JP2019077760A - Granular detergent - Google Patents

Abstract

To provide a granular detergent having a small reduction in fluidity even when stored under high temperature conditions.SOLUTION: There is provided a granular detergent containing granules (A), granules (B), granules (C) and granules (D). Granules (A): granules of anionic surfactant-containing granules (a) containing 40 mass% or more of an anionic surfactant having a content of an anionic surfactant higher than a content of the other surfactants. Granules (B): granules of nonionic surfactant-containing granules (b) containing 30 mass% or more of a nonionic surfactant and 25 mass% or more of a water-swellable clay mineral and having a content of a nonionic surfactant higher than a content of the other surfactants. Granules (C): granules of water-soluble inorganic salt-containing granules containing no percarbonate, containing 70 mass% or more of a water-soluble inorganic salt and having an average particle diameter of 500 μm or more. Granules (D): granules of percarbonate-containing granules (d) containing 80 mass% or more of a percarbonate.SELECTED DRAWING: None

Description

  The present invention relates to granular detergents.

Among granular cleaners, surfactant concentration and powder bulk density have become mainstream from the viewpoints of transportation cost, reduction of space required for storage and display, and omission of weighing operation in general homes.
As a method of achieving concentration of surfactant and high bulk density of powder, there is known a method of dry blending granules containing surfactant at high concentration.
In Patent Document 1, surfactant particles containing a strong crystalline anionic surfactant at a high concentration are used in combination with particles containing a nonionic surfactant as a main agent to suppress fine powder and maintain good fluidity. A method has been proposed.

JP 10-09 599 A

Depending on the storage place and use place of the detergent, the detergent 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 high temperature, the fluidity may be reduced, and it may be difficult to spoon it.
The present invention is directed to particulate detergents which exhibit a small decrease in fluidity even when stored at high temperature conditions.

The present invention has the following aspects.
[1] A particulate detergent comprising 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 in which the content of the anionic surfactant is higher than the content of other surfactants.
Particle group (B): A nonionic interface comprising 30% by mass or more of a nonionic surfactant and 25% by mass or more of a water-swellable clay mineral, wherein the content of the nonionic surfactant is higher than the content of other surfactants Particle group of activator-containing particles (b).
Particle group (C): A group of water-soluble inorganic salt-containing particles (c) containing 70% by mass or more of a water-soluble inorganic salt without containing a percarbonate, and having 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] The granular detergent of [1], further comprising the following particle group (E):
Particle group (E): a group of water-soluble inorganic salt-containing particles (e) containing at least 80 mass% of a water-soluble inorganic salt, containing neither surfactant nor percarbonate, and having an average particle size of less than 500 μm Particle group.
[3] The granular detergent of [1] or [2] having a water content of 3% by mass or less.
[4] The granular detergent according to any one of [1] to [3], wherein the content of the zeolite is 10% by mass or less based on the total mass of the granular detergent.
[5] The average particle diameter of the particle group (D) is 500 μm or more, and the absolute value of the difference between the average particle diameter of the particle group (C) and the average particle diameter of the particle group (D) is 300 μm or less Granular detergent according to any one of [1] to [4].

  According to the present invention, it is possible to obtain a granular detergent having a small decrease in fluidity even when stored at high temperature conditions.

[Measuring 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 an evaporative volatile matter after heating at 130 ° C. for 20 minutes with an infrared moisture meter (for example, Kett moisture meter manufactured by Kett Scientific Research Co., Ltd.) It is.
[Method of measuring bulk density]
In the present specification, the bulk density of the particle group is a value measured according to JIS K3362 (2008).

[Method of measuring 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 classification operation using sieves of 10 stages of sieves with openings of 1,400 μm, 1180 μm, 1000 μm, 710 μm, 500 μm, 425 μm, 355 μm, 250 μm, 150 μm and 75 μm and a tray.
Classification operation, in the pan, stacked in order from small sieves with large openings to large sieves with large openings, put 100 g / times of sample from the top of the 1400 μm sieve, cover it, and cover with a low-tap sieve shaker (stock The product is attached to Iida Mfg. Co., Ltd., tapping: 156 times / min, rolling: 290 times / min), vibrated for 10 minutes, and then the samples (classified samples) remaining on the respective sieves and pans are collected every sieve. Do. The mass of the classified sample of each particle diameter is measured, and the mass frequency (%) is calculated.
When the average particle size is to be determined, let the mesh size of the first sieve with an integrated mass frequency of 50% or more be “a μm”, the mesh size of the sieve one step larger than a μm be “b μm”, and the mesh size of a μm from the receiving tray Assuming that the integrated value of the mass frequency up to “c%” and the mass frequency on the a μm screen “d%”, the average particle size (50 mass% particle size) is determined by the following equation (1) 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, anionic surfactant-containing particles (a) constituting the particle group (A), nonionic surfactant-containing particles (b) constituting the particle group (B), and the particle group (C) The water-soluble inorganic salt-containing particles (c) and the percarbonate-containing particles (d) constituting the particle group (D) are present as independent particles.

<Particle group (A)>
The particle group (A) contains 40% by mass or more of an anionic surfactant, and the anionic surfactant-containing particles (a) (hereinafter simply referred to simply as "the content of the anionic surfactant is higher than the content of other surfactants. Also referred to as "particles (a)".
The particle group (A) contained in the granular detergent may be of one type or of two or more types having different compositions. The composition of the particles (a) constituting one kind of particle group (A) is assumed to be 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-sulfo fatty acid alkyl ester salt.
The type of the α-sulfo fatty acid alkyl ester salt (hereinafter also referred to as α-SF salt) is not particularly limited. What is represented by following formula (1) is preferable.
R ¹ -CH (SO ₃ M) -COOR ² (1)
In the formula (1), R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, preferably 14 to 16 carbon atoms, or a linear or branched alkenyl group having 8 to 20 carbon atoms It is. R ² is an alkyl group having 1 to 6 carbon atoms, and preferably 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; ammonium salts and the like. Among them, alkali metal salts are preferred.

(1-2) Linear or branched alkyl benzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(1-3) C10-C20 alkanesulfonic acid salt.
(1-4) C10-C20 alpha-olefin sulfonate (AOS).
(1-5) C10-C20 alkyl sulfate or alkenyl sulfate (AS).
(1-6) 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), an average of 0. Alkyl (or alkenyl) ether sulfate (AES) which has C10-C20 linear or branched alkyl (or alkenyl) group which 5-10 mol added.
(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), the average of 3 to 3 The alkyl (or alkenyl) phenyl ether sulfate which has the C10-C20 linear or branched alkyl (or alkenyl) group which 30 mol was added.
(1-8) 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), an average of 0. The alkyl (or alkenyl) ether carboxylate which has a C10-C20 linear or branched alkyl (or alkenyl) group which 5-10 mol added.
(1-9) alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(1-10) Monoalkyl, dialkyl or sesquialkyl phosphate having an alkyl group of 10 to 20 carbon atoms.
(1-11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(1-12) C10-C20 higher fatty acid salt (soap).
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 used alone or in combination of two or more.
As an anionic surfactant, (alpha) -SF salt is preferable and (alpha) -sulfo fatty acid methyl ester sodium salt (MES) is more preferable.

The particles (a) may contain a surfactant other than an anionic surfactant. For example, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be mentioned.
Examples of the nonionic surfactant include (2-1) to (2-8) described later.
The nonionic surfactant may be used alone or in combination of two or more.

The following may be mentioned as cationic surfactants.
(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" represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.
"Short-chain alkyl" includes substituents such as phenyl group, benzyl group, hydroxy group and hydroxyalkyl group, and may have an ether bond between carbons. Among them, alkyl groups having 1 to 4 carbons, preferably 1 to 2 carbons; benzyl groups; hydroxyalkyl groups having 2 to 4 carbons, preferably 2 to 3 carbons; polys having 2 to 4 carbons, preferably 2 to 3 carbons An oxyalkylene group is mentioned as a suitable thing.
The cationic surfactant may be used alone or in combination of two or more.

Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants, amide betaine-based and amine oxide-based amphoteric surfactants, and the like. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauric acid amidopropyl betaine, alkylamine oxide can be mentioned.
The amphoteric surfactant may be used alone or in combination of two or more.

40 mass% or more is preferable, as for content of the sum total of surfactant with respect to the total mass of particle | grains (a), 50 mass% or more is more preferable, and 60 mass% or more is more preferable. The upper limit may be 100% by mass. It is preferable at the point which can reduce the compounding quantity of particle | grains (a) required in order to exhibit cleaning performance as it is more than the lower limit of the said range, and can suppress dusting.
The total amount of anionic surfactant contained in the particle (a) is the total amount of each of the other surfactants (for example, the total amount of nonionic surfactant, the total amount of cationic surfactant, or amphoteric surfactant More than the total amount of
The total content of anionic surfactants is 40% by mass or more, preferably 50% by mass or more, based on the total mass of the particles (a). The upper limit may be 100% by mass. It is preferable at the point which can reduce the compounding quantity of particle | grains (a) required in order to exhibit cleaning performance as it is more than the lower limit of the said range, and can suppress dusting.
80-100 mass% is preferable with respect to content of the sum total of surfactant in particle | grains (a), and 90-100 mass% is more preferable, and 95-100 mass is preferable. % Is more preferred.

[Other optional ingredients]
The particles (a) may further contain other optional components other than the surfactant, as necessary. As other optional components, known components to be incorporated into particulate detergents can be used, such as organic builders, water-soluble inorganic salts, water-insoluble inorganic salts, fluorescent agents, polymers, enzyme stabilizers, anti-caking agents, Examples include reducing agents, metal ion scavengers, pH adjusters, and the like.

  Examples of the organic builder include citrate, amino carboxylate, hydroxyamino carboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid, and the like.

Examples of water-soluble inorganic salts include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate and sodium sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite Crystalline layered sodium silicate, amorphous alkali metal silicate; Sulfate such as sodium sulfate and potassium sulfate; Alkali metal chloride such as sodium chloride and potassium chloride; Pyrophosphate, tripolyphosphate, orthophosphoric acid And phosphates such as metaphosphates, hexametaphosphates and phytates; complexes of sodium carbonate and amorphous alkali metal silicates etc.
In addition, as sodium carbonate and sodium sulfate, an anhydride is used suitably. The descriptions of “sodium carbonate” and “sodium sulfate” in the present specification refer to an anhydride.

Examples of water-insoluble inorganic salts include aluminosilicates and clay minerals. As a clay mineral, the below-mentioned water-swellable clay mineral can be illustrated.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used. Crystalline aluminosilicates are preferred from the viewpoint of cation exchange capacity. As the crystalline aluminosilicate, zeolites such as A-type, X-type, Y-type and P-type zeolites are preferable.

  20 mass% or less is preferable with respect to the total mass of particle | grains (a), and 15 mass% or less is more preferable. It may be zero. It is excellent by the storage stability of percarbonate as it is below the upper limit of the said range.

7 mass% or less is preferable, and, as for the water content of particle group (A), 6 mass% or less is more preferable. The lower limit is not particularly limited. Substantially 0.5 mass% or more is preferable. It is excellent by the storage stability of percarbonate as it is below the upper limit of the said range.
When the granular detergent contains two or more 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 (particles) The same applies to groups (B) to (E).

250-550 micrometers is preferable and, as for the average particle diameter of particle group (A), 350-450 micrometers is more preferable. When the average particle diameter of the particle group (A) is at least the lower limit of the above range, powdering is small and handling is easy, and when it is at the upper limit or less, the solubility in water is good.
When the particulate detergent contains two or more particle groups (A) having different compositions, the preferred range of the average particle size of the particle group (A) means the preferred range of the average particle size of each particle group (The same applies to particle groups (B) to (E)).

0.6-1.0 g / cm < ³ > is preferable and, as for the volume density of particle group (A), 0.6-0.7 g / cm < ³ > is more preferable. Classification can be suppressed when the bulk density of the particle group (A) is at least the lower limit value of the above range, and the difference with the bulk density of the particle group (B) becomes smaller when the volume density is at the upper limit value or less. Dust generation can be suppressed.
When the particulate detergent contains two or more particle groups (A) having different compositions, the preferred range of the bulk density of the particle group (A) means the preferred range of the bulk density of each particle group (particles (particles) The same applies to groups (B) to (E).

  4-15 mass% is preferable, as for content of the sum total of particle group (A) with respect to the total mass of granular detergent, 7-15 mass% is more preferable, and 9-12 mass% is further more preferable. The adhesion of the particle group (B) can be suppressed when the content of the particle group (A) is not less than the above lower limit, and the dustability of the particle detergent and the particle detergent after storage can be suppressed when the content is not more than the above upper limit. In terms of the fluidity of

The method for producing the particle group (A) may be any method as long as the content of the anionic surfactant in the particle (a) can be 40% by mass or more, and any known method can be used. A commercial item may be used as 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 an α-SF salt (pasting step), flakes are prepared from the paste Processing (flaking process), preparing noodles from the flakes (noodleing process), preparing pellets from the noodles (pelletizing process), pulverizing the flakes, noodles or pellets to obtain particles The method which has a (grinding process) is mentioned.
The above (noodleing step) and (pelletizing step) are optional steps and may be omitted. Moreover, you may provide the process (classification process) which classifies particle groups after the above (grind process). Furthermore, after the above (flaking step), (noodleing step) or (pelletizing step), a step (aging step) of aging the flakes, noodles or pellets may be provided before the grinding step.

<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 the content 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 of one type or of two or more types having different compositions. The composition of the particles (b) constituting one kind of particle group (B) is assumed to be uniform.

The nonionic surfactant is not particularly limited as long as it is conventionally used in granular detergents, and examples thereof include the following.
(2-1) 3 to 20 moles, preferably 3 to 20 moles, more preferably 5 to 20 moles 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 Added polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. As aliphatic alcohol used here, a primary alcohol and a secondary alcohol are mentioned. Also, the alkyl group may have a branched chain. As aliphatic alcohol, primary alcohol is preferred.
(2-2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(2-3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long chain fatty acid alkyl ester.
(2-4) polyoxyethylene sorbitan fatty acid ester.
(2-5) polyoxyethylene sorbite fatty acid ester.
(2-6) Polyoxyethylene fatty acid ester.
(2-7) polyoxyethylene hydrogenated castor oil.
(2-8) Glycerin fatty acid ester.
The nonionic surfactant may be used alone or in combination of two or more.

  The particles (b) may contain a surfactant other than the nonionic surfactant. For example, anionic surfactant, cationic surfactant, amphoteric surfactant etc. are mentioned. These include the same as the anionic surfactant, the cationic surfactant and the amphoteric surfactant in the particles (a).

30 mass% or more is more preferable, and, as for content of the sum total of surfactant with respect to the total mass of particle | grains (b), 40 mass% or more is further more preferable. The upper limit is 75% by mass, preferably 60% by mass or less. The lower limit value of the above range is preferable in view of the cleaning performance. The flowability of particle | grains (b) becomes favorable for it to be below an upper limit.
The total amount of nonionic surfactant contained in the particles (b) is the total amount of each of the other surfactants (for example, the total amount of anionic surfactant, the total amount of cationic surfactant, or 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). An upper limit is 75 mass%, 70 mass% or less is preferable, and 65 mass% or less is more preferable. Dust generation of other particle groups can be favorably suppressed as it is more than the lower limit value of the said range, and balance with other components is good as it is less than the upper limit value.
The content of the total of the nonionic surfactant is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and more preferably 95 to 100% with respect to the total content of the surfactant in the particles (b). % Is more preferred.

The "water-swellable clay mineral" means a clay mineral having a swelling power of 20 mL / 2 g or more. Here, the "swelling power" is expressed by the swelling volume (mL) of 2 g of water-swellable clay mineral, applying the test method of bentonite defined in the 15th revision Japanese Pharmacopoeia.
As water-swellable clay minerals, smectite clays such as bentonite, montmorillonite, saponite, beidellite, hectorite, stevensite, sauconite and nontronite, natural clays such as vermiculite, halloysite and swelling mica, synthetic clays of these, And mixtures thereof.
One or more water-swellable clay minerals may be used.

  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 based on the total mass of the particles (b). An upper limit is 70 mass%, 60 mass% or less is preferable, and 50 mass% or less is more preferable. The oil absorption capacity of the nonionic surfactant is good when it is at least the lower limit value of the above range, and the balance with other components is good when it is at the upper limit value or less.

  The particles (b) may further contain other optional components that do not correspond to either a surfactant or a water-swellable clay mineral, if necessary. Other optional components include those similar to the other optional components in particle (a) (with the exception of water-swellable clay minerals).

10 mass% or less is preferable, and, as for the water content of particle group (B), 5 mass% or less is more preferable. The lower limit is not particularly limited. It is preferably substantially 1% by mass or more. It is excellent by the storage stability of percarbonate as it is below the upper limit of the said range.
300-600 micrometers is preferable and, as for the average particle diameter of particle group (B), 400-500 micrometers is more preferable. When the average particle diameter of the particle group (B) is at least the lower limit of the above range, powdering is small and handling is easy, and when it is at the upper limit or less, the solubility in water is good.
0.5-0.9 g / cm < ³ > is preferable and, as for the bulk density of particle group (B), 0.6-0.8 g / cm < ³ > is more preferable. Classification can be suppressed as it is more than the lower limit value of the said range, a difference with the volume density of particle group (A) becomes small as it is less than the upper limit value, mixing property becomes favorable, and dust generation can be suppressed.
2-15 mass% is preferable, and, as for content of the sum total of particle group (B) with respect to the total mass of granular detergent, 4-10 mass% is more preferable. Dust generation of other particle groups can be suppressed as content of particle group (B) is more than the said lower limit, and it is preferable at the point of the fluidity | liquidity after preservation | save of granular detergent as it is below the said upper limit.

A known method can be used as a method of producing the particle group (B). A commercial item may be used as particle group (B).
For example, it can be manufactured by a method of stirring and mixing a water-swellable clay mineral and other optional components as needed, adding a nonionic surfactant thereto, and stirring and granulating.

<Particle group (C)>
The particle group (C) is a water-soluble inorganic salt-containing particle (c) (hereinafter, also simply referred to as "particle (c)") containing no percarbonate and containing 70% by mass or more of a water-soluble inorganic salt. It is a group, and is a particle group having an average particle diameter of 500 μm or more.
The particle group (C) contained in the granular detergent may be of one type or of two or more types having different compositions. The composition of the particles (c) constituting one kind of particle group (C) is assumed to be uniform.

Examples of the water-soluble inorganic salt include the same water-soluble inorganic salts as the other optional components in the particles (a).
The particles (c) are preferably granules containing a water-soluble inorganic salt and a binder. By using a granulated material, control of the average particle size and bulk density is facilitated.
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 which 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 at 100C per 100 g of water. The organic water-soluble polymer compound may be used alone or in combination of two or more.
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 polysulfonic acid salts, polyvinyl pyridine salts, polyvinyl imidazolium salts and the like. The polysaccharides include various natural or synthetic polysaccharides.
Examples of polyester-based polymer compounds include copolymers or terpolymers of terephthalic acid and ethylene glycol and / or propylene glycol units.
Examples of peptide-based polymer compounds or derivatives thereof include gelatin, casein, albumin, collagen, polyglutamate, polyaspartate, polylysine, polyarginine and derivatives thereof.
Water-soluble polyurethane etc. are mentioned as polyurethane.
Other water-soluble polymer compounds such as polyethylene glycol can also be used.

In particular, when a water-soluble inorganic salt is granulated in the presence of water using a water-soluble organic polymer compound having a hydrophilic functional group such as anionic, amphoteric or nonionic as a binder, the water-soluble inorganic salt is hydrated It is preferable in that it is easy to do.
Examples of the water-soluble organic polymer compound having an anionic group include polymer compounds having a carboxyl group and a sulfo group, and water-soluble polysaccharides 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 salts thereof, and copolymers of these monomers with other vinyl monomers and vinyl polycarboxylic acids (salts) such as salts thereof. Examples of the water-soluble polymer compound having a sulfo group include monomers obtained by polymerizing monomers such as acrylamidopropanesulfonic acid, methacrylamidopropanesulfonic acid, styrenesulfonic acid, salts thereof, and these polymers and other vinyl compounds. Examples thereof include vinyl polysulfonic acid (salts) such as copolymers with polymers and salts thereof. Examples of water-soluble polysaccharides having an anionic group include, for example, polyuronate, alginate, polyaspartate, carrageenan, hyaluronate, chondroitin sulfate, carboxymethyl cellulose and the like.

As the amphoteric water-soluble polymer compound, for example, a copolymer of a vinyl monomer having an anionic group and a vinyl monomer having a cationic group, a vinyl compound having a carboxybetaine group or a sulfobetaine group An amphoteric polymer is mentioned, and an acrylic acid / dimethylamino ethyl methacrylic acid copolymer, an acrylic acid / diethylamino ethyl methacrylic acid copolymer etc. are mentioned specifically ,.
Examples of the nonionic water-soluble polymer compound include synthetic polymer compounds such as polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl ethyl 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 which 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 at 100C per 100 g of water.
It will not be specifically limited if it is such an inorganic water soluble high molecular compound, It can be used individually by 1 type or in combination of 2 or more types suitably. As the inorganic water-soluble polymer compound, a compound obtained by subjecting a solution containing a precursor compound of a metal alkoxide to a hydrolysis and condensation polymerization reaction is preferable, a silicate is more preferable, and sodium silicate is particularly preferable.

Granules containing a water-soluble inorganic salt and a binder can be produced by adding a binder and water to particles of the water-soluble inorganic salt, and granulating using known granulation methods.
0.1-10 mass% is preferable with respect to the total mass of particle | grains (c), and 0.5-8 mass% is more preferable.
0.1-30 mass% is preferable with respect to the total mass of particle | grains (c), and 0.5-20 mass% is more preferable.

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 based on the total mass of the particles (c). 100 mass% may be sufficient.
2 mass% or less is preferable, and, as for the water content of particle group (C), 1 mass% or less is more preferable. It may be zero. It is excellent by the storage stability of percarbonate as it is below the upper limit of the said range.
The average particle diameter of particle group (C) is 500 micrometers or more, 700-1100 micrometers are preferable, and 800-1000 micrometers are more preferable. When the average particle diameter of the particle group (C) is at least the lower limit value of the above range, the effect of improving the flowability of the granular detergent is excellent, and when it is at the upper limit value or less, the solubility in water is excellent.
0.9-1.3 g / cm < ³ > is preferable and, as for the bulk density of particle group (C), 1.0-1.2 g / cm < ³ > is more preferable. Fluidity becomes favorable in it being more than a lower limit of the above-mentioned range, and classification can be controlled as it is below an upper limit.
10-30 mass% is preferable, and, as for content of the sum total of particle group (C) with respect to the total mass of granular detergent, 15-25 mass% is more preferable. The content of the particle group (C) is preferably at least the lower limit value in terms of fluidity after storage of the granular detergent, and at not more than the 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) (hereinafter, also simply referred to as "particles (d)") containing 80% by mass or more of a percarbonate.
Percarbonate generates hydrogen peroxide when dissolved in water and contributes to the bleaching effect. When water, other detergent components and the like come in contact with the surface of the percarbonate, decomposition of the percarbonate may occur. Therefore, in order to prevent this, it is preferable to apply a treatment such as coating. As particles in the coated form, it is possible to use previously proposed oxygen bleach particles. For example, bleach particles described in Japanese Patent No. 2918991 can be mentioned. The bleach particles are granules formed by separately spraying a boric acid aqueous solution and an alkali metal silicate aqueous solution onto sodium percarbonate particles kept in a fluidized state and drying them. Stabilizers such as conventionally known chelating agents may be used in combination with the coating agent.

The content of the 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 is preferably 95% by mass or less 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, and 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 diameter 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 value of the above range, the stability of the particles (d) is excellent, and when it is at the upper limit value or less, 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. It is excellent in the fluid improvement effect by using particle group (C) as it is in this range. When at least one of the particle group (C) or the particle group (D) is contained in the particulate detergent, the difference between the average particle size of the particle group (C) and the average particle size of the particle group (D) is most A large value may be within the above range.
0.7-1.1 g / cm < ³ > is preferable and, as for the volume density of particle group (D), 0.8-1.0 g / cm < ³ > is more preferable. If it is not less than the lower limit value of the above range and not more than the upper limit value, the difference from the bulk density of the other particle groups is small, and classification hardly occurs.
10-50 mass% is preferable, and, as for content of the sum total of particle group (D) with respect to the total mass of granular detergent, 20-40 mass% is more preferable. The content of the particle group (D) is preferably the above lower limit value or more in view of the cleaning performance, and the content is less than the above upper limit value and the balance with other particle groups is good.

<Particle group (E)>
The particle group (E) does not contain a surfactant and a percarbonate, and contains 70% by mass or more of a water-soluble inorganic salt (water-soluble inorganic salt-containing particles (e) (hereinafter simply referred to as "particles (e)") Group of particles having an average particle size of less than 500 μm.
The particle group (E) contained in the granular detergent may be of one type or of two or more types having different compositions. The composition of the particles (e) constituting one kind of particle group (E) is assumed to be uniform.

Examples of the water-soluble inorganic salt include the same water-soluble inorganic salts as the other optional components in the particles (a).
The particles (e) may be granules containing the same binder as the particles (c), but particles made of crystals of a water-soluble inorganic salt are preferred.
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 based on the total mass of the particles (e). 100 mass% may be sufficient.
2 mass% or less is preferable, and, as for the water content of particle group (E), 1 mass% or less is more preferable. It may be zero. It is excellent by the storage stability of percarbonate as it is below the upper limit of the said range.

The average particle diameter 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 diameter of the particle group (E) is at least the lower limit value of the above range, it is preferable from the viewpoint of fluidity of the granular detergent, and when it is at the upper limit value or less, the solubility in water is excellent.
0.8-1.3 g / cm < ³ > is preferable and, as for the bulk density of particle group (E), 0.9-1.2 g / cm < ³ > is more preferable. If it is not less than the lower limit value of the above range and not more than the upper limit value, the difference from the bulk density of the other particle groups is small, and classification hardly occurs.
15-55 mass% is preferable, and, as for content of the sum total of particle group (E) with respect to the total mass of granular detergent, 25-45 mass% is more preferable. When the content of the particle group (E) is not less than the lower limit value and not more than the upper limit value, the balance with other particle groups is good.

<Optional component>
The granular detergent may contain an optional component which does not correspond to any of the particle groups (A) to (E), as long as the effects of the present invention are not impaired, as needed. For example, bleach activators, bleach activation catalysts, enzymes, antifoaming agents, surface coating agents (such as zeolite), perfumes, dyes and the like can be mentioned.
These optional components may be powder mixed with the particle groups (A) to (E) as other particle groups, and may be attached to the particle groups (A) to (E) by spraying, for example.
The total content of optional components 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, relative to the total mass of the granular detergent.

3 mass% or less is preferable, as for the water content of granular detergent, 2 mass% or less is more preferable, and 1.5 mass% or less is more preferable. It is excellent in the storage stability of percarbonate salt as it is below the upper limit of the said range. The lower limit is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, and still more preferably 1.0% by mass or more from the viewpoint of solubility of the granular detergent.
10 mass% or less is preferable with respect to the total mass of granular detergent, 7.5 mass% or less is more preferable, 5 mass% or less is more preferable. It is excellent in the storage stability of percarbonate salt as it is below the upper limit of the said range. The lower limit is preferably 1.5% by mass or more, more preferably 3% by mass or more, and still more preferably 4.5% by mass or more from the viewpoint of cleaning performance.

<Method of Producing Granular Detergent>
The granular detergent comprises powder-mixing the particle group (A), the particle group (B), the particle group (C), the particle group (D), and the other particle groups as required in a predetermined ratio. Can be manufactured by
A known powder mixing method can be used to mix the particle groups, and for example, all the particle groups are charged into a conventionally known powder mixing device (for example, a horizontal cylindrical rolling mixer or a V-type mixer). And mixing methods. Two or more types of particle groups may be introduced simultaneously, one by one, or a combination of these. After mixing all particle groups, liquid components such as perfume may be added by spraying or the like and mixed.

<How to use granular detergent>
Granular detergents can be used to wash articles. As a washing method of the to-be-washed | cleaned material which used granular detergent, the washing | cleaning liquid diluted with 50 to 5000 times water is used, for example, so that the density | concentration of granular detergent may be 0.02-2 mass% (200-20000 ppm), A conventionally known cleaning method may be mentioned, such as a method of washing the material to be washed with a washing machine to which the material to be washed is added so that the bath ratio is 3 to 50 times or immersing the material to be washed in a cleaning solution.
Examples of the material to be washed include textiles such as clothes, fabrics, curtains and sheets.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited by the following description.

(Raw material used)
<Particle group (A)>
Particle group (A-1): group of anionic surfactant-containing particles produced in Production Example 1 Content of anionic surfactant 83 mass%, water content 5 mass%, average particle diameter 370 micrometers, bulk density 0.68 g / cm ³ .
Particle group (A-2): A group of alkyl sulfate ester particles having 12 to 14 carbon atoms (trade name "Sulfopon 1214G" manufactured by BASF Corporation). Content of anionic surfactant 99 mass% or more, water content less than 1 mass%, average particle diameter 440 micrometers, bulk density 0.64 g / cm ³ .

<Particle group (A ')>
Particle group (A′-1): group of anionic surfactant-containing particles produced in Production Example 2. Content of anionic surfactant 15.5 mass%, content of nonionic surfactant 4.2 mass%, water content 7.5 mass%, average particle diameter 380 micrometers, bulk density 0.84 g / cm ³ .

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

<Particle group (C)>
Particle group (C-1): Group of sodium sulfate granules (trade name "Detergent White Speckle" manufactured by Zhejiang HANSHA Detergents), content of sodium sulfate 98% by mass, content of sodium silicate 1% by mass, content of carboxymethylcellulose 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), content of sodium percarbonate 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 Jinke Chemicals, no coating), content of sodium percarbonate 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 mass%, water content less than 1 mass%, average particle diameter 280 μm, bulk density 0.95 g / Cm ³ .
Particle group (E-2): Group of sodium hydrogencarbonate particles (trade name "sodium hydrogen carbonate" manufactured by Aoshima 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: A-type zeolite, trade name "Silton B" manufactured by Mizusawa Chemical Co., Ltd., 80% by mass in pure part.
Enzyme: A mixture of "Savinase 12T" / "Cannase 24T" / "LIPEX 100T" / "Cellclean 4500T" (all trade names, manufactured by Novozymes) = 4/4/1/1 (mass ratio).
Fluorescent agent: “Tynopearl CBS-X” (distyrylbiphenyl derivative, water-soluble fluorescent agent) / “Tynopearl AMS-GX” (bis (triazinylaminostilbene) disulfonic acid derivative, semi-dispersive fluorescent agent) (all are commercial products Name, manufactured by BASF Corp.) = 1/1 (mass ratio) mixture.
Perfume: Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.

Production Example 1: Preparation of Particle Group (A-1)
[Production of α-sulfo fatty acid alkyl ester salt paste]
Methyl palmitate (trade name "Pastel M-16" manufactured by Lion Corporation) and methyl stearate (trade name "Pastel M-180" manufactured by Lion Corporation) are mixed so as to be 80:20 (mass ratio) , And fatty acid methyl ester mixture.
In a 1 kL reactor equipped with a stirrer, 330 kg of the fatty acid methyl ester mixture were placed. With stirring, anhydrous sodium sulfate was added as a coloring inhibitor in an amount of 5% by mass with respect to the fatty acid methyl ester mixture. While stirring at a reaction temperature of 80 ° C., it takes 3 hours while bubbling 110 kg of SO ₃ gas (sulfonation gas) diluted to 4 vol% with nitrogen gas (1.1 moles per mol of fatty acid methyl ester mixture) Blew in at a constant speed. Aging was further performed for 30 minutes while maintaining the temperature at 80 ° C.
After transferring to the esterification tank, 14 kg of methanol was supplied, and the esterification reaction was carried out at 80 ° C. Aging was further performed for 30 minutes while maintaining the temperature at 80 ° C.
Furthermore, the esterified product withdrawn from the reactor was continuously neutralized by adding an equivalent amount of aqueous sodium hydroxide solution using a line mixer.
Next, this neutralized product is injected into the bleaching agent mixing line, and 35% hydrogen peroxide water is converted to 1 to 2% by mass in terms of pure component with respect to AI (active ingredient: α-sulfo fatty acid alkyl ester metal salt) The mixture was bleached by mixing while maintaining at 80 ° C. to obtain an α-sulfo fatty acid alkyl ester salt-containing paste.

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

  Next, the melt is cooled to 20-30 ° C. in 0.5 minutes using a belt cooler (made by Nippon Belting Co., Ltd.), and α-sulfo is further made using a disintegrator (made by Nippon Belting Co., Ltd.) Fatty acid alkyl ester salt flakes were obtained.

  1 kg of the above flakes is aged at 30 ° C. for 28 days (crystallization treatment), and the obtained MES flakes are ground with a speed mill (grinding conditions: rotation speed 1500 rpm, screen hole diameter 1.0 mm, temperature 25 ° C. inside grinder) Thus, α-sulfo fatty acid methyl ester sodium salt (MES) -containing particles were obtained. The particles and the A-type zeolite were charged into a container rotary mixer and mixed to obtain a particle group (A-1). Content of the (alpha)-sulfo fatty acid methyl ester salt in this particle group was 83 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, particle groups (A'-1) were 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 having 16 carbon atoms of fatty acid residue: 18 carbon atoms = 83: 17 (mass ratio) (manufactured by Lion Corporation, AI = 70% by mass, the balance being unreacted fatty acid methyl ester, Sodium sulfate, methyl sulfate, hydrogen peroxide, water etc.).
LAS-Na: Linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid sodium salt (trade name "Lipon LH-200" manufactured by Lion Corporation, LAS-H pure 96% by mass) at the time of preparation of surfactant composition % Aqueous sodium hydroxide solution).
AE (C12 EO 7): nonionic surfactant, trade name "LMAO-90" manufactured by Lion Chemical Co., Ltd., polyoxyethylene lauryl ether having an average added mole number of oxyethylene groups of 7;
Soap: fatty acid sodium having 14 to 20 carbon atoms (manufactured by Lion Corporation, pure 66% by mass, fatty acid composition; C14 = 1.0% by mass, C16 = 43.3% by mass, C18F0 (stearic acid) = 6.6% %, 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 diameter 490 μm, bulk density 1.30 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
Glass salt: Sodium sulfate: trade name "Neutral Anhydrous Glass A 0" manufactured by Shikoku Kasei Kogyo Co., Ltd.
Zeolite: A-type zeolite, trade name "Silton B" manufactured by Mizusawa Chemical Co., Ltd., 80% by mass in pure part.
PA: sodium polyacrylate, trade name "Sokalan PA30CL" manufactured by BASF.
Fluorescent agent: “Tynopearl CBS-X” (distyrylbiphenyl derivative, water-soluble fluorescent agent) / “Tynopearl AMS-GX” (bis (triazinylaminostilbene) disulfonic acid derivative, semi-dispersive fluorescent agent) (all are commercial products Name, manufactured by BASF Corp.) = 1/1 (mass ratio) mixture.

・ Step (1)
A portion of LAS-Na (an amount of 25% by mass with respect to MES) is added to an aqueous slurry of MES (prepared to have a water content of 25% by mass) obtained by sulfonation and neutralization of a raw material fatty acid ester. The mixture was concentrated under reduced pressure using a thin-film dryer until the water content reached 11% by mass to obtain a mixed concentrate of MES and LAS-Na.

・ Step (2)
Water was added to a jacketed mixing vessel equipped with a stirrer and the temperature was adjusted to 80.degree. To this was added the surfactant excluding the mixed concentrate (MES and part of the LAS-Na) and stirred for 10 minutes. Subsequently, PA was added. After stirring for a further 10 minutes, a part of the zeolite (from the compounding amount described in Table 1 below, 1.0% by mass for addition at the time of addition to be added in the following step (3), 5.0% for a grinding aid %, Sodium carbonate and sodium sulfate were added. After further stirring for 20 minutes to prepare a slurry for spray drying having a water content of 38% by mass, spray drying is carried out using a countercurrent type spray drying tower under conditions of a hot air temperature of 280 ° C., average particle diameter 320 μm, bulk density 0.30 g Spray-dried particles of / cm ³ and water content of 6% by mass were obtained.

・ Step (3)
The obtained spray-dried particles, the mixed concentrate obtained in step (1), 1.0% by mass of zeolite, a fluorescent agent, and water are introduced into a continuous kneader (KRC-S12, manufactured by Kurimoto Kosho Co., Ltd.) The mixture was kneaded under the conditions of a rotation speed of 135 rpm of a kneader and a jacket temperature of 60 ° C. to obtain a hydrate having a water content of 7% by mass containing a surfactant (kneading treatment). The extrusion is cut with a cutter (cutter peripheral speed is 5 m / s) while extruding with a pelleter double (EXDFJS-100 type manufactured by Fuji Paudal Co., Ltd., model: 10 m) equipped with a die with a hole diameter of 10 mm. A pellet-like molding of about 5 to 30 mm was obtained.
Subsequently, a 5.0% by mass equivalent amount of zeolite as a grinding aid was added to the obtained pellet-like molded product, and Fitzmill (three stages connected in series in the presence of cold air (10 ° C., 15 m / s)) Milled using Hosokawa Micron, DKA-3) (Screen hole diameter: 1st stage 12 mm 2nd stage 7 mm 3rd stage 3 mm, rotational speed: 1 st stage 4700 rpm 2 st stage 4700 rpm 3 st stage 4700 rpm ), Particle group (A'-1) was obtained.

Production Example 3 and 4: Preparation of Particle Groups (B-1) and (B-2)
According to the composition shown in Table 2, particle groups (B-1) and (B-2) were manufactured by the following method.
The raw materials shown in Table 2 are as follows.
Nonionic surfactant: Brand name "EMALEX 707" manufactured by Nippon Emulsion Co., Ltd., polyoxyethylene lauryl ether having an average added mole number of oxyethylene groups of 7.
Sodium carbonate: trade name "grain ash" manufactured by Asahi Glass Co., Ltd.
Bentonite: trade name "Laundrosil PRW414" manufactured by Sued Chemie.

  Bentonite and sodium carbonate among the compounding components shown in Table 2 are loaded into a Lädige mixer (Matsubo M20 type) equipped with a scalloped shovel and the clearance between the shovel and the wall is 5 mm (filling rate 50 volume %), And agitation of 200 rpm main shaft and 200 rpm chopper 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 conditions of a jacket temperature of 30 ° C. to obtain a target particle group.

(Examples 1 to 17, Comparative Examples 1 to 3)
Among the compositions shown in Tables 3 and 4, the components other than the perfume were simultaneously charged into the container rotary cylindrical mixer at a speed of 15 kg / min and mixed. In this container rotary type cylindrical mixer, the container has 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, an internal mixing blade has a height of 0.1 m, a length It is of the specification which attached four flat wings of 1.4m every 90 degrees. The number of revolutions of the internal mixing blade was adjusted so that the Froude number was 0.2.
The container was tumbled to spray the perfume onto the fluidized particles, and rolled for 1 minute to obtain a granular detergent.

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

<Storage test>
The following storage test was conducted on the granular detergent produced in each example.
Using a paper consisting of three layers of 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 ) from the outside A box 15 cm long × 9.3 cm wide × 18.5 cm high was prepared, and 1.0 kg of granular detergent was placed in this box. It was sealed in a box containing granular detergent and stored in a constant temperature and humidity chamber for 30 days. The constant temperature and humidity chamber was operated repeatedly at 45 ° C., 75% RH for 8 hours, and at 25 ° C., 55% RH for 16 hours. After storage for 30 days, the box was taken out of 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 repose angle]
The fluidity was evaluated by measuring the angle of repose (°) by the following method.
Place an acrylic measuring instrument with a horizontal lid (10 cm high x 10 cm deep x 3 cm wide) with a graduated angle on a flat surface, and the horizontal lid of the measuring instrument (one side of 10 cm high x 3 cm wide) In the closed state, the granular detergent after the above storage test was poured into the measuring device from the position where the height from the upper surface of the measuring device is 1 to 2 cm.
The granular detergent gently opened the side cover when the height from the upper surface of the measuring instrument exceeded 0-1 cm and was in a heaped state, and was naturally discharged by the granular detergent gravity.
After the discharge, the angle (tilt angle) between the surface (inclined surface) of the granular detergent remaining in the measuring device 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 repose angle. The liquidity was evaluated based on the following evaluation criteria. A or B is preferred, and A is particularly preferred, from the viewpoint of easy spooning.
As the acrylic measuring device, a horizontal lid was provided on one of the side surfaces having a height and a width, and a scale of the angle was drawn on the side surface having a height and a depth.
Evaluation criteria A: Repose angle is 40 degrees or less.
B: Repose angle is more than 40 ° and less than 50 °.
C: Repose angle is more than 50 ° and less than 60 °.
D: Repose angle is over 60 °.

Dust control
The amount of dust generation was investigated by the following method.
LD-3 digital dust meter (trade name, Kuwata Scientific Instruments Co., Ltd.) that can measure the amount of fine powder (dust) generated in the container at the top of a 40 cm high x 30 cm wide x 30 cm deep container. Manufactured by Kogyo Co., Ltd.).
Maintain the atmosphere in the container at a temperature of 25 ° C. and a relative humidity of 60%, drop 50 g of granular detergent from the sample inlet provided at the top of the container into the container, and turn on the digital dust meter at the same time. The dust counts after standing for 5 minutes were read.
The dust control property was evaluated based on the following evaluation criteria. A or B is preferred, and A is particularly preferred, from the viewpoint of easy spooning.
Evaluation criteria A: Dust count number is 100 or less.
B: Dust count number is more than 100, 300 or less.
C: Dust count number is more than 300, 500 or less.
D: Dust count number is over 500.

<Storage stability of percarbonate>
[Measurement of residual rate of sodium percarbonate]
After completion of the above storage test, after thoroughly mixing the whole granular detergent in the box, the granular detergent was sampled by the following procedure, and the residual ratio of sodium percarbonate was measured.
The box containing the granular detergent was allowed to stand on a horizontal table, and one spoonful (about 50 g) of granular detergent was poured from the center using a spoon. About 25 g of the granulated granular detergent (sample) was precisely weighed to 10 mg.
About 25 g of precisely weighed sample was placed in a 1 L beaker, 200 mL of 33% by mass aqueous acetic acid solution was added, and the mixture was dissolved by stirring with a magnetic stirrer. Subsequently, 40 mL of 10 mass% potassium iodide aqueous solution was added, and the obtained solution was titrated with 1 mol / L sodium thiosulfate solution. On the way, when the solution became colorless, 2-3 drops of saturated ammonium molybdate were added, and when the solution became pale yellow, the titration was continued further, and the titration was finished when the solution became colorless again. 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 effective oxygen (%) was determined by the following equation.
Effective oxygen content (%) = {f × p × (1/2) × (1/1000) × 16} / g × 100 [wherein, f is a factor of 1 mol / L sodium thiosulfate solution, p is 1 mol Sodium thiosulfate solution titration volume (unit: mL) / g, g is the mass of the sample (unit: g). ]

The remaining half amount of the sample, about 25 g, was also determined for the effective oxygen amount by the above method. The average value of these was taken as the effective oxygen amount of the sample.
Separately, the effective oxygen amount (%) of the particle group (D) used for the production of the granular detergent was determined by the same calculation method as described above.
From these effective oxygen amounts, the residual ratio (%) of sodium percarbonate was determined by the following equation.
Residual rate of sodium percarbonate (%) = (effective oxygen amount of sample (%) / effective oxygen amount of particle group (D) (%)) x 100 (%)
The storage stability of percarbonate was evaluated based on the following evaluation criteria. A or B is preferred, A is particularly preferred.
Evaluation criteria A: Residual rate of sodium percarbonate is over 70%.
B: Residual rate of sodium percarbonate is more than 55% to 70% or less.
C: Remaining rate of sodium percarbonate is more than 40% to 55% or less.
D: Remaining 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 control property and excellent in ease of scooping by a spoon. In addition, when stored under high temperature and severe conditions, the fluidity was good and the ease of spooning was maintained. Furthermore, the performance of percarbonate was well maintained even when stored under high temperature and severe conditions.
In particular, the particle group (A-1) contains an α-SF salt having high crystallinity at a high concentration among the anionic surfactants, so the particles become brittle with time and dusting and fluidity decrease. However, in Examples 1 to 3 and 5 to 17, generation of dust and reduction in fluidity were suppressed.

On the other hand, in Comparative Example 1 in which the particle group (C) was not included, the fluidity was significantly reduced as compared with Example 3.
In Comparative Example 2 in which the particle group (B) is not included, the dust suppression property is largely reduced as compared with Example 3, and the flowability is also inferior.
In Comparative Example 3 which does not contain the particle group (B) and the content of the anionic surfactant in the particle group (A) is low, the storage stability of the percarbonate is largely reduced, and the fluidity and the dust suppressing property are also reduced. It is inferior.
Comparative Example 3 is an example in which the particle group (A) was manufactured by a method of compression-mixing powder raw materials containing spray-dried particles and liquid raw materials in a kneader and then grinding (powder kneading method). Zeolite is contained in the composition for the purpose of preventing the adhesion of the raw material to the spray drying apparatus, the kneader and the grinder, and the water derived from the liquid raw material is also contained. In the granular detergent of Comparative Example 3, the relatively high content of such zeolite and water is considered to cause a decrease in the storage stability of the percarbonate.

Claims (5)

A particulate detergent comprising 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 in which the content of the anionic surfactant is higher than the content of other surfactants.
Particle group (B): A nonionic interface comprising 30% by mass or more of a nonionic surfactant and 25% by mass or more of a water-swellable clay mineral, wherein the content of the nonionic surfactant is higher than the content of other surfactants Particle group of activator-containing particles (b).
Particle group (C): A group of water-soluble inorganic salt-containing particles (c) containing 70% by mass or more of a water-soluble inorganic salt without containing a percarbonate, and having 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 at least 80 mass% of a water-soluble inorganic salt, containing neither surfactant nor percarbonate, and having an average particle size of less than 500 μm Particle group.   The granular detergent according to claim 1 or 2 whose water content is 3 mass% or less.   The granular detergent as described in any one of Claims 1-3 whose content of a zeolite is 10 mass% or less with respect to the total mass of granular detergent.   The average particle diameter of the particle group (D) is 500 μm or more, and the absolute value of the difference between the average particle diameter of the particle group (C) and the average particle diameter of the particle group (D) is 300 μm or less. The granular detergent as described in any one of -4.