
Particle group (A-2): A group of alkyl sulfate ester salt particles having 12 to 14 carbon atoms (trade name "Sulfopon1214G" manufactured by BASF). The content of the anionic surfactant is 99% by mass or more, the water content is less than 1% by mass, the average particle size is 440 μm, and the bulk density is 0.64 g / cm ³ .

<Particle group (A')>
Particle group (A'-1): A group of anionic surfactant-containing particles produced in Production Example 2. The content of anionic surfactant is 15.5% by mass, the content of nonionic surfactant is 4.2% by mass, the water content is 7.5% by mass, the average particle size is 380 μm, and the bulk density is 0.84 g / cm ³ .

<Particle group (B)>
Particle group (B-1): A group of nonionic surfactant-containing particles produced in Production Example 3. The content of nonionic surfactant is 50% by mass, the content of water-swellable clay mineral is 40% by mass, the water content is 4% by mass, the average particle size is 480 μm, and the bulk density is 0.68 g / cm ³ .
Particle group (B-2): A group of nonionic surfactant-containing particles produced in Production Example 4. The content of nonionic surfactant is 30% by mass, the content of water-swellable clay mineral is 60% by mass, the water content is 6% by mass, the average particle size is 430 μm, and the bulk density is 0.63 g / cm ³ .

<Particle group (C)>
Particle group (C-1): Group of Glauber's salt granules (trade name "Detergent White Speckle" manufactured by Zhejiang HANSHA Detergents), sodium sulfate content 98% by mass, sodium silicate content 1% by mass, carboxymethyl cellulose content 1% by mass, water content less than 1% by mass, average particle size 880 μm, bulk density 1.1 g / cm ³ .

<Particle group (D)>
Particle group (D-1): Group of sodium percarbonate particles (trade name "SPCC", manufactured by Zhejiang Jinke Chemicals, with coating), sodium percarbonate content 82.5% by mass, water content 1% by mass, average. Particle size 830 μm, bulk density 0.94 g / cm ³ .
Particle group (D-2): Group of sodium percarbonate particles (trade name "SPC", manufactured by Zhejiang Chemicals, uncoated), sodium percarbonate content 87% by mass, water content 1.5% by mass, average Particle size 690 μm, bulk density 0.91 g / cm ³ .

<Particle group (E)>
Particle group (E-1): Group of sodium carbonate particles (trade name "grain ash" manufactured by Asahi Glass Co., Ltd.), sodium carbonate content 99% by mass, water content less than 1% by mass, average particle size 280 μm, bulk density 0.95 g / Cm ³ .
Particle group (E-2): Group of sodium hydrogen carbonate particles (trade name "sodium hydrogen carbonate" manufactured by Qingdao Kaiwan Co., Ltd.), sodium hydrogen carbonate content 99% by mass, water content less than 1% by mass, average particle diameter 250 μm, bulk Density 1.2 g / cm ³ .

<Other ingredients>
Zeolite: Type A zeolite, trade name "Silton B" manufactured by Mizusawa Industrial Chemicals, Inc., pure content 80% by mass.
Enzyme: A mixture of "Sabinase 12T" / "Cannase 24T" / "LIPEX100T" / "Cellclean 4500T" (trade name, manufactured by Novozymes) = 4/4/1/1 (mass ratio).
Fluorescent agent: "Tinopearl CBS-X" (distyrylbiphenyl derivative, water-soluble fluorescent agent) / "Tinopearl AMS-GX" (bis (triazinylaminostilbene) disulfonic acid derivative, semi-dispersible fluorescent agent) (both commercial products Name, manufactured by BASF) = 1/1 (mass ratio) mixture.
Perfume: Perfume composition A according to Tables 11 to 18 of JP-A-2002-146399.

(Production Example 1: Preparation of particle group (A-1))
[Manufacturing of α-sulfofatty acid alkyl ester salt paste]
Methyl palmitate (trade name "Pastel M-16" manufactured by Lion) and methyl stearate (trade name "Pastel M-180" manufactured by Lion) are mixed so as to have an 80:20 (mass ratio). , Fatty acid methyl ester mixture.
330 kg of the fatty acid methyl ester mixture was placed in a reactor equipped with a stirrer and having a capacity of 1 kL. While stirring, anhydrous sodium sulfate was added as a color inhibitor in an amount of 5% by mass based on the fatty acid methyl ester mixture. While continuing stirring at a reaction temperature of 80 ° C., 110 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with nitrogen gas (1.1 times mol with respect to the fatty acid methyl ester mixture) was bubbled over 3 hours. I blew it at a constant speed. Further, aging was carried out for 30 minutes while keeping the temperature at 80 ° C.
After transfer to the esterification tank, 14 kg of methanol was supplied and an esterification reaction was carried out at 80 ° C. Further, aging was carried out for 30 minutes while keeping the temperature at 80 ° C.
Further, the esterified product extracted from the reaction apparatus was continuously neutralized by adding an equivalent amount of sodium hydroxide aqueous solution using a line mixer.
Then, this neutralized product was injected into the bleach mixing line, and the 35% hydrogen peroxide solution was added to 1 to 2% by mass in terms of pure content with respect to AI (active ingredient: α-sulfofatty acid alkyl ester metal salt). It was bleached by supplying it in an amount of 1 and mixing it while keeping it at 80 ° C. to obtain an α-sulfofatty acid alkyl ester salt-containing paste.

The obtained α-sulfo fatty acid alkyl ester salt-containing paste was introduced into a vacuum thin film evaporator (heat transfer surface: 4 m ² , manufactured by Ballestra) at 200 kg / hour, and the inner wall heating temperature was 100 to 160 ° C. and the degree of vacuum was 0. It was concentrated at 01 to 0.03 MPa and taken out as a melt having a temperature of 100 to 130 ° C.

Then, this melt is cooled to 20 to 30 ° C. in 0.5 minutes using a belt cooler (manufactured by Nippon Belting Co., Ltd.), and further α-sulfon using a crusher (manufactured by Nippon Belting Co., Ltd.). Fatty acid alkyl ester salt flakes were obtained.

1 kg of the above flakes are aged at 30 ° C. for 28 days (crystallization treatment), and the obtained MES flakes are crushed with a speed mill (crushing conditions: rotation speed 1500 rpm, screen hole diameter 1.0 mm, temperature inside the crusher 25 ° C). Then, a group of particles containing α-sulfofatty acid methyl ester sodium salt (MES) was obtained. The particles and A-type zeolite were put into a container rotary mixer and mixed to obtain a particle group (A-1). The content of α-sulfofatty acid methyl ester salt in the particle group was 83% by mass. The zeolite content was 12% by mass.

(Production Example 2: Preparation of particle group (A'-1))
According to the composition shown in Table 1, the particle group (A'-1) was produced by the following steps (1) to (3).
The raw materials shown in Table 1 are as follows.
MES: Sodium salt of fatty acid methyl ester sulfonate with 16 carbon atoms of fatty acid residue: 18 carbon atoms = 83:17 (mass ratio) (manufactured by Lion, AI = 70% by mass, the rest is unreacted fatty acid methyl ester, Sodium sulfate, methyl sulfate, fatty acid, water, etc.).
LAS-Na: Linear alkyl (10 to 14 carbon atoms) Sodium benzenesulfonate (trade name "Rypon LH-200" manufactured by Lion, LAS-H pure content 96% by mass) at the time of preparing the surfactant composition by 48 mass Neutralize with% aqueous sodium hydroxide solution).
AE (C12EO7): Nonionic surfactant, trade name "LMAO-90" manufactured by Lion Chemical Co., Ltd.), polyoxyethylene lauryl ether having an average number of moles of 7 oxyethylene groups added.
Soap: Fatty acid sodium with 14 to 20 carbon atoms (manufactured by Lion, pure content 66% by mass, fatty acid composition; C14 = 1.0% by mass, C16 = 43.3% by mass, C18F0 (stearic acid) = 6.6% by mass %, C18F1 (oleic acid) = 41.6% by mass, C18F2 (linoleic acid) = 7.2% by mass, C20 = 0.3% by mass, molecular weight; 291).
Sodium carbonate: Trade name "grain ash" manufactured by Asahi Glass Co., Ltd., average particle diameter 320 μm, bulk density 1.07 g / cm ³ .
Potassium carbonate: Potassium carbonate (powder), average particle size 490 μm, bulk density 1.30 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
Glauber's salt: Sodium sulfate: Trade name "Neutral anhydrous Glauber's salt A0" manufactured by Shikoku Chemicals Corporation.
Zeolite: Type A zeolite, trade name "Silton B" manufactured by Mizusawa Industrial Chemicals, Inc., pure content 80% by mass.
PA: Sodium polyacrylate, trade name "Sokaran PA30CL" manufactured by BASF.
Fluorescent agent: "Tinopearl CBS-X" (distyrylbiphenyl derivative, water-soluble fluorescent agent) / "Tinopearl AMS-GX" (bis (triazinylaminostilbene) disulfonic acid derivative, semi-dispersible fluorescent agent) (both commercial products Name, manufactured by BASF) = 1/1 (mass ratio) mixture.

・ Process (1)
A part of LAS-Na (25% by mass with respect to MES) was added to the aqueous slurry of MES (prepared to have a water content of 25% by mass) obtained by sulfonated and neutralized the fatty acid ester of the raw material. Then, the mixture was concentrated under reduced pressure in a thin film dryer until the water content reached 11% by mass to obtain a mixed concentrate of MES and LAS-Na.

・ Process (2)
Water was placed in a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 80 ° C. A surfactant excluding the mixed concentrate (MES and a part of the above LAS-Na) was added thereto, and the mixture was stirred for 10 minutes. Subsequently, PA was added. After further stirring for 10 minutes, a part of zeolite (from the blending amount shown in Table 1 below, 1.0% by mass for addition at the time of mixing added in the following step (3), 5.0% by mass for crushing aid). %), Sodium carbonate and sushi were added. After further stirring for 20 minutes to prepare a spray-drying slurry having a water content of 38% by mass, the spray-dried product was spray-dried under the condition of a hot air temperature of 280 ° C. using a countercurrent spray-drying tower, and the average particle size was 320 μm and the bulk density was 0.30 g. Spray-dried particles at / ^cm3 and water content of 6% by mass were obtained.

・ Process (3)
The obtained spray-dried particles, the mixed concentrate obtained in step (1), 1.0% by mass of zeolite, a fluorescent agent, and water were put into a continuous kneader (KRC-S12 type, manufactured by Kurimoto, Ltd.). Then, the particles were kneaded under the conditions of a kneader rotation speed of 135 rpm and a jacket temperature of 60 ° C. to obtain a kneaded product containing a surfactant and having a water content of 7% by mass (kneading treatment). While extruding the kneaded product with a peretter double (EXDFJS-100 type manufactured by Fuji Powder Co., Ltd.) equipped with a die with a hole diameter of 10 mm, cut it with a cutter (cutter peripheral speed is 5 m / s) and lengthen it. A pellet-shaped molded product having a diameter of about 5 to 30 mm was obtained.
Next, an amount equivalent to 5.0% by mass of zeolite as a pulverizing aid was added to the obtained pellet-shaped molded product, and the Fitzmill was arranged in three stages in series in the coexistence of cold air (10 ° C., 15 m / s). Grinding using (DKA-3, manufactured by Hosokawa Micron) (screen hole diameter: 1st stage 12 mm / 2nd stage 7 mm / 3rd stage 3 mm, rotation speed: 1st stage 4700 rpm / 2nd stage 4700 rpm / 3rd stage 4700 rpm ), A particle group (A'-1) was obtained.

(Production Examples 3 and 4: Preparation of particle groups (B-1) and (B-2))
Particle groups (B-1) and (B-2) were produced by the following methods according to the composition shown in Table 2.
The raw materials shown in Table 2 are as follows.
Nonion Surfactant: Trade name "EMALEX707" Polyoxyethylene lauryl ether manufactured by Nippon Emulsion Co., Ltd., having an average number of moles of oxyethylene groups added of 7.
Sodium carbonate: Brand name "grain ash" manufactured by Asahi Glass Co., Ltd.
Bentonite: Product name "Laundrosil PRW414" manufactured by Zudochemy.

Of the ingredients shown in Table 2, bentonite and sodium carbonate are put into a radige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a plow blade-shaped excavator and having a clearance between the excavator and the wall surface of 5 mm (filling rate 50 volumes). %), And stirring of the spindle 200 rpm and the chopper 200 rpm was started. Thirty seconds after the start of stirring, a nonionic surfactant was added in 2 minutes, and the mixture was stirred and granulated under the condition of a jacket temperature of 30 ° C. to obtain a desired particle group.

(Examples 1 to 17, Comparative Examples 1 to 3)
Of the compositions shown in Tables 3 and 4, components other than the fragrance were simultaneously put into a container rotary cylindrical mixer at a rate of 15 kg / min and mixed. This container rotary cylindrical mixer has a container with a diameter of 0.7 m, a length of 1.4 m, an inclination angle of 3.0 °, an outlet weir height of 0.15 m, and an internal mixing blade with a height of 0.1 m and a length. It is a specification in which four 1.4 m flat blades are attached every 90 °. Further, the rotation speed of the internal mixing blade was adjusted so that the Froude number was Fr = 0.2.
The fragrance was sprayed on the fluidized particles by rotating the container, and the particles were rolled for 1 minute to obtain a granular detergent.

(Evaluation methods)
The granular detergents obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 3 and 4.

<Preservation test>
The following storage tests were performed on the granular detergents produced in each example.
From the outside, using a paper consisting of three layers: coated cardboard (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ). A box having a length of 15 cm, a width of 9.3 cm, and a height of 18.5 cm was prepared, and 1.0 kg of granular detergent was put in this box. The box containing the granular detergent was sealed and stored in a constant temperature and humidity chamber for 30 days. The constant temperature and humidity chamber was repeatedly operated at 45 ° C. for 75% RH for 8 hours and at 25 ° C. for 55% RH for 16 hours. After storage for 30 days, the box was taken out from the constant temperature and humidity chamber and left at a temperature of 25 ° C. and a relative humidity of 60% for 6 hours.

<Evaluation of liquidity>
[Measurement of angle of repose]
The liquidity was evaluated by measuring the angle of repose (°) by the following method.
Place an acrylic measuring instrument with a horizontal lid (height 10 cm x depth 10 cm x width 3 cm) with an angle scale on a flat surface, and place the measuring instrument's horizontal lid (height 10 cm x width 3 cm side). In the closed state, the granular detergent after the completion of the above-mentioned storage test was poured into the measuring instrument from a position where the height from the upper surface of the measuring instrument was 1 to 2 cm.
When the height from the upper surface of the measuring instrument exceeded about 0 to 1 cm and the granular detergent became heaped, the side lid was gently opened and the granular detergent was naturally discharged by gravity.
After the completion of the discharge, the angle (inclination angle) between the surface (inclined surface) of the granular detergent remaining in the measuring instrument and the horizontal plane was read from the scale. The above operation was performed three times, and the average value was taken as the value of the angle of repose. Liquidity was evaluated based on the following evaluation criteria. A or B is preferable, and A is particularly preferable because it is easy to scoop with a spoon.
As the acrylic measuring instrument, a horizontal lid was provided on one of the sides formed by the height and the width, and the angle scale was written on the side surface formed by the height and the depth.
Evaluation Criteria A: The angle of repose is 40 ° or less.
B: The angle of repose is over 40 ° and 50 ° or less.
C: The angle of repose is over 50 ° and 60 ° or less.
D: The angle of repose is over 60 °.

<Dust generation suppression>
The amount of dust generated was investigated by the following method.
LD-3 type digital dust meter (trade name, Shibata Scientific Instruments) that can measure the amount of fine powder (dust) of granular detergent generated in the container on the top of the container with a height of 40 cm, a width of 30 cm, and a depth of 30 cm. (Made by Kogyo Co., Ltd.) was installed.
Keeping the atmosphere inside the container at a temperature of 25 ° C. and a relative humidity of 60%, 50 g of granular detergent was dropped into the container from the sample inlet provided at the top of the container, and at the same time, the switch of the digital dust meter was turned on. The dust count after standing for 5 minutes was read.
The dust generation suppression property was evaluated based on the following evaluation criteria. A or B is preferable, and A is particularly preferable because it is easy to scoop with a spoon.
Evaluation Criteria A: The dust count is 100 or less.
B: The dust count is over 100 and 300 or less.
C: The dust count is over 300 and 500 or less.
D: The dust count is over 500.

<Storage stability of percarbonate>
[Measurement of residual rate of sodium percarbonate]
After the above storage test was completed, the entire granular detergent in the box was thoroughly mixed, and then the granular detergent was sampled according to the following procedure to measure the residual ratio of sodium percarbonate.
The box containing the granular detergent was placed on a horizontal table, and a spoon was used to scoop a spoonful (about 50 g) of the granular detergent from the center. About 25 g of the scooped granular detergent (sample) was precisely weighed up to 10 mg.
About 25 g of the finely weighed sample was placed in a 1 L beaker, 200 mL of a 33 mass% acetic acid aqueous solution was added, and the mixture was stirred and dissolved with a magnetic stirrer. Then, 40 mL of a 10 mass% potassium iodine aqueous solution was added, and the obtained solution was titrated with a 1 mol / L sodium thiosulfate solution. On the way, 2-3 drops of saturated ammonium molybdate were added when the solution became colorless, further titration was continued when the solution became pale yellow, and titration was completed when the solution became colorless again. The amount of effective oxygen (%) was determined by the following formula from the titration amount p (mL) of the 1 mol / L sodium thiosulfate solution dropped from the start of titration to the end of titration.
Amount of active oxygen (%) = {f × p × (1/2) × (1/1000) × 16} / g × 100 [In the formula, f is a factor of 1 mol / L sodium thiosulfate solution, and p is 1 mol. / L sodium thiosulfate solution titration (unit: mL), g is the mass of the sample (unit: g). ]

The amount of effective oxygen was determined by the above method for the remaining half of the sample, about 25 g. The average value of these was taken as the effective oxygen content of the sample.
Separately, the effective oxygen amount (%) of the particle group (D) used for producing the granular detergent was determined by the same calculation method as described above.
From these amounts of effective oxygen, the residual rate (%) of sodium percarbonate was determined by the following formula.
Residual rate of sodium percarbonate (%) = (effective oxygen amount (%) of sample / active oxygen amount (%) of particle group (D)) × 100 (%)
The storage stability of percarbonate was evaluated based on the following evaluation criteria. A or B is preferable, and A is particularly preferable.
Evaluation Criteria A: The residual rate of sodium percarbonate is over 70%.
B: The residual rate of sodium percarbonate is more than 55% to 70% or less.
C: The residual rate of sodium percarbonate is more than 40% to 55% or less.
D: The residual rate of sodium percarbonate is 40% or less.

As shown in Tables 3 and 4, all of the granular detergents of Examples 1 to 17 are excellent in dust generation suppressing property and excellent in scooping with a spoon. In addition, the fluidity was good even when stored under harsh conditions of high temperature, and the ease of scooping with a spoon was maintained. Furthermore, the performance of percarbonate was maintained well even when stored under harsh conditions of high temperature.
In particular, since the particle group (A-1) contains a high concentration of α-SF salt having high crystallinity among the anionic surfactants, the particles become brittle with time by themselves, and dust generation and fluidity decrease. However, in Examples 1 to 3, 5 to 17, dust generation and a decrease in fluidity were suppressed.

On the other hand, the fluidity of Comparative Example 1 not including the particle group (C) was significantly lower than that of Example 3.
Comparative Example 2 not containing the particle group (B) has a significantly reduced dust generation inhibitory property and is also inferior in fluidity as compared with Example 3.
In Comparative Example 3 which does not contain the particle group (B) and has a low content of the anionic surfactant in the particle group (A), the storage stability of the percarbonate is greatly reduced, and the fluidity and dust generation inhibitory property are also improved. Inferior.
Comparative Example 3 is an example in which the particle group (A) is produced by a method (kneading pulverization method) in which a powder raw material containing spray-dried particles and a liquid raw material are compression-mixed by a kneader and then pulverized. Zeolites are included in the composition for the purpose of preventing the adhesion of raw materials to spray dryers, kneaders and crushers, and also include water derived from liquid raw materials. It is considered that the granular detergent of Comparative Example 3 contains a relatively large amount of such zeolite and water, which causes a decrease in the storage stability of the percarbonate.

Claims (6)

A granular detergent containing the following particle group (A), the following particle group (B), the following particle group (C), and the following particle group (D).
A granular detergent in which the content of the particle group (A) is 4 to 15% by mass with respect to the total mass of the granular detergent.
Particle group (A): A particle group of anionic surfactant-containing particles (a) containing 40% by mass or more of an anionic surfactant and having an anionic surfactant content higher than that of other surfactants.
Particle group (B): Nonion interface containing 30% by mass or more of a nonionic surfactant and 25% by mass or more of a water-swellable clay mineral, and the content of the nonionic surfactant is higher than the content of other surfactants. A group of particles of the activator-containing particle (b).
Particle group (C): A group of water-soluble inorganic salt-containing particles (c) that do not contain percarbonate and contain 70% by mass or more of water-soluble inorganic salt, and have an average particle diameter of 500 μm or more.
Particle group (D): A particle group of percarbonate-containing particles (d) containing 80% by mass or more of percarbonate. The granular detergent according to claim 1, further comprising the following particle group (E).
Particle group (E): A group of water-soluble inorganic salt-containing particles (e) containing neither a surfactant nor a percarbonate and containing 80% by mass or more of a water-soluble inorganic salt, and having an average particle diameter of less than 500 μm. A group of particles that are. The granular detergent according to claim 1 or 2, wherein the water content is 3% by mass or less. The granular detergent according to any one of claims 1 to 3, wherein the content of zeolite is 10% by mass or less with respect to the total mass of the granular detergent. Claim 1 in which the average particle size of the particle group (D) is 500 μm or more, and the absolute value of the difference between the average particle size of the particle group (C) and the average particle size of the particle group (D) is 300 μm or less. The granular detergent according to any one of 4 to 4. The content of the particle group (B) is 2 to 15% by mass, the content of the particle group (C) is 10 to 30% by mass, and the particle group is based on the total mass of the granular detergent. The granular detergent according to any one of claims 1 to 5, wherein the content of (D) is 10 to 50% by mass.