JP5529373B2 - Particle surface modification method - Google Patents

Description

  The present invention relates to a particle surface modification method and surface modified particles.

Many techniques for applying an active ingredient such as a surfactant, a solvent, a fragrance, silicone, or a water-soluble polymer compound to a powdery composition are known. For example, it is a technique of a granule on which a surfactant is supported, and a technique using clay as a surfactant-carrying particle is disclosed (for example, see Patent Document 1). Moreover, the technique of the foaming property regulator which hold | maintained the fragrance | flavor particle | grains containing a fragrance | flavor, cyclodextrin, and a calcium phosphate and a silicone to the bathing agent and the silicone was disclosed is disclosed (for example, patent document 2 and 3). reference). As described above, a number of techniques for supporting an active ingredient on a particle are known. However, since the active ingredient generally exhibits tackiness, there is a problem that the fluidity of the particle is deteriorated, and a liquid or paste-like active ingredient is eliminated. When used, there is a problem that the active ingredient stains from the particles during storage, and the particles aggregate, solidify, and caking.
In order to solve these problems, a technique of performing treatment with a powder for surface modification has been proposed, and it has been suggested that zeolite, clay and the like can be used as a surface modified powder (for example, patents). References 4-6). However, these techniques do not have sufficient adhesion to the particles of the surface-modified powder, and are not sufficient in terms of suppressing caking (caking resistance) and suppressing bleeding out of the active ingredient.

  On the other hand, composite particles containing a nonionic surfactant and a clay mineral are already known as a technique using a clay mineral as a supporting particle for a nonionic surfactant in a powder detergent (see Patent Documents 7 and 8). . However, the composite particles used here are particles that carry nonionic surfactant-carrying particles, and the use and effect of such composite particles can be used for surface modification. There is no suggestion about.

JP-A-9-183613 JP 11-209784 A JP 7-10039 A Japanese Patent No. 2965905 JP 2005-325304 A JP 2004-143394 A Japanese Patent Laid-Open No. 5-005100 Japanese Patent Laid-Open No. 6-009997

  It is an object of the present invention to provide a surface modification method and surface modified particles that impart storage stability such as excellent fluidity, excellent caking resistance, and suppression of stains of active ingredients to particles. .

The present inventors have found that the above problem can be solved by bringing particles having specific properties, a specific layered clay mineral, and a nonionic surfactant into contact with each other, and then bringing the fine powder into contact therewith. The present invention has been completed based on such findings.
That is, the gist of the present invention is as follows.

1. A method for modifying the surface of particles comprising the following steps [1] and [2].
Step [1]: At least a particle A having an average particle diameter of 100 to 3000 μm carrying an active ingredient, a layered clay mineral (b-1) having an average particle diameter of 10 to 100 μm, and a nonionic surfactant (b-2) The process of making it contact.
Step [2]: A step of bringing the particles C obtained in the step [1] into contact with the fine powder D having an average particle size of 0.1 to 10 μm.
2. From the composite B containing the layered clay mineral (b-1) and nonionic surfactant (b-2) having an average particle diameter of 10 to 100 μm on the surface of the particle A having an average particle diameter of 100 to 3000 μm carrying the active ingredient Surface-modified particles obtained by sequentially laminating a layer composed of a fine powder D having an average particle diameter of 0.1 to 10 μm.
3. 3. A detergent composition containing the surface-modified particles according to 2 above.

  By the particle surface modification method of the present invention, it is possible to obtain surface modified particles having excellent storage stability such as excellent fluidity, resistance to caking, and suppression of stains of active ingredients.

The surface modification method for particles according to the present invention comprises a step [1]: at least particles A having an average particle size of 100 to 3000 μm carrying an active ingredient, a layered clay mineral (b-1) having an average particle size of 10 to 100 μm, and The step of bringing the nonionic surfactant (b-2) into contact, and the step [2]: the step of bringing the particles C obtained in the step [1] into contact with the fine powder D having an average particle size of 0.1 to 10 μm , Has. Further, the surface modified particles of the present invention have a layered clay mineral (b-1) having an average particle diameter of 10 to 100 μm and a non-layered clay mineral (b-1) on the surface of the particle A having an average particle diameter of 100 to 3000 μm carrying one or more active ingredients. A layer made of the composite B containing the ionic surfactant (b-2) and a layer made of the fine powder D having an average particle size of 0.1 to 10 μm are sequentially laminated.
First, each component constituting the surface modified particles according to the present invention will be described in detail.

[Particle A]
The particle A is a particle having an average particle diameter of primary particles supporting an active ingredient of 100 to 3000 μm. The average particle diameter of the particles A is preferably 150 to 2500 μm, more preferably 200 to 2000 μm, and further preferably 250 to 1500 μm from the viewpoint of solubility and flow characteristics. Here, the average particle diameter in the present invention is measured using a laser diffraction / scattering particle size distribution measuring apparatus having a dry measurement unit. Specifically, measurement can be performed by optionally connecting a dry measurement unit G0310630 to Partica LA-950 (manufactured by Horiba, Ltd.) using the Mie scattering method. Moreover, the setting of the compressed air for dispersion | distribution of powder is measured by normal, and the obtained median diameter is made into the average particle diameter of a layered clay mineral (b-1).

  As the particles A, organic and inorganic particles can be used. Examples of the organic and inorganic particles include water-soluble inorganic salts such as sodium carbonate, calcium carbonate, and sodium sulfate, silicates / aluminosilicates, sugars / polysaccharides, and the like. Specific examples of silicates and aluminosilicates include amorphous silicate ("Toceal NR (trade name)" manufactured by Tokuyama Co., Ltd.), bentonite ("Round Rosil DGA powder (trade name)" manufactured by Zoot Chemi), Preferred examples include calcium silicate ("FLORITE (trade name)" manufactured by Tokuyama Co., Ltd.) and aluminum silicate ("Tixorex 25 (trade name)" manufactured by Han-France Chemical Co., Ltd.). From the viewpoint of sufficiently supporting the above, amorphous silicate and calcium silicate are more preferable.

  Specific examples of the sugar / polysaccharide include cellulose, starch, and derivatives thereof. Specific examples of cellulose include carboxymethyl cellulose (“Sunrose (trade name)” manufactured by Nippon Paper Industries Co., Ltd.), methyl cellulose (“Metroses (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd.), hydroxypropyl methyl cellulose (“Marporose ( Product name) ”: Matsumoto Yushi Seiyaku Co., Ltd.), cationized cellulose (“ Poise 60H (product name) ”: Kao Corporation,“ JR30M (product name) ”,“ LR400 (product name) ”: Dow Chemical Company Specific examples of starch include dextrin (“Pine Flow KH (trade name)” manufactured by Matsutani Chemical Industry Co., Ltd.), dextrin (“Paindex (trade name)” manufactured by Matsutani Chemical Industry Co., Ltd.). ), Cationized starch (“Posiparin (trade name)” manufactured by Matsutani Chemical Industry Co., Ltd.), and the like. Of these, carboxymethylcellulose and cationized cellulose are preferred from the viewpoints of flow characteristics, emulsifying ability, and moisture retention ability. Moreover, as the particles A, the above-mentioned particles can be used alone, but it is preferable to use a combination of them from the viewpoint of sufficiently supporting the active ingredient.

[Spray-dried particles]
As the particles A, spray-dried particles obtained by spray-drying an aqueous solution or dispersion containing a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt can be preferably used. These particles are preferably used as a carrier for supporting a surfactant as an active ingredient, and can be suitably used for a powder composition that needs to be quickly dissolved in low-temperature water, particularly a powder detergent for clothing.

The water-insoluble inorganic substance is preferably an inorganic substance capable of dissolving less than 10 g (preferably less than 5 g, more preferably less than 1 g) in 100 g of water at 20 ° C., specifically, an aluminosilicate having a sequestering ability; Examples include silicon dioxide, hydrated silicate compounds, and clay compounds such as perlite.
As the water-soluble polymer, those capable of dissolving 1 g or more (preferably 5 g or more, more preferably 10 g or more) in 100 g of water at 20 ° C. are preferable. Specific examples include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, saccharides, etc., and have a weight average molecular weight of several thousand in terms of sequestering ability, dispersibility of solid dirt / particle dirt and ability to prevent recontamination. 100,000 to carboxylic acid polymers are preferred. Particularly preferred are acrylates and salts of acrylic acid-maleic acid copolymers.
As the water-soluble salts, the same water-soluble salts as the above water-soluble polymers are preferable. Specifically, alkali metal salt, ammonium salt, or amine each having an alkali ability carbonate ion, hydrogen carbonate ion, silicate ion, sulfate ion, sulfite ion, hydrogen sulfate ion, hydrochloric acid ion, phosphate ion, or the like Examples thereof include water-soluble inorganic salts typified by salts, and low molecular weight water-soluble organic salts such as citric acid and fumarate having a sequestering ability.

The contents of the water-insoluble inorganic substance, the water-soluble polymer, and the water-soluble salt contained in the aqueous solution or dispersion are 20 to 90% by mass, 2 to 30% by mass, and 5 to 78% by mass, respectively, based on the solid content. The range of 30 to 75% by mass, 3 to 20% by mass, and 10 to 67% by mass is more preferable, and 40 to 70% by mass, 5 to 20% by mass, and 20 to 55% by mass are further included. preferable. When spray-dried particles are used as the particles A, the average particle diameter, bulk density, supportability, and particle strength can be controlled by adjusting the drying method and drying conditions within the above composition range.
Further, in the aqueous solution or dispersion solution, in addition to the above water-insoluble inorganic substance, water-soluble polymer, and water-soluble salt, as other components, particles suitable for the cleaning composition obtained by the production method of the present invention, salts, Auxiliary components such as surfactants and dyes may be included. For example, salts such as heavy sodium carbonate (dense ash), powdered surfactants and the like can be mentioned. The blending amount of the other components is preferably 10% by mass or less in the aqueous solution or dispersion.

The particles A preferably have the following structure (1) and / or (2).
Structure (1): When surface-modified particles are dissolved in water, the particle diameter of the surface-modified particles is preferably 1/10 or more, more preferably 1/5 or more, still more preferably 1/4 or more, and particularly preferably It is preferable to have pores capable of releasing bubbles having a diameter of 1/3 or more.
Structure (2): An uneven distribution containing water-insoluble inorganic substances, water-soluble polymers and water-soluble salts, and having more water-soluble polymers and / or water-soluble salts (hereinafter referred to as water-soluble polymers) near the surface than inside. It is preferable to have properties.
When the particle A has the structure of the structure (1), in the process of dissolving the surface-modified particles in water, when a small amount of water first enters the particles, bubbles of a predetermined size are released from the inside of the particles, Next, when a large amount of water intrudes into the particle, the particle itself collapses (self-disintegration), so that not only dissolution from the vicinity of the surface but also dissolution and collapse from the inside of the particle occur, so that the surface-modified particle becomes high-speed. It has solubility.

  This bubble emission phenomenon can be confirmed with a digital microscope or an optical microscope, and the bubble diameter (equivalent circle diameter) can be measured. The pore diameter of the particles A is preferably 1/10 to 4/5, more preferably 1/5 to 4/5 of the particle diameter. The pore diameter can be measured as follows. Cut the surface with the maximum particle diameter with a scalpel so as not to break the particle A, observe the cut surface with a scanning electron microscope, and the equivalent circle diameter (γ μm) of the cut surface of the cut particle and the presence of pores inside the particle Is confirmed, the equivalent circle diameter (δ μm) of the pores is measured. When a plurality of pores are confirmed, the equivalent circle diameter of the largest pore is δ μm. Then, the ratio of pore diameter to particle diameter (δ / γ) is obtained.

  In addition, since the particle A has the structure of the structure (2), the water-soluble component in the vicinity of the surface dissolves faster in water, and the dissolution behavior that promotes the disintegration of the surface-modified particles from the particle surface is exhibited. Thus, high-speed solubility can be expressed. In addition, as the most preferable aspect to express the high-speed solubility, the particles A have both the structures (1) and (2).

The uneven distribution of water-soluble polymers and the like can be confirmed by the following method. First, a particle A to be measured and a particle A pulverized product in which the particle A is sufficiently pulverized with an agate mortar or the like to obtain a uniform state are prepared. A method using both Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS) under the condition that information from the surfaces of the particles A and the pulverized particles A to about 10 μm is obtained. (Hereinafter referred to as “FT-IR / PAS”). When the amount of the former water-soluble polymer or the like is larger than the amount of the latter, the particle A to be measured has a structure in which more water-soluble polymer or the like is present near the surface than inside. As measurement conditions for obtaining information from the surface of the pulverized product of the particles A and the base particles A to about 10 μm, for example, conditions of a resolution of 8 cm ⁻¹ , a scan speed of 0.63 cm / s, and a total of 128 times can be mentioned. Examples of the apparatus used include an FTS-60A / 896 type infrared spectrophotometer (Bio-Rad Laboratories) as an infrared spectrophotometer, and a 300 type photoacoustic detector (manufactured by MTEC) as a PAS cell. It is done. In addition, FT-IR / PAS is APPLIED SPECTROCOPY VOL. 47 1311-1316 (1993).

[Active ingredients]
Particle A carries an active ingredient. The active ingredient is at least one selected from a surfactant, a solvent, a fragrance, silicone, a water-soluble polymer compound, and a wax-based antifoaming agent, and is appropriately selected according to the use of the surface modified particles of the present invention. It is used. The active ingredient is supported by impregnating, adsorbing, absorbing, and occluding the particles A. The properties of the active ingredient are those that are liquid or paste at 20 ° C., or tacky at 20 ° C., from the viewpoint of sufficiently exerting the effect of the active ingredient and facilitating loading onto the particles. Those having are preferably selected.

  The amount of the active ingredient supported on the particles A is preferably 40 to 200% by volume, more preferably 60 to 175% by volume, and still more preferably 80 to 150% by volume with respect to the oil absorption capacity of the particles A described above. If the loading amount of the active ingredient is within the above range, the loading effect of the active ingredient can be sufficiently exhibited.

[Active ingredient: Surfactant]
The particles A carrying the surfactant can be suitably used for uses such as a detergent for clothing, a detergent for automatic dishwashers, and a powdery pipe cleaner. The surfactant used in such applications is obtained by blending at least one selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants as necessary. It is done.
Examples of nonionic surfactants include alkanediyl oxide adducts of higher alcohols, preferably ethylene oxide adducts, ethylene oxide and / or propylene oxide adducts, aliphatic alkanolamides, alkyl polyglycosides, etc. From the viewpoint of hard water resistance and biodegradability, ethylene oxide and / or propylene oxide adducts (polyoxyalkanediylalkyl (or alkenyl) ethers) of higher alcohols are preferred. Preferred examples of the higher alcohol include aliphatic alcohols having 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms. The average added mole number of ethylene oxide and / or propylene oxide is 2 to 200. Are preferable, 4-50 are more preferable, and 4-15 are more preferable.

Anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or alkyls thereof. Examples thereof include an anionic surfactant having a sulfate group or a sulfonate group such as an ester salt or a fatty acid salt. In particular, a linear alkylbenzene sulfonate having 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, and a sulfate ester salt of a higher alcohol having 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms are preferable.
Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines and fatty acid aminopropyl betaines, and examples of cationic surfactants include mono (or di) long chain alkyl quaternary ammonium salts.

  Among these, from the viewpoint of detergency, the surfactant is preferably a polyoxyalkanediyl alkyl ether which is an alkanediyl oxide adduct having an average addition mole number of 4 to 15 aliphatic alcohols having 10 to 14 carbon atoms. While this polyoxyalkanediyl alkyl ether has a high detergency, it is liquid or paste at 20 ° C., and when it is supported on particles, it is generally known that stains during storage tend to occur remarkably. . However, according to the surface modification method of the present invention, it is possible to use polyoxyalkanediyl alkyl ether without causing stains while making full use of high detergency.

[Active ingredient: Solvent]
The particles A carrying the solvent can be suitably used particularly for an automatic dishwasher detergent. As the solvent, polypropylene glycol described in JP-A-11-61181 is preferable. Specifically, polypropylene glycol having an average addition mole number of 3 to 30 and monoalkyl ether or dialkyl ether having 1 to 5 carbon atoms thereof. Can be mentioned.
These solvents have high detergency, but are known to have a high risk of causing inconveniences such as stains during storage. According to the surface modification method of the present invention, it is possible to use these solvents without causing stains while sufficiently exhibiting such a high detergency.

[Active ingredient: Perfume]
The particles A carrying a fragrance can be suitably used for applications such as powder cleaning agents, bath agents, and fragrances. Preferred examples of the fragrances include fragrances having a boiling point of 200 ° C. or higher at normal pressure (1013 hPa). For example, fragrances such as aldehydes, ketones, esters, ethers, and alcohols are preferable. Among them, aldehydes and ketones are preferable. And fragrances of esters are more preferred.

  Examples of such aldehydes include lyial (p-tert-butyl-α-methylhydrocinnamic aldehyde), cyclamenaldehyde (p-isopropyl-α-methylhydrocinnamic aldehyde), lyral [4- (4- Hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde], helional, hydroxycitronellal and the like.

  Examples of ketones include damascone (α-, β-isomer) (2,6,6-trimethyl-trans-1-crotonylcyclohexene-1 or 2), damasenone (α-, β-isomer), methyl- β-naphthyl ketone, benzophenone, tonalide (7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene), acetyl cedrin, methyl cedrin, isomethyl ionone (α-, β-form), Iron ( α-, β-, γ-form), maltol, ethyl maltol, cis jasmon, dihydro jasmon, l-carvone and the like.

  Examples of the esters include nonyl acetate, boronyl acetate, linalyl benzoate, flutate, poirenate, diethyl phthalate, ethyl cinnamate, hexyl salicylate, benzyl salicylate, terpinyl acetate, anisyl acetate, phenylethyl isobutyrate, Examples include methyl dihydrojasmonate, γ-undecalactone, γ-nonyllactone, and coumarin.

Examples of ethers include thymol, galaxolide, and methyl eugenol. Examples of alcohols include nerol, citronellol, and eugenol.
The perfume having a boiling point of 200 ° C. or higher at normal pressure as described above is preferably used as a perfume composition obtained by mixing with the above solvent, other courageous solvents, water, and the like. The content of the fragrance is preferably 50% by mass or more, and more preferably 70% or more.

[Active ingredient: Silicone]
The particles A carrying silicone can be suitably used for applications such as a foamability modifier. Silicone can be used without any particular limitation. For example, silicone oil made of polysiloxane which may be modified and used for antifoaming agent and the like can be mentioned. The modified silicone oil is one in which various organic groups are introduced into a part of the methyl group of polysiloxane. For example, amino modification, epoxy modification, carboxy modification, carbinol modification, (meth) acryl modification, mercapto modification, phenol modification. , Polyether modification, alkyl modification, fluorine modification, and the like. In the present invention, the above modified silicone oil can be used without limitation. The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation.

[Active ingredient: Water-soluble polymer compound]
The particles A carrying a water-soluble polymer compound can be suitably used for applications such as powder detergents, dispersants such as detergents for automatic dishwashers, and surface modifiers. As the water-soluble polymer compound, those capable of dissolving less than 10 g (preferably less than 5 g, more preferably less than 1 g) in 100 g of water at 20 ° C. are preferable.
Specific examples of such water-soluble polymer compounds include homopolymers of polymerizable unsaturated carboxylic acids such as (meth) acrylic acid (salt), maleic acid (salt), and maleic anhydride, or copolymers thereof. Copolymers with polymerizable unsaturated compounds, such as methyldiallylamine, (meth) acryloylaminopropyldimethylamine, (meth) acryloyloxyethyldimethylamine, and quaternized products thereof such as acrylamidomethylpropanesulfonic acid (salt) A homopolymer of a polymerizable unsaturated carboxylic acid amide compound or a polymerizable unsaturated carboxylic acid ester compound, or a copolymer with an unsaturated compound copolymerizable therewith is preferred.

[Active ingredient: Wax-based antifoaming agent]
The particles A carrying the wax-based antifoaming agent can be suitably used for applications such as powder detergents that suppress the amount of foam generated during washing, detergents for automatic dishwashers, and surface modifiers. it can.
As the wax-based antifoaming agent, it is unnecessary to use water and has a melting point of 25 to 135 ° C., and any known antifoaming ability can be used without limitation. For example, hydrocarbons, higher fatty acids and higher alcohols And those having a fatty acid amide as a main component.
Examples of the hydrocarbons include petroleum waxes such as paraffin wax and microcrystalline wax, synthetic waxes such as Fischer-Tropsch wax and polyethylene wax, and mineral waxes such as petrolatum, ozokerite wax and ceresin wax.
The ester of a higher fatty acid and a higher alcohol may be any of animal, plant, mineral, and synthetic waxes, and those having 16 to 32 carbon atoms as the main component are preferred. As for what has fatty acid amide as a main component, what mixed fatty acid amide and silica etc. are mentioned, for example.
What has a hydrocarbon as a main component is preferable, and paraffin wax having a high defoaming ability is particularly preferable.

Moreover, it is preferable to use a wax-type antifoamer as a wax-type antifoamer composition containing a wax-type antifoamer and a binder component. As a binder component, the thing similar to the binder component mentioned as another component mentioned later can be used, and polyethyleneglycol is especially preferable. The wax-based antifoaming agent composition is obtained by supplying a wax-based antifoaming agent having a melting point or higher and a binder component to an extruder-type kneader, a twin-screw kneading extruder, etc., and kneading and extrusion molding. .
The content of the wax-based antifoaming agent in the wax-based antifoaming agent composition is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass from the viewpoint of obtaining fluidity and an excellent defoaming effect. preferable. In addition, the content of the binder component in the wax-based antifoaming agent is preferably 10 to 80% by mass, and more preferably 15 to 70% by mass from the viewpoint of obtaining a good addition effect, operability, and storage stability.
The average particle size of the wax-based antifoaming agent composition is preferably 100 to 2000 μm, more preferably 150 to 1500 μm, and further preferably 250 to 750 μm, from the viewpoint of fluidity and solubility.

[Particle properties]
The particle A has an average primary particle size of 100 to 3000 μm as described above, and is preferably 150 to 2500 μm, more preferably 200 to 2000 μm, and further preferably 250 to 1500 μm from the viewpoint of solubility and flow characteristics. Particles.
The oil-absorbing ability of the particles A is preferably 100 mL / 100 g or more and less than 800 mL / 100 g from the viewpoint of suppressing smearing. In particular, those having an oil absorption capacity of 150 mL / 100 g or more and less than 600 mL / 100 g are preferable for the purpose of supporting an active ingredient. Here, the oil absorption capacity is a value measured based on JIS K5101.

The bulk density of the particles A is preferably 400 g / L or more, and more preferably 500 g / L or more, from the viewpoint that detergent particles having excellent solubility can be obtained and compactness can be achieved. The bulk density of the particles A is a value measured according to JIS K3362.
The particles A are preferably hard particles. Specifically, the particle strength is preferably 100 kg / cm ² or more, more preferably 200 kg / cm ² or more. If the particle strength is within the above range, the base particles can be sufficiently prevented from collapsing during the production process. Here, the particle strength of the particle A is a value measured as follows. 20 g of sample is put in a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapped 30 times (Tsutsui Rikenki Co., Ltd., TVP1 type tapping type densely packed bulk density measuring device, tapping condition; period 36 times / min, 60 mm Free fall from the height. The sample height immediately after the end of the tapping operation is measured and set as the initial sample height. Thereafter, the entire upper end surface of the sample held in the container by a pressure tester is pressurized at a speed of 10 mm / min, and a load-displacement curve is measured. The initial sample height is multiplied by the slope of the straight line when the displacement rate in the curve is 5% or less, and the value obtained by dividing the obtained value by the pressurized area is defined as the particle strength.

[Layered clay mineral (b-1)]
The layered clay mineral (b-1) needs to have an average particle size of 10 to 100 μm, and is preferably used as the composite B by being brought into contact with a nonionic surfactant (b-2) described later in advance. . The average particle diameter of the layered clay mineral (b-1) is preferably 1 to 60 μm, more preferably 1 to 40 μm, since sufficient effect of improving caking resistance can be expected after avoiding a decrease in solubility. 1-20 micrometers is further more preferable. Here, the average particle diameter of the layered clay mineral (b) is a value measured in the same manner as the particle A.
Moreover, the average particle diameter of the layered clay mineral (b-1) has a preferable range depending on the relationship with the particles A. Specifically, the ratio of (average particle diameter of particles A) / (average particle diameter of layered clay favorite (b-1)) is preferably 2.5 to 150, more preferably 5 to 100, and 7.5 to 50 is more preferable.

  As the layered clay mineral (b-1), talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald) Mica, muscovite, paragonite, ceradonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, sudowite, dombasite, etc.), brittle mica (clinentite, margarite, etc.), sulite, serpentine mineral (Antigolite, Lizardite, Chrysotile, Amesite, Klonsteadite, Burcellin, Greenerite, Garnierite, etc.), kaolin minerals (kaolinite, dickite, nacrite, halloysite, etc.) . Of these, talc, smectite, swellable mica, vermiculite, chrysotile, kaolin mineral and the like are preferable from the viewpoint of flexibility, smectite is more preferable, and montmorillonite is further preferable. These may be used alone or in appropriate combination of two or more.

In addition, the following general formula (I):

It is preferable that a clay mineral represented by Here, a, b and x are 0 <a ≦ 6, 0 <b ≦ 4, x = 12-2a-3b, and Me is Na, K, Li, Ca ^1/2 , Mg ^1/2 and It is at least one ion selected from NH ₄ .

  Since such a layered clay mineral (b-1) has swelling and caking properties, it is excellent in the ability to absorb liquid components between layers, and suppresses stains on the liquid surfactant. Further, when the liquid component is contained, the adhesiveness is increased, and fine powder D described later can be maintained on the particle surface and peeling can be suppressed. Therefore, it can be preferably used from the viewpoint of improving the coverage of fine powder D.

Examples of the layered clay mineral represented by the general formula (I) include “Round rosyl DGA212”, “Round rosyl PR414”, “Round rosyl DG214”, “Round rosyl DGA powder”, “Hulasoft-1 powder” (above, Sued Chemi). ), “Detasoft GIS”, “Detasoft GIB”, “Detasoft GISW” (manufactured by Raviossa), pure bentonite, standard bentonite, premium bentonite (manufactured by CSM) and the like. Among the above-mentioned examples of layered clay minerals, there are granulated granule types added with a binder component, but the binder component may be added as long as the effects of the present invention are not impaired. Good.
When using the lamellar clay minerals listed above as the lamellar clay mineral (b-1), it is preferable to crush in advance until a suitable particle size is obtained for efficient dispersion on the surface of the base particles as an intermediate layer. Examples of the crusher that can be used for crushing include impact crushers such as hammer crushers, impact crushers such as atomizers and pin mills, and shear crushers such as flash mills. These may be a single-stage operation or a multi-stage operation of the same or different pulverizers.

From the viewpoints of storage stability and solubility, the layered clay mineral represented by the general formula (I) is composed of alkali metal ions (total of Na ions, K ions, Li ions) and alkaline earth metal ions (Ca ions). , Mg ion) (Na + K + Li) / (Ca + Mg) is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.0 or more.
In order to obtain a layered clay mineral with a high ratio of alkali metal ions, if it is a natural product, it is sufficient to select the production area, and when producing a granulated granule, it is also possible to adjust by adding an alkali metal salt. it can. Moreover, if it is a synthetic | combination product, it can adjust arbitrarily by a well-known method.
Further, as a method for producing a layered clay mineral having a high alkali metal ion ratio, the following production method is useful. A process that includes a step of drying after adding an alkali metal salt such as powdered sodium carbonate to a raw clay ore containing 20% or more of water and mixing it, or making a clay mineral pulverized into a powder with a granulator This is a production method including a step of adding a powder or an aqueous solution of an alkali metal salt such as sodium carbonate when granulating.

  The ratio of alkali metal ions and alkaline earth metal ions in the layered clay mineral (b-1) is measured by the following method. The layered clay mineral (b-1) is pulverized in a mortar, and 0.1 g of a sample that has passed through a sieve having an opening of 125 μm is decomposed with sulfuric acid-hydrogen peroxide using a microwave wet ashing device (automatic). The volume is made up to 50 mL, measured with an ICP emission spectrometer, and the amounts of Na, K, Li, Ca, and Mg are determined and calculated.

  As addition amount of a layered clay mineral (b-1), it is preferable that it is 1-25 mass parts with respect to 100 mass parts of particle | grains A, In order to fully acquire the effect of this invention, More preferably, it is 1.5 mass parts. It is above, More preferably, it is 2 mass parts or more. Moreover, 23 mass parts or less are preferable, 20 mass parts or less are more preferable, More preferably, it is 15 mass parts or less. In addition, since the layered clay mineral (b-1) contains impurities such as quartz, cristobalite, calcite, feldspar and the like, particularly in the case of natural, the content of the layered clay mineral (b-1) Is also included.

[Nonionic surfactant (b-2)]
Examples of the nonionic surfactant (b-2) include polyoxyalkanediyl alkyl ether, alkylene polyglycoside, polyoxyalkanediylalkylphenyl ether, polyoxyalkanediyl sorbitan fatty acid ester, polyoxyalkanediyl glycol fatty acid ester, polyoxy Ethylene polyoxypropylene block polymer and polyoxyalkanediylalkylolamide are preferably mentioned.

  The HLB of a nonionic surfactant suitable for the surface modification method of the present invention is preferably 6 to 16, more preferably 6 to 15, further preferably 6 to 14, and most preferably 6 to 13. If the HLB of the nonionic surfactant is within this range, the swellability when mixed with the layered clay mineral (b-1) increases, and it is very suitably used as a binder for surface modification.

As nonionic surfactants, in particular the following general formula (II):

A polyoxyalkanediyl alkyl ether obtained by adding an alkanediyl oxide such as ethylene oxide (EO) or propylene oxide (PO) to the alcohol represented by

Here, X, Y, and Z are average addition mole numbers, and satisfy | fill X> 0, Z> 0, X + Y + Z = 4-20. R is a hydrocarbon group having 8 to 18 carbon atoms, EO is an ethylene oxide group, and PO is a propylene oxide group. X, Y, and Z are preferably X> 0, Z> 0, and X + Y + Z = 4-9.
In general formula (II), carbon number is 8-18, and 10-16 are preferable. Moreover, as alkylene oxide average addition mole number, it is 4-20, 4-16 are more preferable, 4-12 are further more preferable, and 4-8 are especially preferable.

  As addition amount of nonionic surfactant (b-2), in order to acquire the effect of this invention enough, 1-20 mass parts is preferable with respect to 100 mass parts of particle | grains A, and 1-15 mass parts is more preferable. 5 to 15 parts by mass is more preferable. Here, the addition amount of the nonionic surfactant (b-2) is a nonionic surfactant other than the nonionic surfactant (b-2) at the time of preparing the slurry used when adjusting the particles A. When added, it does not include the added amount of the surfactant.

[Fine powder D]
The fine powder D is used for the purpose of modifying the surface of the particle C obtained by contacting the particle A, the layered clay mineral (b-1), and the nonionic surfactant (b-2). It is a thing made to contact. The surface of the particle C is modified with the fine powder D, so that the fluidity and storage stability of the particle are remarkably improved.
The fine powder D is preferably organic or inorganic particles that have not been treated with the above-described active ingredients, and the average particle size of the primary particles is preferably 10 μm or less, and preferably 0.1 to 10 μm. More preferably, it is 0.1-5 micrometers. If the average particle size is within this range, the coverage of the particle surface is improved, which is preferable from the viewpoint of improving the fluidity and caking resistance of the particles, that is, enabling good modification. The average particle diameter of the fine powder is a value measured in the same manner as the average particle diameter of the particles A described above. Moreover, when the particle | grains of this invention are used as a detergent, it is preferable from a washing | cleaning surface that the fine powder D has a high ion exchange ability and a high alkali ability.

As the fine powder D, sodium sulfate, calcium silicate, silicon dioxide, amorphous silica derivatives, silicate compounds such as crystalline silicate compounds, bentonite, talc, clay, crystalline or amorphous aluminosilicate are preferably mentioned. . Also preferred are metal soaps having primary particles of 0.1 to 10 μm, powdered surfactants (eg alkyl sulfates) and water-soluble organic salts. When a crystalline silicate compound is used, it is preferably used by mixing with a fine powder other than the crystalline silicate compound for the purpose of preventing deterioration due to moisture absorption or agglomeration of the crystalline silicate due to carbon dioxide gas.
As the usage-amount of the fine powder D, 10-70 mass parts is preferable with respect to 100 mass parts of particle | grains A, 10-65 mass parts is more preferable, and 10-60 mass parts is further more preferable. If the usage-amount of the fine powder D exists in the said range, fluidity | liquidity will improve and will give a favorable usability | use_condition to a consumer.

[Other components: Binder component]
In the present invention, in order to improve the adhesion between the layered clay mineral (b-1) and the fine powder D, it is preferable to add a binder component.
Examples of the binder component include one or more selected from the above-described nonionic surfactant (b-2), polyethylene glycol, (meth) acrylic acid polymer, cellulose derivative, and an aqueous solution thereof. Polyethylene glycol having an average molecular weight of 4000 or more and 20000 or less is preferable from the viewpoint of solidification at a temperature at which a detergent is usually used (˜40 ° C.) and solubility after surface treatment. Examples of the cellulose derivative include carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose and the like.

Moreover, as a binder component, the acid precursor of the anionic surfactant shown below can also be mentioned preferably. The acid precursor of the anionic surfactant is a substance that causes a neutralization reaction with the alkaline agent contained in the spray-dried particles, such as alkylbenzene sulfonic acid, alkyl or alkenyl ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-olefin. Examples include sulfonic acid, α-sulfonated fatty acid, alkyl or alkenyl ether carboxylic acid, and fatty acid. Among them, those having high water resistance are preferable. Particularly preferred acid precursors include fatty acids, hydroxy fatty acids, alkyl phosphoric acids and the like. In particular, one or more selected from fatty acids having 10 to 22 carbon atoms or hydroxy fatty acids are preferable from the viewpoint of solubility. Particularly preferred is one or more selected from saturated fatty acids having 12 to 20 carbon atoms in terms of the strength of the surface modified particles.
As addition amount of a binder component, 0.1-8 mass parts is preferable with respect to 100 mass parts of particle | grains A, 0.5-6 mass parts is more preferable, 1-4 mass parts is further more preferable. The binder component can be used alone or in combination.

[Other ingredients: Alkaline buffer]
In the present invention, as other components, particles A and powders and / or granules (hereinafter referred to as alkali buffering agents) having an alkali buffering ability can be mixed and used in advance. Examples of the alkali buffer include alkali metal silicates and carbonates.
As the alkali metal carbonate, sodium carbonate is preferable, and either dense ash (heavy ash) or light ash (light ash) may be used. It is also possible to adjust the bulk density by changing the ratio of dense ash and light ash.

  In addition, the alkali metal silicate is preferably one having ion exchange ability and dissolved in water to exhibit alkalinity. The ion exchange capacity can be measured, for example, by a method for measuring the Ca ion exchange capacity. The value is not particularly limited, but is preferably 10 to 250 mg / g, and particularly preferably 50 to 250 mg / g. More preferably, it is 120-250 mg / g, and the thing of this area | region is effective at the point which can be mix | blended with a compact detergent, when using as a Ca ion exchanger for detergents, and is effective at a small quantity.

  As an alkali metal silicate having such ion exchange ability, the following general formula (III)

A composition represented by the formula is preferred. Here, M represents Na and / or K, Me represents Ca and / or Mg, y / x = 0.5 to 4.0, z / x = 0 to 1.0, Mg / in MeO Ca (molar ratio) = 0 to 10. Examples of the alkali metal silicate having such a composition include sodium metasilicate, potassium metasilicate, powder No. 1 sodium silicate, powder No. 2 sodium silicate and the like. In addition, a crystalline alkali metal silicate described in JP-B-1-41116 is exemplified as an alkali metal silicate having a particularly high ion exchange capacity.
As a more preferable alkali metal silicate that expresses a higher ion exchange capacity, y / x = 1.0 to 2.1, z / x = 0.001 to 1.0 in the above composition formula (III). Alkali metal silicates. As the alkali metal silicate having such a composition, a synthetic inorganic builder described in Japanese Patent No. 2525318 is suitable.

Moreover, the storage stability can be further improved by using an alkali metal silicate containing potassium. As a composition of such an alkali metal silicate containing potassium, in the above formula (III), y / x = 1.4 to 2.1, z / x = 0.001 to 1.0, A composition represented by K / Na (molar ratio) in M ₂ O = 0.09 to 1.11. As such an alkali metal silicate, a crystalline alkali metal silicate described in Japanese Patent No. 2525342 is particularly preferable.

Among the crystalline alkali metal silicates, the most preferable is the crystalline layered sodium disilicate Na _{2 in which} x = 1, y = 2, z = 0 and M = Na in the general formula (III). Si ₂ O ₅ .wH ₂ O. Crystalline layered sodium disilicate is composed of polymorphic phases with varying proportions of α, β, δ and ε. In commercial products, an amorphous fraction may also be present, so the value of y in commercial products may be an odd number. Preferably, y is 1.9 or more and 2.2 or less. Preferred crystalline layered sodium disilicate is α-sodium disilicate in a proportion of 0-40% by mass, β-sodium disilicate in a proportion of 0-40% by mass, δ-sodium disilicate in a proportion of 40-100% by mass. , And consists of an amorphous fraction in a proportion of 0 to 40% by mass. Particularly preferred crystalline layered sodium disilicate is α-sodium disilicate in a proportion of 7 to 21% by mass, β-sodium disilicate in a proportion of 0 to 12% by mass, δ-disilicate in a proportion of 65 to 95% by mass. Sodium, consisting of an amorphous fraction with a proportion of 0-20% by weight. Most preferred is crystalline layered sodium disilicate containing δ-sodium disilicate in a proportion of 80 to 100% by mass. As the crystalline alkali metal silicate, those exemplified above may be used alone, or several kinds may be mixed and used as a mixture.

  10-50 mass parts is preferable with respect to 100 mass parts of particle | grains A, and, as for the compounding quantity of the alkaline buffer mixed beforehand with particle | grains A, 20-40 mass parts is more preferable. If it is in this range, sufficient cleaning performance and oil absorption ability can be expected.

[Particle surface modification method]
The surface modification method for particles according to the present invention comprises a step [1]: at least particles A having an average particle size of 100 to 3000 μm carrying an active ingredient, a layered clay mineral (b-1) having an average particle size of 10 to 100 μm, and The step of bringing the nonionic surfactant (b-2) into contact, and the step [2]: the step of bringing the particles C obtained in the step [1] into contact with the fine powder D having an average particle size of 0.1 to 10 μm , Has.

[Step [1]]
Step [1] is a step of bringing the particle A, the layered clay mineral (b-1), and the nonionic surfactant (b-2) into contact, and the layered clay mineral (b-1) and the nonionic surfactant are brought into contact with each other. After forming (B-2) in advance to form the composite B, the composite B and the particles A are preferably contacted. The step [1] includes the step of adjusting the particles A [A] and the carrying step [B] of bringing the obtained particles A, the layered clay mineral (b-1) and the nonionic surfactant (b-2) into contact with each other. It is divided roughly into. Further, in the preparation step [A] of the particles A, when spray-dried particles are used as the particles A, a step of preparing a slurry [A1], and a step of spray-drying the slurry to prepare spray-dried particles [A2] And [A3] for supporting the active ingredient.

[Preparation Step of Particle A [A]]
As the particles A, commercially available organic or inorganic particles may be used as described above, or spray drying obtained by spray drying an aqueous solution or dispersion containing a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt. Particles may be used.
When spray-dried particles are used as the particles A, the step [A] of preparing the particles A in the step [1] is preferably a step [A1] of preparing a slurry, and spray-drying the slurry to prepare spray-dried particles. It has process [A2] and the process [A3] which carries an active ingredient.

[Step [A1]]
The slurry used in the step [A1] may be a non-curable slurry that can be pumped, and such a slurry and each component constituting the slurry are as described above.
The temperature of a slurry becomes like this. Preferably it is 30-80 degreeC, More preferably, it is 35-65 degreeC. If it exists in this range, since the residual amount of water-soluble salts, such as sodium carbonate, will decrease, it is preferable.
The slurry moisture is generally preferably 30 to 70% by mass, more preferably 35 to 60% by mass, and most preferably 40 to 55% by mass. If the slurry moisture is within the above range, the amount of water-soluble salts dissolved is sufficient, and the increase in slurry viscosity can be suppressed, which is preferable in terms of pumping property. Further, since the amount of water evaporated in the step [A2] is suppressed, productivity does not decrease.

  As a method for forming the slurry, the method and order of adding the components constituting the slurry can be appropriately changed depending on the situation. For example, all or almost all of the water is first added to the mixing vessel, preferably after the water temperature has nearly reached the set temperature, the other ingredients are added sequentially or simultaneously. As a normal addition order, first, a water-soluble polymer and a liquid component such as a surfactant added as necessary are added, and then a water-soluble powder raw material such as a water-soluble salt is added. At this time, a small amount of auxiliary components such as a dye may be added. Next, a water-insoluble inorganic substance such as zeolite is added. For the purpose of improving the mixing efficiency, the water-insoluble inorganic substance may be added in two or more portions. In addition, powder raw materials such as water-insoluble inorganic substances and water-soluble salts may be mixed in advance and then added to an aqueous medium, or water may be added to adjust viscosity and slurry moisture after all components are added. . In order to finally obtain a homogeneous slurry, after all components are added to the slurry, it is preferably mixed for 10 minutes or more, more preferably 30 minutes or more.

[Step [A2]]
Step [A2] is a step of preparing spray-dried particles by spray-drying the slurry obtained in step [A1]. As a method for drying the slurry, spray drying in which the particle shape is substantially spherical is used. As the spray-drying tower, a countercurrent tower is more preferable because thermal efficiency and particle strength of the spray-dried particles are improved. The slurry atomizer may be any of a pressure spray nozzle, a two-fluid spray nozzle, and a rotating disk type, but a pressure spray nozzle is particularly preferable in order to obtain a desired average particle size.
The moisture of the spray-dried particles can be adjusted by adjusting the temperature of the gas supplied to the spray-drying tower and the amount of gas blown. As the gas to be supplied, those generally used for a heat medium can be used, and examples thereof include air and nitrogen. The temperature of the gas supplied to the spray-drying tower is preferably as high as possible in terms of oil absorption capacity, but in consideration of productivity, ease of production and safety, preferably 200 to 360 ° C. Preferably it is 220-340 degreeC, Most preferably, it is 240-320 degreeC. The temperature of the gas discharged from the spray drying tower is preferably 80 to 130 ° C., more preferably 80 to 125 ° C., and particularly preferably 80 to 120 ° C. in terms of thermal efficiency of the spray drying tower. Further, the spray-dried particles after spray-drying may be further dried by an air flow dryer, a fluidized bed dryer, a rotary dryer, or the like.

[Step [A3]]
Step [A3] is a step of supporting the active ingredient on particles A (commercially available organic or inorganic particles, or spray-dried particles obtained as described above).
As a method for supporting the active ingredient on the particles A, a conventionally known method can be employed. For example, when the active ingredient is a surfactant, the surfactant is converted into particles by the methods described in JP-A-5-5100, JP-A-6-9997, JP-A-9-183613, and the like. A can be supported on A. When the active ingredient is a fragrance or a water-soluble polymer compound, the fragrance or the water-soluble polymer compound is supported on the particles A by a method described in JP-A No. 2002-121582, JP-A No. 2005-330362, or the like. Can be made. When the active ingredient is silicone, the silicone can be supported on the particles A by the methods described in JP-A-7-1003009, JP-A-10-176197, and the like.

Examples of the method of supporting the active ingredient on the particles A include a method of mixing and supporting using an agitating and mixing device. Stir-mixers include “Henschel Mixer” (Mitsui Miike Chemical Co., Ltd.), “High Speed Mixer” (Fukae Kogyo Co., Ltd.), “Vertical Granulator” (Powrec Co., Ltd.), “Lady” Preferred examples include “Gemixer” (manufactured by Matsuzaka Giken Co., Ltd.), “Pro-Share Mixer” (manufactured by Taiheiyo Kiko Co., Ltd.), “Nauta Mixer” (manufactured by Hosokawa Micron Co., Ltd.), and the like. Among them, it is an apparatus in which a strong shearing force is not easily applied to the particle A (the particle A is difficult to disintegrate), and an apparatus with good mixing efficiency is preferable from the viewpoint of the dispersion efficiency of the active ingredient, and a horizontal mixing layer is provided at the center of the cylinder. A Readyge mixer, a Proshear mixer, and the like, which are mixers (horizontal mixers) of a type having a stirring shaft and mixing the particles by attaching a stirring blade to the shaft, are particularly preferable.
Further, the active ingredient may be supported on the particles A using the continuous apparatus of the above mixer. Examples of continuous mixers other than the above include “flexomix type” (manufactured by Pauletta Co., Ltd.), “turbulator” (manufactured by Hosokawa Micron Co., Ltd.), and the like.
The temperature in the apparatus at the time of mixing is preferably equal to or higher than the temperature at which the active ingredient has fluidity, and lower than the temperature at which the active ingredient significantly undergoes thermal decomposition and volatile evaporation. Specifically, it can be carried out at a temperature equal to or higher than the melting point of the active ingredient (in the case of a polymer compound, the glass transition point) and 100 ° C. or lower, more preferably 90 ° C. or lower.

  When the active ingredient is a polymer compound or a surfactant, a method in which an aqueous solution of the polymer compound or surfactant is prepared, mixed with a carrier, and then dried can be suitably employed. Specifically, it is possible to employ a method in which an aqueous solution of a polymer compound or a surfactant is mixed using a stirring / mixing device with an additional drying function and then dried. As a stirring and mixing device having a drying function, a vertical mixing dryer (manufactured by Shinko Environmental Solution Co., Ltd.), a vacuum stirring dryer (manufactured by Mitsubishi Materials Techno Co., Ltd.), a vacuum stirring dryer (Nippon Industries Co., Ltd.) Manufactured). Here, 10-100 mass% is preferable, as for content of the high molecular compound and surfactant of said aqueous solution, 20-100 mass% is more preferable, and 30-100 mass% is further more preferable.

[Supporting process [B]]
The supporting step [B] is a step of bringing the particles A obtained in the step [A], the layered clay mineral (b-1) and the nonionic surfactant (b-2) into contact with each other, and the layered clay mineral (b- It is preferable that after 1) and the nonionic surfactant (b-2) are contacted in advance to form the complex B, the complex B and the particle A are contacted. When the composite B is formed in advance, the supporting step [B] includes a step [B1] for preparing the composite B and a supporting step [B2] for bringing the composite B into contact with and supporting the particles A. Further, when the composite B is not formed, the particles A, the layered clay mineral (b-1) and the nonionic surfactant (b-2) can be contacted at the same time as in the supporting step [B2] described later. That's fine.

[Process [B1]]
Step [B1] is a step of preparing a composite B containing the layered clay mineral (b-1) and the nonionic surfactant (b-2).
When the ratio of the nonionic surfactant is small in the ratio of the liquid nonionic surfactant and the solid (powdered) layered clay mineral, the same method as the method of supporting the active ingredient on the particles A described above Can be adopted. On the other hand, when the ratio of the layered clay mineral is small, a method of dispersing and mixing the layered clay mineral in the nonionic surfactant composition is preferable. As a method for dispersing the layered clay mineral in the nonionic surfactant, for example, a method in which the layered clay mineral is added to the nonionic surfactant and then wet pulverized can be mentioned. Examples of the wet pulverizer include “TK homomic line mill (trade name)” (manufactured by Tokushu Kika Kogyo Co., Ltd.) and “Dyno-Mill (trade name)” (Willie A Bacofen AG Masashi). Preferable examples include a media mill type pulverizer typified by Nenefabric Switzerland (manufactured by Willy A. Bachofen AG Machinenfabrik Switzerland). Such a media mill type pulverizer is particularly suitable because of high pulverization efficiency.
When a high load is applied to the media mill due to its high viscosity, the layered clay mineral is uniformly dispersed in a low-viscosity liquid such as water in advance by dispersing it by treating it twice or more with a media mill type pulverizer. A method such as wet pulverization by a suitable pulverizer such as a mill and dispersion in a surfactant composition is preferably employed. Especially, the method of processing twice or more with a grinder is preferable at the point which can make the particle size distribution of a layered clay mineral sharper.

[Step [B2]]
Step [B2] is a step in which the composite B is brought into contact with and supported by the particles A.
As a method for supporting the composite B containing the layered clay mineral (b-1) and the nonionic surfactant (b-2) on the particles A, for example, a method using a batch type or continuous type known mixer is used. Can be mentioned. When the batch method is used, the mixing method is as follows: (1) While operating the mixer, the particles A are charged into the mixer and then the composite B is charged; (2) the particles A and the mixer are charged; A method of charging the composite B little by little, (3) charging a part of the particles A into the mixer, and then charging the remaining particles A and the composite B little by little. Among these methods, the above (1) is particularly preferable.

  As the mixer used in the step [B2], the same mixer as used when the active ingredient is supported on the particles A can be used without limitation. The same is true in that the preferred mixer is a Redige mixer or a Proshear mixer, and a continuous apparatus may be used.

The temperature in the mixer is preferably higher than the temperature higher than the melting point of the active ingredient (in the case of a polymer compound, the glass transition point). More specifically, the temperature is preferably higher than the melting point and up to 50 ° C higher than the melting point, more preferably 10 ° C to 30 ° C higher than the melting point. Moreover, when adding the acid precursor of the said surfactant at this process, it is more preferable if it heats up to the temperature which can react the acid precursor of the said anionic surfactant, and it mixes.
In addition, the batch mixing time for obtaining suitable base particles and the average residence time in continuous mixing are preferably 1 to 20 minutes, and more preferably 2 to 10 minutes.

Further, a water-soluble nonionic organic compound having a melting point of 45 to 100 ° C. and a molecular weight of 1000 to 30000 (hereinafter referred to as a melting point raising agent), or an aqueous solution, which is a melting point raising agent of the nonionic surfactant, is added to the complex B. Before, simultaneously with the addition, in the middle of the addition, after the addition, or in advance mixed with the nonionic surfactant (b-2). By adding a melting point-increasing agent, it is possible to suppress caking resistance and bleed-out of active ingredients such as surfactants in the surface-modified particles. Examples of the melting point raising agent used in the present invention include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic type nonionic surfactant.
The amount of the melting point raising agent used is preferably 5 parts by mass or less with respect to 100 parts by mass of the particles A from the viewpoint of maintaining mononuclearity of the surface-modified particles, high-speed solubility, and suppression of blemishes and caking properties. 3 parts by mass or less is particularly preferable and most preferably not included. As a method for adding the melting point increasing agent, mixing with the nonionic surfactant (b-2) by an arbitrary method in advance or adding a melting point increasing agent after the addition of the complex B It is advantageous for suppressing the bleeding out property and caking property.

In the step [B2], it is preferable to add a binder component because adhesion of the layered clay mineral (b-1) and the fine powder D is increased. The binder component may be added at the same time as adding the composite B to the particles A inside the mixer while operating the mixer, or when adjusting the composite B. When a binder component is added in the preparation of the composite B, the timing and conditions for the addition are not particularly limited.
Moreover, when using 2 or more types of binder components, you may add simultaneously and may add separately before and after adding the composite B to a mixer. The binder component that is solid at room temperature is preferably supplied after being melted, and is preferably supplied by spraying at a temperature higher than the internal temperature of the mixer.

[Step [2]]
Step [2] is a step in which the particles C obtained in step [1] are brought into contact with fine powder D to obtain surface-modified particles, and the treatment of adding fine powder D is performed at least once. It is. The fine powder D is brought into contact with the particle C obtained by bringing the layered clay mineral (b-1) and the nonionic surfactant (b-2) or the composite B containing them into contact with the surface of the particle A. By passing through the step [2], the high-speed solubility, fluidity and non-caking property of the surface-modified particles can be improved.
The apparatus used in the step [2] is not particularly limited, and a known mixer can be used, but the mixer exemplified in the step [A3] for supporting the active ingredient on the particles A is preferably used. The mixing time using the mixer is preferably 0.1 to 5 minutes, more preferably 0.5 to 3 minutes from the viewpoint of sufficiently adding the fine powder D onto the intermediate layer. Process at least once.

[Surface modified particles]
The surface modified particles of the present invention are composed of a composite layer composed of a composite B containing a layered clay mineral (b-1) and a nonionic surfactant (b-2) on the surface of the particle A, and a fine powder D. These fine powder layers are sequentially laminated. Such surface-modified particles can be preferably produced by the above-described particle surface modification method.
The composite layer and the fine powder layer are sequentially laminated from the surface of the particle A toward the surface side of the surface modified particles, but the composite layer does not necessarily need to cover the entire surface of the particle A, and the fine powder layer Does not necessarily need to cover the entire surface of the composite layer. That is, a fine powder layer may be present on the surface of the particle A, a composite layer may be present on the surface of the surface-modified particle, and there are places where the particle A is exposed. Sometimes. The entire surface of the particle A is preferably covered with either a composite layer or a fine powder layer, but it is not essential, and 30 to 100% of the surface of the particle A is covered with any layer. Preferably, 40 to 100% is more preferable, and 50 to 100% is more preferable.

The surface modified particles of the present invention are preferably mononuclear surface modified particles having the particle A as a nucleus. The mononuclear surface modified particles are, as necessary, a composite B containing fine particles and a layered clay mineral (b-1) and a nonionic surfactant (b-2) on a particle A carrying an active ingredient. D and surface-modified particles having other components added as necessary, the surface-modified particles having one particle A as a nucleus in one surface-modified particle That means. A method for producing such mononuclear surface modified particles is sometimes referred to as a mononuclear granulation method. As the mononuclear factor, the particle growth degree can be used, and the particle growth degree of the surface-modified particles obtained in the step [2] is expressed by the following formula (IV).
Particle growth rate = (average particle diameter of surface modified particles) / (average particle diameter of particles A) (IV)
It is represented by
The particle growth degree of the surface modified particles obtained in the step [2] is preferably 1.5 or less, more preferably 1.3 or less, and further preferably 1.2 or less from the viewpoint of the dissolution rate in washing. Since such surface-modified particles are prevented from aggregating between particles, for example, the generation of aggregated particles that are outside the range of the average particle size of the desired surface-modified particles is suppressed, and the surfactant Since the variation of the average particle size and the particle size distribution of the surface modified particles obtained with respect to the variation of the blending amount is reduced, homogeneous surface modified particles can be obtained in a high yield.

[Detergent composition]
The surface modified particles of the present invention are suitably used as surface modified particles for detergent compositions. There is no restriction | limiting in particular in the manufacturing method of a detergent composition, For example, the surface modification particle | grains of this invention and the detergent component added separately are mixed and obtained. The detergent composition can be used without particular limitation as long as it is an application using a powder detergent. For example, it can be preferably used as a powder detergent for clothing, a detergent for automatic tableware, and the like.
Separately added detergent components include, for example, known detergent base materials such as surfactants and builder granules, bleach (percarbonate, perborate, bleach activator, etc.), bleach activator, Examples include anti-staining agents (such as carboxymethyl cellulose), softening agents, reducing agents (such as sulfites), fluorescent brighteners, antifoaming agents (such as silicone), enzymes such as cellulase and protease, dyes, and fragrances.
The content of the surface-modified particles in the detergent composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more from the viewpoint of detergency. The content of the separately added detergent component in the detergent composition is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. .

The detergent composition produced by the production method of the present invention was evaluated according to the following method.
1. The average particle diameter was determined using a sieve specified in JIS Z 8801.
For example, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm, a low-tapping machine (made by HEIKO SEISAKUSHO, tapping: 156 times / min, rolling: 290 times / minute), 100 g of the sample was shaken for 5 minutes and sieved, and then the saucer and each sieve in the order of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm. When the mass frequency is accumulated below, the opening of the first sieve with an accumulated mass frequency of 50% or more is x _j μm, and the opening of the sieve smaller by one is x _{j + 1} μm. When the sum of the mass frequency from the saucer to the x _j μm sieve is Q _j %, x from the saucer _When the sum of the mass frequency up to the _{j + 1} μm sieve is Q _{j + 1} %, it can be obtained by the following equation. The average particle size x _a can be obtained by the formulas (1) and (2).

2. Bulk density It measured by the method prescribed | regulated by JISK3362.
3. Moisture Measured by a method defined by JIS K0068.
4). Storage stability (screening rate)
Using a filter paper (No. 2, manufactured by ADVANTEC), make a box without a top with a length of 10.2 cm, a width of 6.2 cm, and a height of 4 cm, and fix the four corners with a stapler. Into this, 50 g of the particles obtained in each Example and Comparative Example are put, and an acrylic resin plate (15 g) and a lead plate (250 g) are placed on the box. This is a temperature of 30 ° C., a humidity of 70% H. The passing rate specified in the following was determined for the caking state after being left for 21 days and 28 days in an atmosphere.
Sieve passing rate: The sample after the test is gently opened on a sieve (aperture 4760 μm defined in JIS Z 8801), the weight of the passed powder is measured, and the sieve passing rate (%) with respect to the sample after the test is obtained.
5. Storage stability (bleaching out property)
The state of spotting at the bottom (non-contact surface with the powder) of the filter paper container subjected to the sieve passing rate test was visually observed and evaluated according to the following criteria of 1 to 5 ranks.
Rank 1: The surface of about 1/4 or less is wet.
Rank 2: About 1/4 to 1/3 is wet.
Rank 3: The surface of about 1/3 to 1/2 is wet.
Rank 4: The surface of about 1/2 to 3/4 is wet.
Rank 5: The entire surface is wet.

In the examples, the following raw materials are used unless otherwise specified.
Sodium sulfate: “Anhydrous neutral sodium sulfate (trade name)” (manufactured by Shikoku Kasei Co., Ltd.)
Sodium sulfite: “Sodium sulfite (trade name)” (Mitsui Chemicals, Inc.)
Fluorescent dye: “Chino Pearl CBS-X (trade name)” (manufactured by Ciba Specialty Chemicals)
Sodium carbonate: “Dense ash (trade name)” (manufactured by Central Glass Co., Ltd.), average particle size: 290 μm
Sodium polyacrylate aqueous solution: manufactured by Kao Corporation, weight average molecular weight: 10,000 Crystalline aluminosilicate: manufactured by Zeobuilder, 4A type, average particle size: 3.5 μm
Crystalline silicate: Pre-feed (manufactured by Tokuyama Siltech Co., Ltd.) is pulverized and used as an average particle size of 10 μm Sodium dodecylbenzenesulfonate: “Neopelex G-25 (trade name)” (manufactured by Kao Corporation), Solid content: 26% by mass
Polyethylene glycol: “PEG 13000 (trade name)” (manufactured by Mitsui Chemicals, Inc.), weight average molecular weight: 10,000, solid content: 60%
Nonionic surfactant: “Emulgen 106 (E-106) (trade name)” (manufactured by Kao Corporation)
Layered clay mineral: “Round rosyl DGA powder (trade name)” (manufactured by Zoot Chemi), average particle size 16 μm, main component: bentonite (sodium bentonite activated with sodium carbonate)

Preparation Example 1: Preparation of spray-dried particles 410 parts by weight of water was added to a 1 m ³ mixing tank having a stirring blade, and after the water temperature reached 45 ° C., 110 parts by weight of sodium sulfate, 8 parts by weight of sodium sulfite, fluorescence 2 parts by weight of the dye was added and stirred for 10 minutes. Next, 120 parts by weight of sodium carbonate and 150 parts by weight of a 40% by weight aqueous sodium polyacrylate solution were added and stirred for 10 minutes, and further 40 parts by weight of sodium chloride and 160 parts by weight of crystalline aluminosilicate were added for 15 minutes. By stirring, a homogeneous slurry having a slurry water content of 50% by mass was obtained. The final temperature of this slurry was 50 ° C.
While supplying nitrogen gas at 285 ° C from the bottom of the tower to the spray drying tower, the slurry is supplied to the spray drying tower (counterflow type) by a pump and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower. Went. Nitrogen gas was discharged at 98 ° C. from the top of the column. The obtained spray-dried particles 1 had a water content of 0%, an average particle size of 290 μm, a bulk density of 510 g / L, a supporting capacity of 65 mL / 100 g, and a particle strength of 350 kg / cm.

Preparation Example 2: Preparation of surfactant composition 840 parts by mass of nonionic surfactant and 69 parts by mass of polyethylene glycol were heated to 80 ° C, 960 parts by mass of dodecylbenzenesulfonic acid, and 258 parts by mass of 48% aqueous sodium hydroxide solution. Parts were added and stirred to prepare a surfactant composition.

Preparation Example 3: Preparation of Surfactant-Supported Particles (Particle A) 50 parts by weight of the spray-dried particles prepared in Preparation Example 1 were charged into a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket). Stirring of the main shaft (rotation speed of stirring blade: 60 rpm, peripheral speed: 1.6 m / s) was started. Warm water at 80 ° C. was passed through the jacket at 10 L / min. Thereto, 25 parts by mass of the surfactant composition prepared in Preparation Example 2 heated to 80 ° C. was added over 2 minutes, and then stirred for 5 minutes to carry the surfactant composition on the spray-dried particles. Thus, surfactant-carrying particles (particle A) were prepared.

Example 1 Preparation of Surface Modified Particle 1 75 parts by mass of the surfactant-carrying particles prepared in Preparation Example 3 were introduced into a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket). Stirring at a rotating speed of the stirring blade: 60 rpm, peripheral speed: 1.6 m / s) was started. 5 parts by mass of layered clay mineral was added, 5 parts by mass of a nonionic surfactant was sprayed, and the mixture was stirred for 5 minutes.
Next, 5 parts by mass of crystalline aluminosilicate is added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) is performed. For 30 seconds. The operating conditions of the Redige mixer are returned to the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), and 10 parts by mass of crystalline aluminosilicate is added. Further, the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were stirred again for 30 seconds, then discharged, and the surface of Example 1 Modified particles 1 were obtained. The composition and evaluation of the obtained surface modified particles 1 are shown in Table 1.

Example 2: Preparation of surface modified particles 2 10 parts by mass of layered clay mineral was put into a readyge mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket), and the main shaft (rotation speed of stirring blade: 60 rpm) , Peripheral speed: 1.6 m / s) was started. Warm water at 80 ° C. was passed through the jacket at 10 L / min. In the state which continued stirring, 5 mass parts nonionic surfactant was thrown in over 1 minute, and it stirred for 5 minutes after that. Further, with the stirring continued, 75 parts by mass of spray-dried particles were charged over 3 minutes, and then stirred for 5 minutes.
Next, 5 parts by mass of crystalline aluminosilicate is added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) is performed. For 30 seconds. The operating conditions of the Redige mixer are returned to the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), and 5 parts by mass of crystalline aluminosilicate is added. Further, the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were stirred again for 30 seconds, then discharged, and the surface of Example 2 Modified particles 2 were obtained. The composition and evaluation of the obtained surface modified particles 2 are shown in Table 1.

Example 3 Preparation of Surface Modified Particle 3 70 parts of polyoxyethylene dodecyl ether (average added mole number of ethylene oxide: 8, melting point: 15 ° C., HLB 10) and 10 parts by weight of palmitic acid (average particle size: 20 μm) were 70 parts. The mixture was heated and mixed to a temperature of 0 ° C. to prepare a mixed solution. Next, 35 parts by mass of dense ash, 10 parts by mass of zeolite 4A and 20 parts by mass of amorphous aluminosilicate were introduced into a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 20 L, with jacket), and the main shaft (150 rpm ) And chopper (4000 rpm). In addition, 75 degreeC warm water was poured by the jacket at 10 L / min. Thereto, the mixed solution was added over 4 minutes, and then stirred for 6 minutes to prepare nonionic detergent particles.
Surface-modified particles 3 were obtained in the same manner as in Example 1 except that 75 parts by mass of the surfactant-carrying particles in Example 1 were changed to 75 parts by mass of the nonionic detergent particles. The composition and evaluation of the obtained surface modified particles 3 are shown in Table 1.

Example 4: Preparation of surface modified particles 4 30 parts by mass of polyoxyethylene dodecyl ether (average number of moles of ethylene oxide added: 8, melting point: 15 ° C., HLB10) and 20 parts by mass of palmitic acid (average particle size: 20 μm) were 70 parts. The mixture was heated and mixed to a temperature of 0 ° C. to prepare a mixed solution. Next, 30 parts by mass of crystalline metal silicate and 23 parts by mass of amorphous aluminosilicate (average particle size 10 μm) were put into a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 20 L, with jacket). (150 rpm) and chopper (4000 rpm) were started for stirring. In addition, 75 degreeC warm water was poured by the jacket at 10 L / min. Thereto, the mixed solution was added over 4 minutes, and then stirred for 6 minutes to prepare nonionic detergent particles.
Surface-modified particles 3 were obtained in the same manner as in Example 1 except that 75 parts by mass of the surfactant-carrying particles in Example 2 were changed to 75 parts by mass of the above nonionic detergent particles. The composition and evaluation of the obtained surface modified particles 3 are shown in Table 1.

Example 5: Preparation of surface modified particles 5 As a component having a vapor pressure of 0.133 to 133 Pa at 25 ° C., a mixture of lyial, furtate, α-damascone and poreate, and a component having a vapor pressure of less than 0.13 Pa at 25 ° C. A blended fragrance in which methyl-β-naphthyl ketone was mixed at a ratio of 80/20 (mass ratio) was prepared. The blended fragrance, dextrin, sodium sulfate, silicon dioxide, bengara, red 226 were charged into a Nauter mixer (manufactured by Hosokawa Micron Corporation) with the following composition, the jacket temperature was set to 75 ° C., and the mixture was heated up. Next, when the temperature of the powder reaches 60 ° C., 21 parts by mass of polyethylene glycol previously melted and polyethylene glycol in a solid state at a ratio of 70/30 (mass ratio) are added and further mixed. The mixture was extracted from. The temperature of the mixture at this time was 66 ° C. Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm by using an extrusion granulator (“Peletter Double EDX-60 type” manufactured by Fuji Powder Co., Ltd.) and consolidated. Further, after cooling the extruded granulated product, it is pulverized with a granulator (pulverized once with a power mill and further pulverized once with a comil) and passed through a sieve to remove particles having a particle size of 355 μm or less. Colored fragrance particles were obtained.
Surface-modified particles 5 were obtained in the same manner as in Example 1 except that 75 parts by mass of the surfactant-carrying particles in Example 1 were changed to 75 parts by mass of the above-described fragrance particles. The composition and evaluation of the obtained surface modified particles 5 are shown in Table 1.
Composition of fragrance particles Blended fragrance: 10 parts by mass Dextrin ("Pine Flow KH": Matsutani Chemical Co., Ltd.): 12 parts by mass Polyethylene glycol ("KPEG-6000LA": Kao Corporation): 21 parts by mass Sodium sulfate ("Pulverized Soda Glass A6": Shikoku Chemical Industry Co., Ltd.): 38 parts by mass Sodium sulfate ("Crushed Soda Glass A12": Shikoku Chemical Industry Co., Ltd.): 5 parts by mass Silicon dioxide ("Tokuseal NR": Tokuyama Soda (Made by Co., Ltd.): 14 parts by mass “Bengara” (Miyoshi Kasei Kogyo Co., Ltd.): 0.02 parts by mass “Red No. 226” (Made by Kasei Chemical): 0.03 parts by mass

Example 6: Preparation of surface-modified particles 6 10 parts by weight of paraffin wax (melting point: about 42 ° C., average particle size: 500 μm), 20 parts by weight of polyethylene glycol (average molecular weight: 6000, melting point: 55 ° C.), 30 parts by weight of sodium sulfate, And 40 parts by mass of rice starch in a powder mixture were charged into an extruder type kneader (“Exlude O Mix (model number)” manufactured by Hosokawa Micron Corporation) heated to 60 to 80 ° C. The mixture was operated at a rotation speed of 150 rpm and kneaded through an intermediate orifice hole diameter of 6 mm and an outlet die hole diameter of 1 mm to obtain a granulated product. Next, 50 parts by mass of the spray-dried particles prepared in Preparation Example 2 are added to the extruder type kneader heated to 60 to 80 ° C., and 25 parts by mass of the granulated product is added to operate at 150 rpm. Then, the mixture was kneaded through an intermediate orifice hole diameter of 6 mm and an outlet die hole diameter of 1 mm to obtain wax-based antifoaming agent-supported particles.
Surface-modified particles 6 were obtained in the same manner as in Example 1 except that 75 parts by mass of the surfactant-carrying particles in Example 2 were changed to 75 parts by mass of the wax-based antifoaming agent-carrying particles. The composition and evaluation of the obtained surface modified particles 6 are shown in Table 1.

Example 7: Preparation of surface-modified particles 7 75 parts by mass of the surfactant-carrying particles of Example 1 were added to “Sokalan CP 45 Granules”: BASF (poly (acrylic acid / maleic acid) sodium, average molecular weight 70000) 75. Surface-modified particles 7 were obtained in the same manner as in Example 1 except that the mass parts were changed. The composition and evaluation of the obtained surface modified particles 7 are shown in Table 1.

Comparative Example 1: Preparation of Particle 1 Particle 1 was obtained in the same manner as in Example 1 except that the layered clay mineral of Example 1 was changed to crystalline silicate. The evaluation of the obtained particles 1 is shown in Table 2.

Comparative Example 2: Preparation of Particle 2 Particle 2 was obtained in the same manner as in Example 2, except that the layered clay mineral of Example 2 was changed to crystalline silicate. The evaluation of the obtained particles 2 is shown in Table 2.

Comparative Example 3: Preparation of Particle 3 Particle 3 was obtained in the same manner as in Example 3, except that the layered clay mineral of Example 3 was changed to crystalline silicate. The evaluation of the obtained particles 3 is shown in Table 2.

Comparative Example 4: Preparation of Particle 4 Particle 4 was obtained in the same manner as in Example 4 except that the layered clay mineral of Example 4 was changed to a crystalline silicate. The evaluation of the obtained particles 4 is shown in Table 2.

Comparative Example 5: Preparation of particles 5 Particles 5 were obtained in the same manner as in Example 5 except that the layered clay mineral of Example 5 was changed to crystalline silicate. The evaluation of the obtained particles 5 is shown in Table 2.

Comparative Example 6: Preparation of Particle 6 Particle 6 was obtained in the same manner as in Example 6 except that the layered clay mineral of Example 6 was changed to crystalline silicate. The evaluation of the obtained particles 6 is shown in Table 2.

Comparative Example 7: Preparation of Particle 7 Particle 7 was obtained in the same manner as in Example 7, except that the layered clay mineral of Example 7 was changed to crystalline silicate. Table 2 shows the evaluation of the particles 7 obtained.

  The surface-modified particles 1 to 7 obtained in Examples 1 to 7 have a layer made of the composite B containing a lamellar clay mineral and a nonionic surfactant, so that both the screen passing rate and the blemishes are obtained. From this, it was shown that the particles were excellent in storage stability. On the other hand, since the particles 1 to 7 obtained in Comparative Examples 1 to 7 do not have a layer made of the composite B containing the layered clay mineral and the nonionic surfactant, the storage stability is inferior to that of the examples. It was confirmed that

Claims (5)

A method for surface modification of particles for a powder composition, comprising the following steps [1] and [2].
Step [1]: At least a layered clay mineral (b-1) having an average particle size of 10 to 100 μm is brought into contact with a nonionic surfactant (b-2) to form a complex B, and then the complex B , A step of contacting the particles A having an average particle diameter of 100 to 3000 μm carrying the active ingredient, the active ingredient being liquid or paste at 20 ° C., surfactant, solvent, fragrance, silicone, water-soluble The process which is 1 or more types chosen from a high molecular compound and a wax-type antifoamer.
Step [2]: Sodium sulfate, calcium silicate, silicon dioxide, amorphous silica derivative, crystalline silicate compound, bentonite having particles C obtained in step [1] and an average particle size of 0.1 to 10 μm A step of contacting fine powder D comprising at least one selected from talc, clay, crystalline aluminosilicate, and amorphous aluminosilicate.   The surface modification method for particles for a powder composition according to claim 1, wherein the fine powder D is crystalline aluminosilicate. The layered clay mineral (b-1) has the following general formula (I)

(Wherein a, b and x are 0 <a ≦ 6, 0 <b ≦ 4, x = 12-2a-3b, and Me is Na, K, Li, Ca ^1/2 , Mg ^1/2. And at least one ion selected from NH _4. The molar ratio (Na + K + Li) / (Ca + Mg) of the alkali metal ion and alkaline earth metal ion represented by the following formula among the ions is 1.0. That's it.)
The surface modification method of the particle | grains for powder compositions of Claim 1 or 2 represented by these.   The surface modification method for particles for a powder composition according to any one of claims 1 to 3, wherein the HLB of the nonionic surfactant (b-2) is 6 to 16. The nonionic surfactant (b-2) has the following general formula (II)

(In the formula, X, Y, and Z are average added mole numbers and satisfy X> 0, Z> 0, and X + Y + Z = 4 to 20. R is a hydrocarbon group having 8 to 18 carbon atoms, EO Is an ethylene oxide group, and PO is a propylene oxide group.)
The method for surface modification of particles for a powder composition according to any one of claims 1 to 4, wherein the polyoxyalkanediyl alkyl ether is represented by the formula: