JP2016011299A - Treatment agent, wood preservation agent and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treatment agent in which, while securing the efficiency of the first treatment agent in which an effective component remains on the surface of the material to be treated, excellent in the efficiency maintaining effect of the second treatment agent in which an effective component infiltrates into the material to be treated, a wood preservation agent and a coating material.SOLUTION: Provided is a treatment agent comprising: a first treatment agent in which an effective component remains on the surface of the material to be treated; and a second treatment agent in which an effective component infiltrates into the material to be treated. The first treatment agent has the average particle diameter of 1 μm or higher and the first particles including the effective component. The second treatment agent has the average particle diameter below 1 μm and the second particle including the effective component.

Description

  The present invention relates to a treatment agent, a wood preservative, and a paint, and more particularly, to a treatment agent and a wood preservative and a paint containing the treatment agent.

  Conventionally, it is known to treat a material to be treated such as wood with a treatment agent such as a wood preservative to protect the material to be treated.

  For example, a wood preservative containing a first preparation in which an active ingredient remains on the surface of wood and a second preparation in which the active ingredient penetrates into the wood has been proposed (see, for example, Patent Document 1 below) .)

  According to the wood preservative described in Patent Document 1, the active ingredient of the first preparation remains on the surface of the wood, and the active ingredient of the second preparation penetrates into the interior of the wood. Excellent efficacy can be expressed both inside the wood.

JP 2008-081466 A

  However, the second preparation of the treatment agent such as the wood preservative may be required to have an excellent effect of sustained efficacy.

  However, the wood preservative described in Patent Document 1 may not be able to satisfy the above requirements.

  The objective of this invention is providing the processing agent, wood preservative, and coating material which are excellent in the effect sustained effect of the 2nd processing agent which an active ingredient osmose | permeates the inside of a to-be-processed material.

  As a result of intensive studies on the above-described treatment agent, wood preservative, and coating material, the present inventors have the second treatment agent contain second particles having an average particle diameter of less than 1 μm and containing an active ingredient. As a result of finding the knowledge that the effect of sustaining the efficacy of the second treatment agent can be sufficiently enhanced, and further researching it, the present invention has been completed.

That is, the present invention
(1) An active ingredient contains the 1st processing agent which remains on the surface of a material to be processed, and the 2nd processing agent which an active ingredient penetrates into the inside of a material to be processed, The 1st processing agent The first particle having an average particle diameter of 1 μm or more and containing an active ingredient is contained, and the second treatment agent has an average particle diameter of less than 1 μm and contains second particles containing an active ingredient. A treatment agent, characterized by
(2) The ratio of the second treating agent to the total amount of the first treating agent and the second treating agent is 60% by mass or more and 95% by mass or less (1) ) Treatment agent,
(3) The ratio of the active ingredient contained in the second treating agent to the total amount of the active ingredient contained in the first treating agent and the active ingredient contained in the second treating agent, 55% by mass or more and 95% by mass or less, the treating agent according to (1) or (2) above,
(4) The second particles are prepared by dissolving a hydrophobic active ingredient with a hydrophobic polymerizable vinyl monomer to prepare a hydrophobic solution, blending water and an emulsifier to prepare an aqueous emulsifier solution, The above (1) is obtained by emulsifying the hydrophobic solution in the aqueous emulsifier solution and polymerizing the polymerizable vinyl monomer by miniemulsion polymerization in the presence of a polymerization initiator. ) To (3),
(5) The processing agent according to any one of (1) to (4) above, wherein the second processing agent contains an antiseptic and fungicidal agent as an active ingredient,
(6) The treating agent according to (5) above, wherein the antiseptic / fungal agent contains an organic iodine compound and / or a triazole compound.
(7) The treatment agent according to any one of (1) to (6) above, wherein the first particles are microcapsules in which an active ingredient is encapsulated by a film.
(8) In the absence of a solvent, the first particles disperse an active ingredient that is hydrophobic and substantially insoluble in the polymerizable vinyl monomer in the hydrophobic polymerizable vinyl monomer. A slurry forming step for preparing a hydrophobic slurry, an aqueous dispersion step for preparing an aqueous dispersion by dispersing the hydrophobic slurry in water, and suspension polymerization of the polymerizable vinyl monomer to produce a polymer. The treatment agent according to any one of (1) to (6) above, which is obtained by a production method including a polymerization step,
(9) a hydrophobic solution preparation step in which the first particles prepare a hydrophobic solution by dissolving a hydrophobic active ingredient in a hydrophobic polymerizable vinyl monomer in the absence of a solvent; It is obtained by a production method comprising an aqueous dispersion step of preparing an aqueous dispersion by dispersing the hydrophobic solution in water, and a polymerization step of producing a polymer by suspension polymerization of the polymerizable vinyl monomer. The treating agent according to any one of (1) to (6) above,
(10) The treatment agent according to (9) above, wherein the hydrophobic active ingredient is compatible with the polymer in the first particles.
(11) The first particles have a phase separation structure formed from a matrix composed of the polymer and a domain composed of the hydrophobic active ingredient separated from the matrix. The treating agent according to (9) above,
(12) The treatment agent according to any one of (1) to (11) above, wherein the first treatment agent contains an insecticide and / or a repellent as an active ingredient.
(13) The treatment agent according to (12) above, wherein the insect repellent contains a neonicotinoid insecticide and / or a pyrethroid insecticide,
(14) The treatment agent according to (12) above, wherein the repellent contains capsaicins.
(15) A wood preservative comprising the treatment agent according to any one of (1) to (14) above,
(16) A paint comprising the treating agent according to any one of (1) to (14) above.

  The treatment agent of the present invention can improve the effect of sustaining the effect of the second treatment agent with respect to the material to be treated. Therefore, an excellent effect of sustaining the effect can be expressed inside the material to be treated.

  Therefore, according to the wood preservative of the present invention containing the above-mentioned treatment agent, the active ingredient of the second treatment agent penetrates into the interior of the wood, and exhibits an excellent effect of sustaining the effect inside the wood. Can do.

  In addition, according to the coating material of the present invention containing the above-described treatment agent, the effective ingredient of the second treatment agent penetrates into the inside of the application target and exhibits an excellent effect of sustaining the effect inside the application target. Can do.

FIG. 1 shows a schematic cross-sectional view of a first multi-domain particle. FIG. 2 shows an image processing diagram of a TEM photograph of the first multi-domain particle of Preparation Example 2. FIG. 3 shows an image processing diagram of a TEM photograph of the first compatible particles in Preparation Example 3. FIG. 4 shows an image processing diagram of a TEM photograph of the first compatible particles of Preparation Example 8. FIG. 5 shows an image processing diagram of a TEM photograph of the first compatible particle in Preparation Example 10.

1. Treatment Agent The treatment agent of the present invention contains a first treatment agent in which an active ingredient remains on the surface of the material to be treated and a second treatment agent in which the active ingredient penetrates into the material to be treated.

2. Active ingredient Active ingredients include hydrophobic antibiotic compounds. Antibiotic active compounds include, for example, a first antibiotic active compound that is substantially insoluble in a polymerizable vinyl monomer (described below), such as a second that is substantially compatible with the polymerizable vinyl monomer. Antibiotic active compounds are mentioned. These first antibiotic active compounds and second antibiotic active compounds can be used alone or in combination of two or more.
2-1. First antibiotic active compound The first antibiotic active compound is substantially insoluble in the polymerizable vinyl monomer, specifically, for example, at room temperature (20-30 ° C., relative to the polymerizable vinyl monomer). More specifically, the solubility at 25 ° C. is extremely small. Specifically, the solubility at room temperature is, for example, 0.1 parts by mass / (used) polymerizable vinyl monomer (mixture) 100 parts by mass. Parts (1000 ppm) or less, preferably 0.05 parts by mass / (use) polymerizable vinyl monomer (mixture) 100 parts by mass (500 ppm) or less.

  The molecular weight of the first antibiotic compound is not particularly limited.

  The melting point of the first antibiotic compound is, for example, 80 ° C. or higher, preferably 100 ° C. or higher, and is 300 ° C. or lower if the compound does not contain a metal atom.

  The first antibiotic active compound has, for example, an antibiotic activity such as insecticide (including ant), insect repellent (including ant), bactericidal, antibacterial, antiseptic, herbicidal, algal, fungicidal, attracting and repelling. Select from insecticides (including anticides), insecticides (including anticides), fungicides, antibacterial agents, antiseptics, herbicides, algae proofers, fungicides, attractants and repellents Is done.

  Specifically, as the first antibiotic compound, for example, as an insecticide, clothianidin ((E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine), Neonicotinoid insecticides such as thiacloprid, thiamethoxam, dinotefuran, diamides such as fulvendiamide and chlorantraniliprole, insect growth control agents such as diflubenzuron, teflubenzuron, chlorfluazuron, tebufenozide, methoxyphenozide, and cyromazine, clofente Examples include acaricides such as gin, and other synthetic drugs such as pymetrozine and sodium oleate. Examples of fungicides include copper-based fungicides such as basic copper chloride, basic copper sulfate, and oxine copper, silver-based fungicides such as metallic silver, organic sulfur-based fungicides such as polycarbamate, fusalides, and tricyclazole. Melanin biosynthesis inhibitors, thiobenzate methyl, MBC, benzimidazole fungicides such as dietofencarb, acid amide fungicides such as isothianyl, sterol biosynthesis inhibitors such as triphorin, isothiazolones such as 1,2-benzisothiazolin-3-one And other synthetic inhibitors such as steric fungicides, dichromidine, fluorimide, captan, chlorothalonil, quinotimeoate, oxolinic acid, benchavaricarb isopropyl, diazofamide, and zinc pyrithione. For example, as herbicidal / algaeproofing agents, urea drugs such as DCMU, cumyluron, carbylate, ethoxysulfuron, halosulfuronmethyl, frazasulfuron, nicosulfuron, thifensulfuronmethyl, imazosulfuron, cyclosulfamuron, flucetos Sulfonyl ureas such as ruflon and trifloxysulfuron sodium salt, triazines such as CAT, atrazine, triadifram, lenacyl, sibulthrin and terbutrin, amino acids such as glyphosate, phenylphthalimides such as flumioxazine, triketones such as mesotrione And other drugs such as quinoclamin and pyriftalide.

These first antibiotic compounds can be used alone or in combination of two or more.
2-2. Second antibiotic active compound The molecular weight of the second antibiotic active compound is, for example, 200 or more, and for example, 600 or less, preferably 500 or less.

  The melting point of the second antibiotic compound is, for example, 100 ° C. or lower, preferably 90 ° C. or lower, more preferably 80 ° C. or lower.

  Specifically, the second antibiotic active compound is an antibacterial agent, antibacterial agent, antiseptic agent, anti-algae having antibiotic activity such as bactericidal, antibacterial, antiseptic, algal, antifungal, insecticidal, attracting and repelling Selected from agents, fungicides, herbicides, insecticides, attractants and repellents. Examples of these antibiotic-active compounds include organic iodine compounds, triazole compounds, carbamoylimidazole compounds, dithiol compounds, isothiazoline compounds, nitroalcohol compounds, paraoxybenzoic acid esters, and the like. Fungicides (including antiseptic fungicides), for example, pyrethroid compounds, neonicotinoid compounds, organochlorine compounds, organophosphorus compounds, carbamate compounds, oxadiazine compounds, anticides (anticides) Etc.

  Examples of the organic iodo compound include 3-iodo-2-propynylbutylcarbamate (IPBC), 1-[[(3-iodo-2-propynyl) oxy] methoxy] -4-methoxybenzene, and 3-bromo-2. , 3-diiodo-2-propenyl ethyl carbonate and the like.

  Examples of the triazole compound include 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole (propico). Nazole), bis (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethylsilane (also known as flusilazole, 1-[[bis (4-fluorophenyl) methylsilyl] methyl] -1H- 1,2,4-triazole) and the like.

  Examples of the carbamoylimidazole compound include N-propyl-N- [2- (2,4,6-trichloro-phenoxy) ethyl] imidazole-1-carboxamide (prochloraz).

  Examples of the dithiol-based compound include 4,5-dichloro-1,2-dithiol-3-one.

  Examples of the isothiazoline-based compound include 2-n-octyl-4-isothiazolin-3-one (OIT) and 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT).

  Examples of the nitroalcohol compound include 2,2-dibromo-2-nitro-1-ethanol (DBNE).

  Examples of the paraoxybenzoic acid ester include butyl paraoxybenzoate and propyl paraoxybenzoate.

  Examples of the pyrethroid compounds include pyrethroid insecticides such as pyrethrin, cineline, and jasmolin obtained from Shirovanamyoyokeiku, and arelesrin, bifenthrin, acrinathrin, alpha cypermethrin, tralomethrin, and cifluthrin ((RS)-) derived therefrom. α-Cyano-4-fluoro-3-phenoxybenzyl- (1RS, 3RS)-(1RS, 3RS) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate. Form I ((1R-3R-αR) + (1S-3S-αS)) [melting point: 57 ° C.], isomer II ((1R-3R-S) + (1S-3S-αR)) [melting point: 74 ° C], isomer III ((1R-3S-αR) + (1S-3R-αS))) [melting point: 66 ° C] Mixture), cyphenothrin, prallethrin, etofenprox (2- (4-ethoxyphenyl) -2-methylpropyl 3- phenoxybenzyl = ether), silafluofen also include pyrethroid insecticides such as fenvalerate.

Examples of neonicotinoid compounds include (E) -N ¹ -[(6-chloro-3-pyridyl) methyl] -N ² -cyano-N ¹ -methylacetamidine (acetamipride).

  Examples of the organic chlorine compound include Kelsen.

  Examples of the organophosphorus compounds include phoxime, pyridafenthione, fenitrothion, tetrachlorvinphos, diclofenthione, propetanephos, and the like.

  Examples of carbamate compounds include fenocarb and propoxur.

  Examples of the oxadiazine compound include indoxacarb.

  Examples of the herbicide include pyraclonyl, pendimethalin, indanophan and the like.

  Examples of the insecticide include pyriproxyfen.

  Examples of the repellent include diet and capsaicin. Preferably, capsaicins are used. Examples of capsaicins include capsaicin (N-[(4-hydroxy-3-methoxyphenyl) methyl] -8-methyl-6-nonenamide) and capsaicin derivatives. Examples of capsaicin derivatives include N-vanillyl nonanamide (VNA), noneric acid vanillylamide, decylic acid vanillylamide, nordihydrocapsaicin, dihydrocapsaicin, homodihydrocapsaicin, homocapsaicin and the like. Preferably, capsaicins include capsaicin and VNA.

  These second antibiotic compounds can be used alone or in combination of two or more.

3. First treatment agent The first treatment agent contains first particles.

  The first particles contain an active ingredient. Specifically, for example, microcapsules in which the active ingredient is encapsulated by a film, for example, active ingredient dispersed particles in which the active ingredient is dispersed in a polymer, for example, Contains flowable particles.

  The average particle diameter of the first particles is calculated as a median diameter and is 1 μm or more, preferably 5 μm or more, and for example, 1 mm or less, preferably 100 μm or less.

In the first particle, examples of the active ingredient include a first antibiotic active compound and a second antibiotic active compound, which can be used alone or in combination. For example, the first antibiotic active compound can be used alone, or the first antibiotic active compound and the second antibiotic active compound can be used in combination.
3-1. Microcapsule The active ingredient encapsulated in the microcapsule is preferably the first antibiotic compound, more preferably an insecticide, still more preferably a neonicotinoid insecticide, particularly preferably clothianidin.

  The microcapsules can be prepared by a known method such as a chemical method, a physicochemical method, a physical and a mechanical method.

  Examples of the chemical method include an interfacial polymerization method, an in situ polymerization method, and a liquid-cured coating method.

  As the interfacial polymerization method, for example, a method of interfacial polymerization of polybasic acid halide and polyol to form a film made of polyester, a method of interfacial polymerization of polybasic acid halide and polyamine to form a film made of polyamide, Examples thereof include a method of forming a film made of polyurethane by interfacial polymerization of polyisocyanate and polyol, and a method of forming a film made of polyurea by interfacial polymerization of polyisocyanate and polyamine.

  In the in-situ polymerization method, for example, a method of forming a film made of polystyrene copolymer by copolymerizing styrene and divinylbenzene, a film made of polymethacrylate copolymer by copolymerizing methyl methacrylate and n-butyl methacrylate The method of forming is mentioned.

  Examples of the submerged cured coating method include a method of curing gelatin, polyvinyl alcohol, epoxy resin, sodium alginate and the like in the liquid.

  Examples of the physicochemical method include a phase separation method from an aqueous solution such as a simple coacervation method, a complex coacervation method, a pH control method, and a non-solvent addition method, and a core cell such as a phase separation method from an organic solvent. Examples include the basation method. In the physicochemical method, examples of the film forming component include gelatin, cellulose, gelatin-gum arabic, and the like. In addition, an interfacial precipitation method using polystyrene or the like can also be exemplified.

  Examples of the physical and mechanical methods include a spray drying method, an air suspension coating method, a vacuum deposition coating method, an electrostatic coalescence method, a melt dispersion cooling method, and an inorganic wall encapsulation method. In the physical and mechanical methods, examples of the film forming component include gelatin, gum arabic, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, sodium alginate and the like.

  Preferably, the microcapsules are prepared by an interfacial polymerization method. Such an interfacial polymerization method can be prepared, for example, in accordance with the description in JP-A No. 2004-189734.

  In the microcapsule, the thickness of the film is, for example, 0.5 μm or less, and, for example, 0.01 μm or more. It is at least 1 part by mass, preferably at least 1 part by mass, for example, at most 100 parts by mass, preferably at most 50 parts by mass.

The average particle diameter of the microcapsules is calculated as a median diameter, and is 1 μm or more, preferably 6 μm or more, more preferably 10 μm or more, and for example, 100 μm or less, preferably 30 μm or less.
3-2. Active ingredient dispersed particles As long as the active ingredient dispersed particles are particles in which an active ingredient is dispersed in a polymer, the dispersion form of the active ingredient is not particularly limited. As the active ingredient dispersed particles, for example, a multi-domain type particle (first multi-domain type particle) having a two-phase structure formed from a polymer and an active ingredient dispersed in the polymer, for example, a polymer Examples thereof include first compatible particles having a homogeneous phase in which the active ingredient is compatible.

(1) Monomer for producing a polymer The monomer for producing a polymer is hydrophobic and is, for example, a polymerizable vinyl monomer having at least one vinyl group in the molecule. Examples of such polymerizable vinyl monomers include (meth) acrylic acid ester monomers, (meth) acrylic acid monomers, aromatic vinyl monomers, vinyl ester monomers, maleic acid ester monomers, vinyl halides, halogens. And vinylidene chloride, a nitrogen-containing vinyl monomer, and a crosslinkable monomer.

  Examples of (meth) acrylic acid ester monomers include methacrylic acid esters and / or acrylic acid esters, specifically, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid. n-propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acrylic acid n-hexyl, (meth) acrylic acid cycloalkyl, etc. (meth) acrylic acid alkyl ester having a linear, branched or cyclic alkyl moiety having 1 to 6 carbon atoms, for example, (meth) acrylic acid (Meth) acrylic acid alkoxyalkyl esters such as 2-methoxyethyl, for example (meth) (Meth) acrylic acid hydroxyalkyl such as acrylic acid hydroxyethyl, for example, like (meth) epoxy group-containing (meth) acrylic acid esters such as glycidyl acrylate. Preferably, (meth) acrylic-acid alkylester is mentioned, More preferably, methyl methacrylate is mentioned.

  Examples of the (meth) acrylic acid monomer include methacrylic acid (MAA) and acrylic acid (AA).

  Examples of the aromatic vinyl monomer include styrene monomers (monovinylbenzene) such as styrene (vinylbenzene), p-methylstyrene, o-methylstyrene, α-methylstyrene, and ethylene vinylbenzene.

  Examples of vinyl ester monomers include vinyl acetate and vinyl propionate.

  Examples of maleate monomers include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the vinyl halide include vinyl chloride and vinyl fluoride.

  Examples of the vinylidene halide include vinylidene chloride and vinylidene fluoride.

  Examples of the nitrogen-containing vinyl monomer include (meth) acrylonitrile, N-phenylmaleimide, vinylpyridine, and the like.

  Examples of the crosslinkable monomer include mono- or polyethylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate (EGDA / EGDMA) and diethylene glycol di (meth) acrylate, such as 1,3-propanediol di (meth) ) Acrylates, 1,4-butanediol di (meth) acrylates, alkanediol di (meth) acrylates such as 1,5-pentanediol di (meth) acrylates, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra Alkane polyols such as (meth) acrylates (PETA / PETM) (meth) acrylate-based crosslinkable monomers such as poly (meth) acrylates, for example, allyl (meth) methacrylate, triallyl (iso Allylic monomers such as cyanurates, for example, divinyl benzene, aromatic crosslinking monomers such as trivinylbenzene. Preferably, mono or polyethylene glycol di (meth) acrylate and divinylbenzene, and more preferably, ethylene glycol di (meth) acrylate and divinylbenzene are used.

  When different types of monomers are used in combination, the monomers are substantially hydrophobic as a whole monomer (that is, a mixture of different types of monomers). The monomer specifically has a very low solubility in water at room temperature (20 to 30 ° C., more specifically 25 ° C.). Specifically, the solubility at room temperature is, for example, 8 parts by mass / 100 water. It is 5 parts by mass / 100 parts by volume of water (50 g / L) or less, more preferably 3 parts by mass / 100 parts by volume of water (30 g / L) or less.

  Since the polymer has a solid surface at room temperature because the polymer is a polymer of the first multi-domain particle, the glass transition temperature is, for example, 30 ° C. or higher, preferably 50 ° C. The monomer composition of the polymer is selected so that the glass transition temperature is obtained.

(2) First multi-domain particle In the first multi-domain particle, as an example of the active ingredient, for example, a first antibiotic compound, preferably an insecticide, more preferably a neonicotinoid type Insecticides, more preferably clothianidin.

A. First Multidomain Type Particle Containing First Antibiotic Active Compound Next, the first multidomain type particle containing the above-described active ingredient will be described with reference to FIG.

  As shown in FIG. 1, the first multi-domain particle is formed, for example, as a spherical particle. The first multi-domain particle 1 has a two-phase structure formed of a matrix 2 and domains 3 dispersed in the matrix 2.

  Specifically, in the first multi-domain particle 1, the matrix 2 forms a medium or a continuous phase, and the domains 3 are dispersed in an isolated state. In the first multi-domain particle 1, the matrix 2 and the domain 3 are incompatible with each other and form a phase separation structure that separates from each other. Further, the first multi-domain particle 1 has a multi-domain structure or a sea-island structure (or a multinuclear structure) having a matrix 2 and a domain 3.

  Specifically, the domain 3 forms a dispersed phase in the matrix 2. The shape of the domain 3 is not particularly limited, and is formed in an appropriate shape such as an indefinite shape, a spherical shape, a block shape, or a plate shape. The average value of the maximum length of the domain 3 is, for example, 0.05 μm or more, preferably 0.1 μm or more, and for example, 20 μm or less, preferably 10 μm or less.

  The matrix 2 is in a region other than the domain 3 in the first multi-domain particle 1.

  Further, both the matrix 2 and the domain 3 are exposed on the surface of the first multi-domain particle 1. In particular, the active ingredient is exposed on the surface of the first multi-domain particle 1 so as to protrude outward, thereby forming a protrusion 4. The protrusion 4 functions to increase the initial sustained release rate of the suspension polymer particles as the first multi-domain particle 1 and to significantly increase the blocking resistance of the dry powder of the suspension polymer particles. . The exposure rate of the protrusions 4 with respect to the entire surface of the suspension polymer particle (that is, the exposure rate of the domain 3) is, for example, 0.1% or more with respect to the entire surface of the first multi-domain particle 1. Preferably, it is 1% or more, and for example, 50% or less, preferably 30% or less. The exposure rate of the matrix 2 is a ratio obtained by subtracting the exposure rate of the protrusions 4 from the entire surface of the first multi-domain particle 1.

  A hole 6 is formed on the surface of the first multi-domain particle 1 by detaching (dropping out) a part of the domain 3 from the matrix 2. The hole 6 is formed so as to correspond to the shape of the active ingredient constituting the domain 3.

  The matrix 2 is made of a polymer produced from the above-described monomer.

  Domain 3 is composed of, for example, an active ingredient, preferably a first antibiotic compound, more preferably an insecticide, still more preferably a neonicotinoid insecticide, particularly preferably clothianidin.

  Next, a method for producing the first multi-domain particle 1 will be described.

  The first multi-domain particle is obtained by dispersing an active ingredient that is hydrophobic and substantially insoluble in a polymerizable vinyl monomer in the absence of a solvent, in the hydrophobic polymerizable vinyl monomer. A slurrying process for preparing a hydrophobic slurry, an aqueous dispersion process for preparing an aqueous dispersion by dispersing the hydrophobic slurry in water, and a polymerization process for producing a polymer by suspension polymerization of a polymerizable vinyl monomer. It is obtained by the manufacturing method provided. Hereinafter, each process is explained in full detail.

(Slurry process)
In the slurrying step, a hydrophobic slurry is prepared by dispersing the active ingredient (preferably the first antibiotic active compound) in the hydrophobic polymerizable vinyl monomer in the absence of a solvent.

  Specifically, the polymerizable vinyl monomer and the active ingredient described above are blended and stirred without blending a solvent (a hydrophobic organic solvent such as hexane, toluene, ethyl acetate).

  In order to disperse the active ingredient in the polymerizable vinyl monomer, for example, a disperser such as a paint shaker, a homodisper (high-speed disperser), a bead mill (including a batch type bead mill), a ball mill, or a rod mill is used. Dispersers can be used alone or in combination. As a disperser, a batch type bead mill is preferably used from the viewpoint that it can be used in a wide viscosity range and can be used for large-scale industrial production.

  The active ingredient is wet-ground by the dispersion described above.

  The blending ratio of the active ingredient to the polymerizable vinyl monomer is, for example, 1/99 or more, preferably 10/90 or more, in mass ratio (that is, mass part of active ingredient / mass part of polymerizable vinyl monomer). For example, it is 90/10 or less, preferably 70/30 or less. Moreover, the content rate in the hydrophobic slurry of an active ingredient is 1 mass% or more, for example, Preferably, it is 10 mass% or more, for example, is 90 mass% or less, Preferably, it is 70 mass% or less.

  In addition, in the dispersion described above, a dispersant (first dispersant) can be blended if necessary. Examples of the dispersant include nonionic, anionic and cationic amphiphilic oligomer type dispersants, nonionic surfactants (first surfactants), and the like. For example, as nonionic amphiphilic polymer type dispersants, EFKA4008, EFKA4009 (above Ciba Specialties urethane polymer dispersant), DISPERBYK-2164, DISPERBYK-164 (above Big Chemie's pigment dispersion) Functional group-modified copolymer), NUOSPERSE 2008, NUOSPERSE FA-196, NUOSPERSE 657 (more from Elementis), Floren D-90, Polyflow KL-100, Polyflow KL-700 (more from Kyoeisha Chemical), Homogenol L-95 (Made by Kao Corporation). For example, as an anionic amphiphilic oligomer type dispersant, Floren G-900 (carboxyl group-modified oligomer manufactured by Kyoeisha Chemical Co., Ltd.), Disparon DA-234, Disparon DA-325, Disparon DA-375, Disparon DA-550, Disparon And AQ-330 (polyether phosphate ester salt manufactured by Enomoto Kasei Co., Ltd.). For example, as a cationic amphiphilic oligomer-type dispersant, Nop Cosperth 092 (manufactured by San Nopco) can be used. For example, nonionic surfactants include amogen CBH (alkylbetaine), amogen SH (alkylamidobetaine), Neugen 100E (polyoxyethylene oleyl ether), Neugen EA73 (polyoxyethylene dodecyl phenyl ether), Neugen ES99 (mono) Polyethylene glycol oleate), Dianol CME (coconut oil fatty acid monoethanolamide), Dianol 300 (coconut oil fatty acid monoethanoldiamide), Sorgen 30 (Sorbitan sesquioleate), Sorgen 40 (Sorbitan monooleate), Sorgen 50 (Sorbitan monostearate), Epan 420 (Polyoxyethylene polyoxypropylene glycol), Epan 720 (Polyoxyethylene polyoxypropylene glycol) ) (All manufactured by Kao Corporation), and the like. Preferably, nonionic and anionic amphiphilic polymer dispersants are used, and more preferably, functional group-modified copolymer dispersants for pigment dispersion are used.

  The blending ratio of the dispersant is, for example, 0.1% by mass or more, preferably 1% by mass or more, and for example, 40% by mass or less, preferably 20% by mass or less with respect to the active ingredient. .

  The average particle size of the active ingredient in the hydrophobic slurry is, for example, 5 μm or less, preferably 2.5 μm or less, and for example, 0.05 μm or more, preferably 0.1 μm or more.

  In this method, for example, a polymerization initiator is blended together with the preparation of the hydrophobic slurry or after the preparation of the hydrophobic slurry. Preferably, after the preparation of the hydrophobic slurry, the polymerization initiator is blended into the prepared hydrophobic slurry.

  Examples of the polymerization initiator include radical polymerization initiators usually used in suspension polymerization, and specific examples include oil-soluble polymerization initiators.

  Examples of the oil-soluble polymerization initiator include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, and diisopropyl. Oil-soluble organic peroxides such as peroxydicarbonate and benzoyl peroxide, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 Examples thereof include oil-soluble azo compounds such as' -azobis (2-methylbutyronitrile).

  The polymerization initiators can be used alone or in combination of two or more.

  The mixing ratio of the polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, for example, 5 parts by mass or less, preferably 100 parts by mass of the polymerizable vinyl monomer. 3 parts by mass or less. When the blending ratio of the oil-soluble polymerization initiator exceeds the above upper limit, the molecular weight of the polymer may be excessively decreased, and when it does not satisfy the above lower limit, the conversion rate is not sufficiently improved and unreacted. In some cases, several% or more of the polymerizable vinyl monomer may remain.

(Water dispersion process)
Next, the hydrophobic slurry is dispersed (suspended) in water.

  That is, the hydrophobic slurry and water are mixed and stirred uniformly to disperse (suspend) the hydrophobic slurry in water. Thereby, an aqueous dispersion (suspension) solution of the hydrophobic slurry is obtained.

  In the aqueous dispersion of the hydrophobic slurry, preferably, a dispersant (second dispersant) and a surfactant (second surfactant) are blended.

  Examples of the dispersant (second dispersant) include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, gelatin, gum arabic, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, cationized starch, polyacrylic acid and its sodium salt, Water-soluble polymers such as styrene maleic acid copolymer and sodium salt thereof, for example, inorganic dispersants such as tricalcium phosphate, colloidal silica, montmorillonite, magnesium carbonate, aluminum hydroxide, zinc white, and the like.

  Among the dispersants, preferably, polyvinyl alcohol (PVA) and tricalcium phosphate are used. More preferably, polyvinyl alcohol (PVA) is mentioned.

  The mixing ratio of the dispersant is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10 parts by mass or less, preferably 100 parts by mass of the hydrophobic slurry. 5 parts by mass or less.

  In order to effectively prevent aggregation of particles during radical polymerization, the surfactant (second surfactant) is preferably used in combination with the above-described dispersant, specifically, sodium dodecylbenzenesulfonate, Anionic surfactants such as sodium lauryl sulfate, sodium di-2-ethylhexyl sulfosuccinate, sodium dodecyl diphenyl ether disulfonate (sodium alkyldiphenyl ether disulfonate), sodium nonyl diphenyl ether sulfonate, and salts of condensation products of aromatic sulfonic acid and formaldehyde Agents such as polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene polyoxypropylene Nonionic surfactants such as down the block copolymer and the like. Preferably, nonionic surfactants, more preferably, polyoxyethylene polyoxypropylene block copolymers are used.

  The blending ratio of the surfactant is, for example, 0.0001 parts by mass or more, preferably 0.001 parts by mass or more, for example, 1.0 parts by mass or less, with respect to 100 parts by mass of the hydrophobic slurry. Preferably, it is 0.1 mass part or less.

  These dispersants and surfactants can be blended, for example, before or after blending the hydrophobic slurry and water, and are preferably blended in water before blending with the hydrophobic slurry. Thereby, an aqueous solution of the dispersant and the surfactant is prepared.

  In the above-described aqueous dispersion (suspension) of the hydrophobic slurry, for example, a disperser such as a homomixer, an ultrasonic homogenizer, a pressure homogenizer, a milder, or a porous membrane press-fit disperser is used, preferably a homomixer. Is used.

  The conditions for water dispersion are appropriately set. When a homomixer is used, the rotation speed is set to, for example, 100 rpm or more, preferably 1000 rpm or more, and for example, set to 10,000 rpm or less, for example, 8000 rpm or less.

  Thus, an aqueous dispersion in which the hydrophobic slurry is dispersed in the aqueous phase is prepared.

  When a dispersant (second dispersant) is blended in the aqueous dispersion, the hydrophobic slurry droplets in the aqueous dispersion are stabilized by the dispersant.

(Polymerization process)
In the polymerization step, a polymerizable vinyl monomer is subjected to suspension polymerization to produce a polymer. For suspension polymerization of the polymerizable vinyl monomer, the aqueous dispersion is heated to a predetermined temperature. In suspension polymerization, the polymerizable vinyl monomer reacts (specifically, radical polymerization) while stirring the aqueous dispersion so that the aqueous dispersion state of the aqueous dispersion is maintained, and A polymer is produced. Suspension polymerization is in-situ polymerization because all the polymerizable vinyl monomers as raw materials are only in water-dispersed particles (hydrophobic liquid phase).

  Specifically, in the suspension polymerization, the aqueous dispersion is heated while being stirred, whereby the polymerizable vinyl monomer is directly polymerized in the aqueous dispersion particles to form a polymer.

  Stirring can be performed, for example, by a stirrer having a stirring blade. As for the stirring speed, the peripheral speed of the stirring blade is, for example, 10 m / min or more, preferably 20 m / min or more, and 400 m / min or less, preferably 200 m / min or less.

  The heating temperature is, for example, 40 ° C. or more, preferably 60 ° C. or more, and for example, 100 ° C. or less, preferably 80 ° C. or less.

  The suspension polymerization proceeds in a state where the active ingredient is incompatible with the polymer.

  The heating time is, for example, 2 hours or more, preferably 3 hours or more, and for example, 12 hours or less, preferably 8 hours or less. Furthermore, after heating to a predetermined temperature, the temperature can be maintained for a predetermined time, and then heating and temperature maintenance can be repeated to heat in stages.

  In suspension polymerization, the active ingredient is substantially insoluble in the polymerizable vinyl monomer, and the active ingredient is non-phasic with respect to the polymerizable vinyl monomer and / or polymer from the start of polymerization to the end of polymerization. The molten state is maintained. Therefore, as shown in FIG. 1, the obtained first multi-domain particle 1 has a two-phase structure formed from a matrix 2 and a domain 3. A part of the active ingredient is exposed on the surface from the inside of the first multi-domain particle 1 and constitutes the protrusion 4.

  Thereafter, the aqueous dispersion after polymerization is cooled by, for example, standing to cool, and filtered through a 100 mesh filter cloth or the like to obtain an aqueous dispersion (suspension) of the first multi-domain particles. Get.

  The cooling temperature is, for example, room temperature (20 to 30 ° C., more specifically 25 ° C.).

  The average particle diameter of the obtained first multi-domain particles is calculated as a median diameter and is 1 μm or more, preferably 5 μm or more, and for example, 1 mm or less, preferably 100 μm or less.

B. First multi-domain particle containing second antibiotic active compound Other examples of active ingredients contained in the first multi-domain particle include, for example, second antibiotic active compound Preferably, repellents, more preferably capsaicins, and still more preferably capsaicin and VNA.

  In the first multi-domain type particle containing the second antibiotic active compound described above, the second antibiotic active compound (preferably capsaicin, VNA) is used for a polymer produced from a polymerizable vinyl monomer. Thus, it is incompatible (insoluble). That is, in such a first multi-domain type particle, a phase separation structure is formed in which the phase of the second antibiotic active compound (preferably capsaicin, VNA) and the phase of the polymer are separated from each other. The polymer forms a matrix and the second antibiotic active compound (preferably capsaicin, VNA) forms domains that are dispersed in the matrix.

  In order to obtain a first multi-domain type particle containing such a second antibiotic active compound, the second antibiotic active compound (preferably capsaicin, VNA) is made hydrophobic in the absence of a solvent. To prepare a hydrophobic solution, disperse the hydrophobic solution in water, radically polymerize the polymerizable vinyl monomer in the presence of an oil-soluble polymerization initiator, and form a polymer. Generate.

  In the aqueous dispersion of the hydrophobic solution, an emulsifier and / or a dispersant described later is blended as necessary.

  The second antibiotic active compound (preferably capsaicin, VNA) is dissolved in the hydrophobic polymerizable vinyl monomer at the start of polymerization and precipitates from the polymer as radical polymerization proceeds, A domain is formed by dispersing in a matrix composed of coalescence.

  The first multi-domain particles thus obtained are made into a powder by, for example, spray drying. Solid-liquid separation by centrifugal separation, fuller press, etc., after washing, if necessary, dried by, for example, fluidized drying, shelf drying, etc., if necessary, disintegrated by atomizer, feather mill, etc., classified by vibrating sieve, etc. Then, it can be formulated into a known dosage form such as powder or granule. Alternatively, if the first treatment agent is aqueous, the aqueous dispersion (suspension) can be used as it is (suspension), that is, as a suspending agent.

(3) 1st compatible system particle 2nd antibiotic activity which is substantially compatible with the polymer produced | generated from a polymerizable vinyl monomer as an active ingredient in the 1st compatible system particle, preferably Compounds, more preferably, at least one selected from insecticides and antiseptics, and more preferably at least one selected from pyrethroid insecticides and organic iodine compounds, particularly preferably Examples include at least one selected from etofenprox and IPBC.

  The first compatible particles are prepared by dissolving an active ingredient in a hydrophobic polymerizable vinyl monomer to prepare a hydrophobic liquid, and dispersing the hydrophobic liquid in water to prepare an aqueous dispersion. Is produced by suspension polymerization to produce a polymer having a mean particle diameter of 1 μm or more. That is, the first compatible particle is a hydrophobic solution preparation step of preparing a hydrophobic solution by dissolving a hydrophobic active ingredient in a hydrophobic polymerizable vinyl monomer in the absence of a solvent, Obtained by a production method comprising an aqueous dispersion step of preparing an aqueous dispersion by dispersing a hydrophobic solution in water, and a polymerization step of producing a polymer having an average particle diameter of 1 μm or more by suspension polymerization of a polymerizable vinyl monomer. It is done. In the first compatible particle, the hydrophobic active ingredient is compatible with the polymer.

The manufacturing method of the 1st compatible particle | grains and the 1st compatible particle | grains obtained by it are described in detail in Unexamined-Japanese-Patent No. 2011-79816.
3-3. Flowable particles In the flowable particles, the active ingredient is preferably a second antibiotic compound, more preferably an antiseptic and fungicide, still more preferably an organic iodine compound, and particularly preferably IPBC.

  The flowable particle is a solid fine particle active ingredient itself which is insoluble in water. Flowable particles are particles in which an active ingredient can be dispersed in water by adding water to / or water.

  In the flowable particle, the active ingredient can be prepared as a flowable agent together with, for example, water, a surfactant and a thickener.

The method for preparing the flowable agent and each of the components described above are described in detail in JP-A-2008-81466.
3-4. Combination of first particles The first particles described above can be used alone or in combination of two or more.

  As the first particles, preferably, the microcapsules are used alone (corresponding to the first embodiment described later), the active ingredient dispersed particles are used alone (the second embodiment, the third embodiment and the eighth embodiment described later). Correspondence), combined use of microcapsules and active ingredient dispersed particles (corresponding to fourth and tenth aspects described later), combined use of microcapsules and flowable particles (corresponding to fifth aspect described later), dispersion of different active ingredients Examples thereof include combined use of particles (corresponding to sixth and tenth aspects described later), and combined use of active ingredient dispersed particles and flowable particles (corresponding to seventh and ninth aspects described later).

  More preferably, as the first particles, the microcapsules are used alone (corresponding to the first aspect described later), the first multi-domain particles are used alone (corresponding to the second aspect described later), the first Use of compatible particles alone (corresponding to the third aspect described later), combined use of microcapsules and first compatible particles (corresponding to fourth and tenth aspects described later), microcapsules and flowable particles Combined use (corresponding to a fifth aspect described later), combined use of first multi-domain particles and first compatible particles (corresponding to sixth and tenth aspects described later), different plural (specifically 2) The combined use of the first compatible particles containing two kinds of active ingredients (corresponding to the eighth aspect described later).

  More preferably, as the first particles, the microcapsules are used alone (corresponding to the first embodiment described later), the first multi-domain particles are used alone (corresponding to the second embodiment described later), and the same type The single use of the first compatible particles (corresponding to a third aspect described later) is exemplified.

4). Second treatment agent The second treatment agent contains second particles.

  The second particle contains an active ingredient. As the second particle, for example, a second phase having a homogeneous phase in which a polymer and an active ingredient (preferably, a second antibiotic active compound) are compatible. 2 compatible particles.

  Each of the first compatible particle and the second compatible particle has a homogeneous phase in which the polymer and the active ingredient are compatible, while the average particle size of the first compatible particle is 1 μm or more. On the other hand, the average particle diameter of the second compatible particles is less than 1 μm.

  Specifically, the average particle diameter of the second treatment agent is calculated as a median diameter, and is less than 1 μm, preferably 750 nm or less, more preferably 500 nm or less, and particularly preferably 400 nm or less. It is 10 nm or more, preferably 50 nm or more.

  The second compatible particles are prepared by dissolving a hydrophobic active ingredient with a hydrophobic polymerizable vinyl monomer to prepare a hydrophobic solution, and blending water and an emulsifier to prepare an aqueous emulsifier solution. It is obtained by emulsifying the solution in an aqueous emulsifier solution and miniemulsion polymerization of the polymerizable vinyl monomer in the presence of a polymerization initiator to form a polymer.

  In the second compatible particles, the active ingredient may be a second antibiotic active compound, preferably an antiseptic / fungal agent, and more preferably an organic iodine compound or a triazole compound. The active ingredient can be used alone or in combination of two or more kinds. Each of the organic iodine compound and the triazole compound can be used alone or in combination thereof, specifically, propiconazole alone, IPBC and A combination of propiconazole is mentioned.

  In the method for producing the second compatible particles, if the active ingredient is the second antibiotic active compound, the second antibiotic active compound acts as a hydrophobe (costabilizer) in miniemulsion polymerization, First, by contributing to stabilization of a miniemulsion (described later) in miniemulsion polymerization, Ostwald ripening is prevented, and enlargement of the miniemulsion particles (increase in particle diameter) is suppressed.

  The polymerizable vinyl monomer may be the same as the polymerizable vinyl monomer described above, and preferably a (meth) acrylic acid ester monomer, a (meth) acrylic acid monomer, or a crosslinkable monomer. The polymerizable vinyl monomer can be used alone or in combination of two or more.

  When the polymerizable vinyl monomer contains a (meth) acrylic acid ester monomer and a crosslinkable monomer, the blending ratio of the (meth) acrylic acid ester monomer is the balance of the crosslinkable monomer and the blending of the crosslinkable monomer. The proportion is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and for example, 80 parts by mass or less, preferably 100 parts by mass of the polymerizable vinyl monomer. Is 50 parts by mass or less, more preferably 20 parts by mass or less.

  When the polymerizable vinyl monomer contains a (meth) acrylic acid ester monomer, a (meth) acrylic acid monomer, and a crosslinkable monomer, the blending ratio of the (meth) acrylic acid monomer is 100 masses of the polymerizable vinyl monomer. Part by mass, for example, 1 part by mass or more, preferably 2 parts by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less. For example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and for example, 80 parts by mass or less, preferably 50 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer. Part or less, more preferably 20 parts by weight or less. The mixing ratio of the (meth) acrylic acid ester monomer is the balance of the crosslinkable monomer.

In addition, as an active ingredient and a polymerizable vinyl monomer, the dipole force term δ _{p, component} of the solubility parameter δ is, for example, 2 [(J / cm ³ ) ^1/2 ] or more, preferably 3 [(J / cm ³ ) ^1/2 ] or more, for example, 8 [(J / cm ³ ) ^1/2 ] or less, preferably 7 [(J / cm ³ ) ^1/2 ] or less, and the hydrogen bond of the solubility parameter δ The force term δ _{h, component} is, for example, 5.5 [(J / cm ³ ) ^1/2 ] or more, preferably 5.8 [(J / cm ³ ) ^1/2 ] or more, for example, 9.5 An active ingredient that is [(J / cm ³ ) ^1/2 ] or less, and a dipole force term δ _{p, polymer of} the solubility parameter δ is, for example, 5 [(J / cm ³ ) ^1/2 ] or more, for example, ^{, 7 [(J / cm 3} ) 1/2] or less, 6.5 [(J / m ^{3) 1/2]} or less, the hydrogen bonding term solubility parameter [delta] [delta] _{h, Polymer,} for ^{example, 8 [(J / cm 3} ) 1/2] or more, preferably, 8.5 [(J / Cm ³ ) ^1/2 ] or more, for example, a combination with a polymerizable vinyl monomer that produces a polymer of 10 [(J / cm ³ ) ^1/2 ] or less is selected.

The dipole force term δ _p and the hydrogen bond force term δ _h of the solubility parameter δ are defined by Hansen, calculated by the van Krevelen and Hoftyzer method, and specifically described in Japanese Patent Application Laid-Open No. 2011-79816. ing.

In addition, subscript component and polymer of each term (delta) ((delta) _p and (delta) _h ) show an active ingredient and a polymer, respectively.

If the dipole force term δ _{p, polymer} and / or the hydrogen bond force term δ _{h, polymer} of _{the polymer} is less than the above range _{, the polymer} becomes excessively hydrophobic and has sufficient compatibility with the active ingredient. Even if compatibility can be obtained, the active ingredient leaks out of the sustained-release particles during the polymerization of the miniemulsion, and the sustained-release particles sufficiently encapsulating the active ingredients Synthesis may be difficult.

On the other hand, when the polymer dipole force term δ _{p, polymer} and / or the hydrogen bond force term δ _{h, polymer} exceeds the above range _{, the polymer} becomes excessively hydrophilic and has a sufficient phase with the active ingredient. In some cases, even if compatibility can be obtained, the free energy of the interface with the aqueous phase in the miniemulsion polymerization becomes low, and the active ingredient is removed from the sustained-release particles during the miniemulsion polymerization. In some cases, it becomes difficult to synthesize sustained release particles sufficiently containing active ingredients.

On the other hand, if the dipole force term δ _{p, component} and / or the hydrogen bond force term δ _{h, component} of the active ingredient is less than the above range, the hydrophobicity of the active ingredient becomes excessively high, and the sufficient amount of the polymer Compatibility may not be obtained.

On the other hand, when the dipole force term δp _{, component} and / or the hydrogen bond force term δh _{, component} of the active ingredient exceeds the above range, the hydrophilicity of the active ingredient becomes excessively high, and the active ingredient is controlled release particles. There are cases where it is difficult to synthesize sustained-release particles that are easy to leak out and contain sufficient active ingredients.

Further, in the solubility parameter δ, a value Δδ _p (= δ _{p, polymer} −δ _{p, component} ) obtained by subtracting the dipole force term δ _{p, component} of the active component from _{the polymer} dipole force term δ _{p, polymer.} Is, for example, −1.1 to 2.8 [(J / cm ³ ) ^1/2 ].

The hydrogen bonding term [delta] _h, a value obtained by subtracting the hydrogen bonding term [delta] _{h, component} of the active ingredient from the _{polymer Δδ h (= δ h,} polymer -δ h, component) of the polymer, for example, -0. 1 to 4.2 [(J / cm ³ ) ^1/2 ].

If .DELTA..delta _p and .DELTA..delta _h is within the range shown above, to secure the excellent compatibility of the active ingredient and polymer, it is possible to ensure excellent sustained release.

The dipole force term δ _{p, component} and the hydrogen bond force term δ _{h, component of the} active component are within the above-mentioned range, and the dipole force term δ _{p, polymer} and the hydrogen bond force term δ _{h of the polymer ,} Polymer is within the above range, the active ingredient is defined as being compatible with the polymer without leaking from the sustained release particles during miniemulsion polymerization. That is, the active ingredient is contained in the polymer.

  Examples of the emulsifier include anionic emulsifiers such as sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium nonyl diphenyl ether sulfonate, and sodium polyoxyethylene alkyl ether sulfate.

  Examples of the emulsifier include nonionic emulsifiers such as polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether, polyoxyalkylene aralkyl aryl ether, polyoxyalkylene block copolymer, and polyoxyalkylene aryl ether.

  Examples of the polyoxyalkylene alkyl ether include polyoxyethylene alkyl ether.

  Examples of the polyoxyalkylene alkyl aryl ether include polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether.

  Examples of the polyoxyalkylene aralkyl aryl ether include polyoxyethylene styrenated phenyl ether (for example, Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.)), polyoxyethylene distyrenylated phenyl ether (for example, Emulgen A-90). , Emulgen A-500 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)).

  Examples of the polyoxyalkylene block copolymer include a polyoxyethylene-polyoxypropylene block copolymer.

  Examples of the polyoxyalkylene aryl ether include polyoxyethylene aryl ether.

  The HLB of the nonionic emulsifier is, for example, 11 or more, preferably 12 or more, more preferably 13 or more, and for example, 20 or less, preferably 19 or less, and more preferably 18 or less.

  The HLB is calculated by the Griffin equation shown by the following equation (1).

HLB = 20 × (sum of formula weight of hydrophilic part / molecular weight) (1)
As a nonionic emulsifier, Preferably, a polyoxyalkylene aralkyl aryl ether is mentioned.

  The emulsifiers can be used alone or in combination of two or more. Preferably, an anionic emulsifier is used alone, or an anionic emulsifier and a nonionic emulsifier are used in combination. More preferably, sodium alkyldiphenyl ether disulfonate is used alone, dioctyl sodium sulfosuccinate and polyoxyalkylene aralkyl aryl ether are used. A combined use of polyoxyethylene alkyl ether sulfate sodium salt and polyoxyethylene distyrenated phenyl ether is used.

  When an anionic emulsifier and a nonionic emulsifier are used in combination, the blending ratio of the anionic emulsifier is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass with respect to the emulsifier. More preferably, the content is 25% by mass or more, and is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less. Is, for example, 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80 mass% or less, more preferably 75 mass% or less.

  In addition, an emulsifier can also be previously mixed and dissolved in water at an appropriate ratio to prepare an emulsifier-containing aqueous solution. The mixing ratio of the emulsifier in the emulsifier-containing aqueous solution is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less.

  Examples of the polymerization initiator include the same radical polymerization initiators used in the above-described suspension polymerization. For example, an oil-soluble polymerization initiator, a water-soluble polymerization initiator and the like can be mentioned. Preferably, an oil-soluble polymerization initiator is used, and more preferably, an oil-soluble organic peroxide is used.

  In the method for producing the second particles, first, a hydrophobic solution is prepared by dissolving an active ingredient (preferably, a second antibiotic active compound) with a hydrophobic polymerizable vinyl monomer.

  That is, an active ingredient and a polymerizable vinyl monomer are blended and stirred uniformly to obtain a hydrophobic solution.

  In addition, the hydrophobic solution is, for example, without blending an active ingredient solvent (hydrophobic organic solvent such as hexane, toluene or ethyl acetate) and / or hydrophobe (costabilizer such as hexadecane or cetyl alcohol). Prepared. Thereby, environmental load can be reduced.

  The mixing ratio of the active ingredient to the polymerizable vinyl monomer is, for example, 0.01 or more, preferably 0.05 or more, on a mass basis (that is, the active ingredient / part by weight of the polymerizable vinyl monomer). For example, it is 4.0 or less, preferably 3.0 or less.

  In the preparation of the hydrophobic solution, when an oil-soluble polymerization initiator is used as the polymerization initiator, an oil-soluble polymerization initiator is blended together with the active ingredient and the polymerizable vinyl monomer.

  The blending ratio of the oil-soluble polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, for example, 5 parts by mass or less, preferably 100 parts by mass of the polymerizable vinyl monomer. Is 3 parts by mass or less.

  In the second method for producing compatible particles, water and an emulsifier are separately blended to prepare an emulsifier aqueous solution.

  Specifically, an aqueous emulsifier solution is obtained by blending water and an emulsifier and stirring them uniformly.

  The amount of emulsifier is sufficient to allow the emulsifier to be adsorbed on the entire surface of the hydrophobic solution emulsified droplets, and the presence of excess emulsifier generates new polymerized vinyl monomer emulsion polymer particles that do not contain active ingredients. Is selected depending on the type of emulsifier, but for example, the effective component amount of the emulsifier is 0.1% by mass or more, preferably 0.2% by mass or more with respect to the hydrophobic solution. For example, it is 20 mass% or less, Preferably, it is 10 mass% or less.

  In the preparation of the aqueous emulsifier solution, when a water-soluble polymerization initiator is used as the polymerization initiator, a water-soluble polymerization initiator is blended together with water and the emulsifier.

  The mixing ratio of the water-soluble polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, for example, 5 parts by mass or less, preferably 3 parts with respect to 100 parts by mass of water. It is below mass parts.

  When the blending ratio of the water-soluble polymerization initiator exceeds the above upper limit, the molecular weight of the polymer may be excessively reduced. When the blending ratio is less than the above lower limit, the conversion rate is not sufficiently improved and unreacted. Of the polymerizable vinyl monomer may remain.

  The aqueous emulsifier solution can also contain a dispersant.

  Examples of the dispersant include polyvinyl alcohol, a condensate of aromatic sulfonic acid and formaldehyde, a polycarboxylic acid type oligomer, and the like, preferably polyvinyl alcohol (hereinafter abbreviated as “PVA”), aromatic. Examples include condensates of sulfonic acid and formaldehyde.

  PVA is a dispersant blended in an aqueous phase to form a protective colloid of a mini-emulsion, for example, a polyvinyl acetate system obtained by polymerizing a vinyl monomer containing vinyl acetate as a main component by an appropriate method. It can be obtained by saponifying the polymer.

  By blending PVA into the emulsifier aqueous solution, a stable hydrated layer is formed by the protective colloid of PVA, and aggregation due to collision between particles is less likely to occur. As a result, for example, even in a formulation with a small amount of emulsifier, the polymerization stability can be improved, for example, the amount of aggregate during miniemulsion polymerization can be reduced. In addition, when the second compatible particles are prevented from agglomerating and caking during storage for a long period of time, or when the second compatible particles are used as a water-based wood preservative (described later), they are diluted with water to obtain a high shear force. Even when the pump or nozzle is passed, the colloidal stability can be improved, for example, the aggregation of the second compatible particles can be prevented.

  The degree of saponification of PVA is, for example, 70% or more, preferably 80% or more, and for example, 99% or less, preferably 90% or less.

  The average degree of polymerization of PVA is, for example, 300 or more, preferably 500 or more, and for example, 4000 or less, preferably 2500 or less.

  PVA has a 4% aqueous solution having a viscosity at 20 ° C. of, for example, 3 mPa · sec or more, preferably 5 mPa · sec or more, and for example, 100 mPa · sec or less, preferably 50 mPa · sec or less.

  The viscosity of PVA can be measured using a B-type viscometer with a 4% aqueous solution at 20 ° C.

  When blending PVA, the blending ratio is selected in an amount sufficient for PVA to be adsorbed on the entire surface of the hydrophobic solution emulsified droplets, and varies depending on the type of PVA. The amount of the active ingredient of PVA is, for example, 0.5% by mass or more, preferably 1% by mass or more, and for example, 10% by mass or less, preferably 8% by mass or less.

  For the preparation of the PVA aqueous solution, for example, PVA is added to and dispersed in cold water at 25 ° C. or lower with stirring, and the temperature is raised to 60 to 90 ° C. and dissolved. After confirming that PVA is completely dissolved in water, it can be carried out by cooling to room temperature.

  Examples of the condensate of aromatic sulfonic acid and formaldehyde include sodium salt of β-naphthalene sulfonic acid formaldehyde condensate. The blending ratio of the condensate of aromatic sulfonic acid and formaldehyde is, for example, 0.001% by mass or more, preferably 0.01% by mass or more, for example, with respect to the hydrophobic solution. 0.5% by mass or less, preferably 0.3% by mass or less, more preferably 0.2% by mass or less.

  These dispersants can be used alone or in combination of two or more.

  In this method, the hydrophobic solution is then emulsified in an aqueous emulsifier solution.

  Specifically, a hydrophobic solution is blended in an emulsifier aqueous solution, and a high shear force is applied to them to emulsify the hydrophobic solution in the emulsifier aqueous solution to prepare a mini-emulsion.

  In emulsification of the hydrophobic solution, for example, an emulsifier such as a homomixer (homogenizer), an ultrasonic homogenizer, a pressure homogenizer, a milder, or a porous membrane press emulsifier is used, and preferably a homomixer is used.

  The stirring conditions are set as appropriate, and when a homomixer is used, the number of rotations is set to, for example, 6000 rpm or more, preferably 8000 rpm or more, more preferably 10,000 rpm or more, for example, 30000 rpm or less.

  If the rotational speed is less than the lower limit, miniemulsion particles having a particle diameter of less than 1 μm may not be formed.

  The stirring time is, for example, 1 minute or longer, preferably 2 minutes or longer, and 1 hour or shorter.

  The blending ratio of the hydrophobic solution is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and for example, 150 parts by mass or less, preferably 90 parts by mass or less with respect to 100 parts by mass of the emulsifier aqueous solution. It is.

  A mini-emulsion of a hydrophobic solution is prepared by the method described above. In the hydrophobic emulsion miniemulsion, the emulsifier is adsorbed on the miniemulsion particles (hydrophobic solution emulsified droplets), and the hydrophobic emulsion miniemulsion particles with an average particle diameter of less than 1 μm are formed in the aqueous medium. Has been.

  The average particle diameter of the mini-emulsion particles is calculated as a median diameter, and is adjusted to less than 1 μm, preferably 750 nm or less, more preferably 500 nm or less, particularly preferably 400 nm or less, and for example, 50 nm or more.

  Note that an emulsifier is adsorbed on the surface of the miniemulsion particles, thereby stabilizing the miniemulsion.

  Thereafter, the polymerizable vinyl monomer in the emulsified hydrophobic solution is subjected to miniemulsion polymerization in the presence of a polymerization initiator to produce a polymer.

  This miniemulsion polymerization is an in situ polymerization because all of the polymerizable vinyl monomers as raw materials are only in the miniemulsion particles (hydrophobic liquid phase).

  That is, in the mini-emulsion polymerization, by heating the mini-emulsion while stirring, the polymerization vinyl monomer starts polymerization in the mini-emulsion particles as it is, and a polymer is generated.

  Agitation can be performed, for example, with a stirrer having a stirring blade, and stirring sufficient to control uniform heat conduction to the miniemulsion, sticking of the miniemulsion particles to the wall, and retention of the miniemulsion on the surface of the miniemulsion. As long as the effect can be realized, excessive stirring causes aggregation of the miniemulsion particles. As for the stirring speed, the peripheral speed of the stirring blade is, for example, 10 m / min or more, preferably 20 m / min or more, and 400 m / min or less, preferably 200 m / min or less.

  The heating conditions are appropriately selected depending on the kind of the polymerization initiator and the active ingredient, and the heating temperature is, for example, not lower than the melting point of the active ingredient, specifically, for example, 30 ° C. or higher, preferably 50 ° C. or higher. Also, for example, it is 100 ° C. or less, and the heating time is, for example, 2 hours or more, preferably 3 hours or more, and for example, 24 hours or less, preferably 12 hours or less. Furthermore, after heating to a predetermined temperature, the temperature can be maintained for a predetermined time, and then heating and temperature maintenance can be repeated to heat in stages.

  As described above, miniemulsion polymerization is clearly different from emulsion polymerization in which the polymerization process is not in situ polymerization but polymerization is performed by mass transfer of a polymerizable vinyl monomer, in that the polymerization process is in situ polymerization. .

  Specifically, emulsion polymerization is carried out in the aqueous phase in the presence of an emulsifier, a polymerizable vinyl monomer, and a polymerization initiator (radical polymerization initiator), and is polymerized by radicals generated by decomposition of the radical polymerization initiator. To start. At this time, the polymerizable vinyl monomer exists in the following three states. That is, (1) a state solubilized in micelles of an emulsifier (state having an average particle diameter of less than several tens of nm), (2) a state dissolved in an aqueous phase, and (3) a state existing as oil droplets (particle diameter The polymerizable vinyl monomer exists in three states (several μm or more).

  The radicals generated by the decomposition of the radical polymerization initiator may collide and invade the three-state polymerizable vinyl monomer and add to the polymerizable vinyl monomer to start polymerization. 1) The micelle of the emulsifier solubilized with the polymerizable vinyl monomer has an overwhelmingly larger number of particles than the oil droplets of the above-described (3) polymerizable vinyl monomer, and therefore has a large surface area and a radical penetration probability. Since it is high, (1) Polymerization starts in the micelle of the emulsifier to form polymer particles. When a highly water-soluble polymerizable vinyl monomer is used as the polymerizable vinyl monomer, (2) radical addition to the vinyl monomer dissolved in the aqueous phase described above occurs, and the produced polymer enters the aqueous phase. When it cannot be dissolved and precipitates, it is stabilized by an emulsifier, and polymer particles are produced. Such an initiation reaction is also observed in the emulsion polymerization process.

  When the emulsion polymerization starts, (3) the polymerizable vinyl monomer is dissolved in the water phase from the oil droplets of the polymerizable vinyl monomer, and then the polymerizable vinyl monomer moves to the polymer particles and the polymerization proceeds. That is, the polymerization field is polymer particles, and the oil droplets of the polymerizable vinyl monomer only serve as a supply source of the polymerizable vinyl monomer, and polymerization, that is, in situ polymerization does not occur on the spot. .

  In contrast, miniemulsion polymerization is highly sheared into oil droplets of polymerizable vinyl monomers in the aqueous phase by the presence of emulsifiers and hydrophobes (costabilizers), using homomixers, homogenizers, and ultrasonic irradiation. When the particle size is reduced to less than 1 μm, preferably less than 0.5 μm by applying force, and the polymerization initiator (radical polymerization initiator) is oil-soluble, the minute and stable polymerizable vinyl monomer In the oil droplets, due to radicals generated by the decomposition of the polymerization initiator, or when the polymerization initiator is water-soluble, the radicals penetrate into the oil droplets, and polymerization starts by the penetrating radicals, This is a polymerization method in which radical polymerization proceeds.

  In detail, the oil droplets of a minute polymerizable vinyl monomer exist stably by adopting an anionic emulsifier as an emulsifier, for example. At the same time, oil droplets of small polymerizable vinyl monomers can be produced from oil droplets of smaller (fine) polymerizable vinyl monomers via the aqueous phase by using hydrophobes (costabilizers). It exists stably by controlling the enlargement (Ostwald ripening) due to the transfer of the polymerizable vinyl monomer to the oil droplets.

  On the other hand, in the second method for producing compatible particles, miniemulsion polymerization in which a polymerizable vinyl monomer is polymerized (radical polymerization) proceeds in miniemulsion particles (fine oil droplets composed of an active ingredient and a polymerizable vinyl monomer). . During miniemulsion polymerization, the polymer of polymerizable vinyl monomer is preferably compatible with the active ingredient. That is, the active ingredient is dissolved in the polymer to form a polymer active ingredient solution, and the active ingredient solution is emulsified in water.

  The polymerizable vinyl monomer is preferably selected so that the polymer of the polymerizable vinyl monomer and the active ingredient are compatible as described above at the polymerization temperature (heating temperature) during the above-described miniemulsion polymerization. Therefore, the phase separation during mini-emulsion polymerization is prevented and the polymer (polymer during reaction) dissolves in the active ingredient, or the polymer (polymer during reaction) is effective. The reaction proceeds in a swollen state with respect to the components, and sustained release particles in which a uniform phase is formed can be obtained. In addition, if an active ingredient is liquid at normal temperature, the state of the active ingredient solution of a polymer will be maintained as it is at normal temperature.

  On the other hand, since the average particle size of the miniemulsion particles is as small as less than 1 μm, the polymerizable vinyl monomer easily diffuses in the water phase. In this miniemulsion polymerization, the active ingredient can act as a hydrophobe. Therefore, as a result of effectively preventing the molecular diffusion described above, Ostwald ripening can be prevented and enlargement of the miniemulsion particles (increase in particle diameter) can be suppressed.

  Thereafter, the emulsion after polymerization is cooled, for example, by standing to cool.

  The average particle diameter of the second compatible particles (polymer) thus obtained is calculated as the median diameter, and is less than 1 μm, preferably 750 nm or less, more preferably 500 nm or less, and particularly preferably 400 nm or less. Most preferably, it is 300 nm or less, for example, 10 nm or more, preferably 50 nm or more.

  Thereby, the emulsion in which the 2nd compatible particle | grains in which an active ingredient exists uniformly can be finely dispersed can be obtained.

  The second compatible particles thus obtained may be used as they are (emulsion), that is, as an emulsion, spray-dried, or frozen / thawed, or salted. After aggregating by analysis, solid-liquid separation is performed by centrifugation, washing, drying, and the like, and for example, it may be formulated into a known dosage form such as a powder or granule.

  Such second particles preferably contain a plurality of types of active ingredients, specifically a plurality of types of second antibiotic active compounds, and more specifically a plurality of types of antiseptics. It contains fungicides, as well as organic iodo compounds and triazole compounds, especially IPBC and propiconazole.

  That is, when the second particle contains one active ingredient and another active ingredient, the one active ingredient and the other active ingredient are dissolved with a hydrophobic polymerizable vinyl monomer, A hydrophobic solution containing an active ingredient and other active ingredients is prepared, the hydrophobic solution is emulsified in an aqueous emulsifier solution, and the polymerizable vinyl monomer is polymerized in a mini-emulsion in the presence of a polymerization initiator. By producing a polymer in which the active ingredient and other active ingredients are compatible, the second particles can be obtained.

  Alternatively, when the second particle contains one active ingredient and another active ingredient, first, the one active ingredient is dissolved with a hydrophobic polymerizable vinyl monomer to contain one active ingredient. A hydrophobic solution is prepared, the hydrophobic solution is emulsified in an aqueous emulsifier solution, the polymerizable vinyl monomer is miniemulsion polymerized in the presence of a polymerization initiator, and a polymer in which one active ingredient is compatible is obtained. Generate. Separately, other active ingredients are dissolved in a hydrophobic polymerizable vinyl monomer to prepare a hydrophobic solution containing the other active ingredients, and the hydrophobic solution is emulsified in an aqueous emulsifier solution. In the presence of a polymerization initiator, miniemulsion polymerization is performed to produce a polymer in which other active ingredients are compatible. Then, the 2nd particle can also be obtained by mix | blending and mixing the polymer in which one active ingredient is compatible, and the polymer in which another active ingredient is compatible.

  Specifically, one active ingredient is preferably an organic iodine compound, more preferably IPBC, and the other active ingredient is preferably a triazole compound, more preferably propiconazole. It is done.

  When one active ingredient is an organic iodo compound (specifically, IPBC) and the other component is a triazole compound (specifically, propiconazole), The ratio of the active ingredient to the total amount is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, less than 50% by mass, preferably 40% by mass or less. The ratio of the active ingredient to the total amount is, for example, 90% by mass or less, preferably 80% by mass or less, and for example, more than 50% by mass, preferably 60% by mass or more. If the ratio of one active ingredient and / or the ratio of another active ingredient is in the above-mentioned range, two kinds of active ingredients can penetrate into the inside of the agent to be treated and exhibit an excellent efficacy sustaining effect.

5. Preparation of Treatment Agent To prepare a treatment agent, the first treatment agent and the second treatment agent described above are mixed. Specifically, the first treatment agent and the second treatment agent are prepared separately, and they are blended and mixed.

  The blending ratio of the first treatment agent to the total amount of the first treatment agent and the second treatment agent is, for example, 5% by mass or more, preferably 10% by mass or more, and, for example, 40% by mass or less. Preferably, it is 35 mass% or less. The blending ratio of the second treatment agent to the total amount of the first treatment agent and the second treatment agent is, for example, 60% by mass or more, preferably 65% by mass or more, and, for example, 95% by mass. % Or less, preferably 90% by mass or less. When the blending ratio of the second treatment agent is equal to or more than the above lower limit, the second treatment agent can penetrate into the material to be treated and exhibit an excellent effect of sustaining effect. If the blending ratio of the second treatment agent is equal to or less than the above upper limit, the effectiveness of the first treatment agent can be reliably ensured on the surface of the material to be treated.

  The content ratio of the active ingredient contained in the first treating agent to the total amount of the active ingredient contained in the first treating agent and the active ingredient contained in the second treating agent is, for example, 5 It is not less than mass%, preferably not less than 8 mass%, and is, for example, not more than 45 mass%, preferably not more than 40 mass%. The content ratio of the active ingredient contained in the second treating agent to the total amount of the active ingredient contained in the first treating agent and the active ingredient contained in the second treating agent is, for example, 55% by mass. As mentioned above, Preferably, it is 60 mass% or more, for example, 95 mass% or less, Preferably, it is 92 mass% or less. When the blending ratio of the active ingredient contained in the second treating agent is equal to or more than the lower limit described above, an excellent efficacy sustaining effect of the active ingredient can be expressed inside the material to be treated. If the blending ratio of the active ingredient contained in the second treatment agent is equal to or less than the above upper limit, the effectiveness of the active ingredient contained in the first treatment agent is surely ensured on the surface of the material to be treated. Can do.

  Furthermore, the total content of the active ingredients in the treatment agent is, for example, 5% by mass or more, preferably 6% by mass or more, and for example, 30% by mass or less, preferably 25% by mass with respect to the treatment agent. % Or less.

  In addition, a well-known additive can be mix | blended with a processing agent in a suitable ratio. The additive can be blended at the time of preparation of the treatment agent, or can be blended at the time of preparation of each of the first treatment agent and the second treatment agent.

  As an additive, Preferably, emulsifiers, such as Neugen EA-177, can be mentioned. The addition amount of the additive is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more with respect to 100 parts by mass of the total amount of the first particles and the second particles. Part or less, preferably 8 parts by weight or less.

  By adding the specific additive described above to the treatment agent, even if a mechanical shear force is applied to the treatment agent, aggregation and destruction of the first particles and the second particles can be prevented. Furthermore, the storage stability of the treatment agent can be improved.

6). Action and Use of Treatment Agent And such a treatment agent can improve the efficacy sustaining effect of the second treatment agent while ensuring the efficacy of the first treatment agent. Therefore, an excellent effect of sustaining the effect can be expressed inside the material to be treated.

Therefore, such a treatment agent is used for various applications, and specifically, for example, it can be applied to water-based wood preservatives, for example, water-based paints, for example, building materials.
6-1. Water-based wood preservative (1) Composition of water-based wood preservative The water-based wood preservative contains the treatment agent described above.

  In the water-based wood preservative, as the treating agent, for example, the first treating agent contains a microcapsule containing an insecticide, and the second treating agent contains a preservative and antifungal agent. 1st aspect containing particle | grains, for example, the 1st processing agent contains the 1st multi domain type particle | grains containing an insecticide, and the 2nd processing agent contains the antiseptic / fungal agent 2nd 2nd aspect containing compatible particle | grains of this, for example, a 1st processing agent contains the 1st compatible particle | grains containing an insecticide, and a 2nd processing agent contains antiseptic | preservative antifungal agent. A third embodiment containing the second compatible particles, for example, the first treatment agent contains microcapsules containing an insecticide and first compatible particles containing a preservative fungicide, A fourth embodiment in which the second treating agent contains second compatible particles containing antiseptic and fungicidal agents, for example The first treating agent contains microcapsules containing an insecticide and flowable particles containing an antiseptic and fungicidal agent, and the second treating agent contains a second compatible system containing an antiseptic and fungicidal agent. 5th aspect containing particle | grains, for example, 1st processing agent contains 1st multi-domain type particle | grains containing an insecticide, and 1st compatible type | system | group particle | grains containing antiseptic | preservative antifungal agent, The 6th aspect in which the 2nd processing agent contains the 2nd compatible system particle containing antiseptic / fungal agent, for example, the 1st processing agent contains the 1st multi domain type particle containing an insecticide, And a flowable particle containing an antiseptic and fungicidal agent, and the second treatment agent contains a second compatible particle containing an antiseptic and fungicidal agent, for example, a first treatment. First compatible particles containing an insecticide and a first compatible system containing an antiseptic and fungicidal agent And the second treatment agent contains second compatible particles containing antiseptic and fungicidal agents, and the first treatment agent contains an insecticide, for example. 9th aspect containing the compatible particle | grains of this, and the flowable particle | grains containing antiseptic / fungicide, and the 2nd processing agent contains the 2nd compatible particle | grains containing antiseptic | fungal agent. It is done. Furthermore, as a treating agent, in the above-described first to ninth embodiments, the tenth embodiment in which the first treating agent further contains first multi-domain particles containing a repellent is also included. In the eighth aspect, the first compatible particle is composed of two types of the first compatible particle containing an insecticide and the first compatible particle containing an antiseptic and fungicidal agent. Is possible.

  In the first aspect, preferably, the first treatment agent contains microcapsules containing clothianidin, and the second treatment agent contains second compatible particles containing IPBC and propiconazole. .

  In the second aspect, preferably, the first treatment agent contains a first multi-domain particle containing clothianidin, and the second treatment agent contains a second phase containing IPBC and propiconazole. Contains soluble particles.

  In the third aspect, preferably, the first treatment agent contains first compatible particles containing etofenprox, and the second treatment agent contains IPBC and propiconazole. Contains compatible particles.

  In the fourth aspect, preferably, the first treating agent contains microcapsules containing clothianidin and first compatible particles containing IPBC, and the second treating agent contains propiconazole. Contains second compatible particles.

  In the fifth aspect, preferably, the first treatment agent contains microcapsules containing clothianidin and flowable particles containing IPBC, and the second treatment agent contains second particles containing propiconazole. Of compatible particles.

  In the sixth aspect, preferably, the first treatment agent contains first multi-domain particles containing clothianidin and first compatible particles containing IPBC, and the second treatment agent is And second compatible particles containing propiconazole.

  In the seventh aspect, preferably, the first treatment agent contains first multi-domain particles containing clothianidin and flowable particles containing IPBC, and the second treatment agent is propiconazole. The 2nd compatible particle | grains containing are contained.

  In the eighth aspect, preferably, the first treatment agent contains first compatible particles containing etofenprox and first compatible particles containing IPBC, and the second treatment agent. Contains second compatible particles containing propiconazole.

  In the ninth aspect, preferably, the first treatment agent contains first compatible particles containing etofenprox and flowable particles containing IPBC, and the second treatment agent is propico. Second compatible particles containing nazole are contained.

  In the tenth aspect, preferably, in the first to ninth aspects, the first treatment agent further contains first multi-domain particles containing capsaicins. Specifically, in the tenth aspect, more preferably, the first treatment agent contains first multi-domain particles containing capsaicins and microcapsules containing clothianidin, and more preferably The first treating agent contains first multi-domain particles containing capsaicins and first compatible particles containing etofenprox or IPBC.

  More preferable examples of the water-based wood preservative include the first aspect, the second aspect, the third aspect, the fourth aspect, the sixth aspect, the eighth aspect, and the tenth aspect, and more preferably. Includes the first and second aspects.

  In the first aspect and the second aspect, the blending ratio of the first treatment agent to the total amount of the first treatment agent and the second treatment agent is, for example, 5% by mass or more, preferably 10% by mass or more. In addition, for example, it is 65% by mass or less, preferably 60% by mass or less. The blending ratio of the second treatment agent to the total amount of the first treatment agent and the second treatment agent is, for example, 60% by mass or more, preferably 65% by mass or more, and, for example, 95% by mass. % Or less, preferably 90% by mass or less. If the blending ratio of the second treatment agent is equal to or more than the lower limit described above, the second compatible particles can penetrate into the interior of the wood and can exhibit an excellent antiseptic and fungicidal sustaining effect. If the blending ratio of the second treatment agent is equal to or less than the above upper limit, the insecticidal efficacy can be reliably ensured on the surface of the wood.

  In the first aspect and the second aspect, the content ratio of the insecticide to the total amount of the insecticide and the antiseptic and fungicidal agent is, for example, 5% by mass or more, preferably 8% by mass or more. For example, it is 45 mass% or less, preferably 40 mass% or less. Further, the content ratio of the antiseptic / antifungal agent to the total amount of the insecticide and the antiseptic / antifungal agent is, for example, 55% by mass or more, preferably 60% by mass or more, and for example, 95% by mass or less, preferably 92 mass% or less. If the blending ratio of the antiseptic / fungal agent is not less than the above lower limit, excellent antiseptic / fungal can be continuously expressed in the wood. If the blending ratio of the antiseptic and fungicide is not more than the above upper limit, the insecticidal effect can be reliably ensured on the surface of the wood.

  Furthermore, the total content of the insecticide and the antiseptic / fungal agent is, for example, 5% by mass or more, preferably 6% by mass or more, and for example, 30% by mass or less, preferably 25% by mass or less.

  In addition, the concentration of the active ingredient in the aqueous wood preservative is about 0.005% by mass or more, preferably 0.01% by mass or more, for example, 30% by mass or less, preferably 2% by mass or less. If necessary, it can be treated with wood after dilution with water.

  Furthermore, an additive usually added to an aqueous wood preservative, specifically, an additive described in Japanese Patent Application Laid-Open No. 2008-081466 can also be added to the aqueous wood preservative at an appropriate ratio. .

  The wood preservative obtained as described above can be processed into wood by a known processing method such as dipping or coating.

  The wood that is a material to be treated with such an aqueous wood preservative is not particularly limited, and examples thereof include building materials such as houses and buildings, and general industrial wood such as furniture.

(2) Effect of water-based wood preservative According to the water-based wood preservative containing the above-described treatment agent, the active ingredient of the first treatment agent remains on the surface of the wood and the second treatment agent While the active ingredient penetrates into the wood, an excellent effect of sustaining the effect can be expressed inside the wood.

  Further, in this aqueous wood preservative, when the second treating agent contains the second compatible particles, the second compatible particles are excellent in dispersibility. The amount used can be reduced. Therefore, the safety of the aqueous wood preservative preparation can be improved.

  Further, in this aqueous wood preservative, when the second treatment agent contains the second compatible particles, the colloidal stability of the second compatible particles is improved. Even when a mechanical shearing force is applied, aggregation and destruction of the second compatible particles can be prevented.

Furthermore, the microcapsules suitably used as the first treatment agent, specifically, clothianidin microcapsules manufactured using interfacial polymerization (microcapsules containing clothianidin) are likely to swell in the wall film in the solvent. Therefore, when the second treating agent is prepared as an emulsion containing the second compatible particles and not containing the solvent, the first treating agent and the second treating agent are blended. Even so, swelling of the first treatment agent, specifically, clothianidin microcapsules can be suppressed.
6-2. Water-based paint (1) Composition of water-based paint The water-based paint contains the treatment agent exemplified for the water-based wood preservative and a film-forming component.

  In the water-based paint, examples of the treating agent include the first to ninth aspects described above.

  Examples of coating film-forming components include acrylic, acrylic-styrene, styrene, vinyl acetate, vinyl acetate-acrylic, polyester, silicone, urethane, alkyd, and fluororesin emulsions or aqueous solutions. Examples thereof include resins and mixtures thereof.

  The total content of the active ingredients contained in the treatment agent is, for example, 0.005 parts by mass or more, preferably 0.01 parts by mass or more, for example, 30 parts by mass, relative to 100 parts by mass of the coating film forming component. Part or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less.

  In order to obtain a water-based paint, a treating agent and a film-forming component are blended and mixed to prepare a mixture. Thereafter, if necessary, the mixture is diluted with water at an appropriate magnification.

  The application target, which is a material to be treated with a water-based paint, is not particularly limited, and examples thereof include various wood products such as the above-described wood, plywood, particle board, laminated wood, and a composite material of wood and plastic. It is done. When wood is an object to be applied, this water-based paint is a wood protective paint.

Processing amount of the active ingredient in water-based paint, to a substrate, for example, 6 mg / ^{m 2} or more, preferably, 12 mg / ^{m 2} or more, and is, for example, 48000mg / ^{m 2} or less, preferably, 3200 mg / m ² or less.

(2) Effect of water-based paint And according to the water-based paint containing the above-described treatment agent, the active ingredient of the first treatment agent remains on the surface of the application target, and the active ingredient of the second treatment agent is While penetrating the inside of the application target, an excellent effect of sustaining the effect can be expressed inside the application target.

  Further, in this water-based paint, when the second treatment agent contains the second compatible particles, the second compatible particles are excellent in dispersibility, so the amount of emulsifier and binder used in the water-based paint is reduced. can do. Therefore, the safety of the water-based paint preparation can be improved.

  Further, in this water-based paint, when the second treatment agent contains the second compatible particles, the colloidal stability of the second compatible particles is improved, so when applying the water-based paint, Even when a mechanical shearing force is applied to the water-based paint, the second compatible particles can be prevented from aggregating and breaking.

In addition, since this water-based paint contains the second treatment agent containing the second particles having an average particle diameter of less than 1 μm, the water-based paint is excellent in miscibility with the coating film forming component.
6-3. Building materials (1) Specific examples and prescriptions of building materials Examples of building materials to which the treatment agent is applied include gypsum board, cement, plaster, ceiling materials, fiber walls, joint agents, sealants, and wallpaper.

  The treatment agent is added to the building material.

  The amount of the treatment agent added is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and, for example, 12 parts by mass or less, preferably 13 parts by mass with respect to 100 parts by mass of the raw material of the building material. It is adjusted so that it becomes less than the part.

(2) Effect of building material And according to the building material containing the treating agent, the active ingredient of the first treating agent remains on the surface of the construction target on which the building material is constructed, and the active ingredient of the second treating agent. Can permeate into the interior of the construction object, and can exhibit an excellent effect of sustaining the effect inside the construction object.

  The preparation examples and examples are shown below to further illustrate the present invention. In addition, this invention is not limited to them at all. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to. In the Preparation Examples and Examples, units such as% mean mass% unless otherwise specified.

1. Details of Abbreviations First, details of abbreviations used in each preparation example are described below.

(1) Antibiotic active compound clothianidin: (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine, molecular weight 250, melting point 176.8 ° C., solubility in water: 330 ppm , First antibiotic active compound, manufactured by Sumitomo Chemical Co., Ltd. etofenprox: 2- (4-ethoxyphenyl) -2-methylpropyl = 3-phenoxybenzyl = ether, molecular weight 377, melting point 37.4 ° C., water Solubility: 22.5 ppb, dipole force term δ _{p, compound of} solubility parameter δ 2.27 [(J / cm ³ ) ^1/2 ], hydrogen bond term δ _{h, compound of} solubility parameter δ: 5. ^{33 [(J / cm 3)} 1/2], the second of the antibiotic compound, Maruzen Pharmaceutical Co., Ltd. IPBC: trade name "fan formate trawl 400", 3-iodo 2-propynyl butyl carbamate, molecular weight 281, melting point: 60 ° C., solubility in water: 150 ppm, solubility parameter polar term of _{δ δ p, compound: 3.23 [} (J / cm 3) 1/2], Hydrogen bonding term δ _{h, compound} : 7.83 [(J / cm ³ ) ^1/2 ] of solubility parameter δ, second antibiotic active compound, Propiconazole manufactured by International Specialty Products: 1- [ 2- (2,4-Dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, molecular weight 342, melting point less than 20 ° C., solubility in water 110 ppm , polar term [delta] _p, Compound solubility parameter ^{δ: 6.55 [(J / cm} 3) 1/2], the solubility parameter [delta] Hydrogen bonding term _{δ h, compound: 9.44 [(} J / cm 3) 1/2], the second antibiotic compound, eight Saiwaidori trading Made Capsaicin: N - [(4- hydroxy-3- Methoxyphenyl) methyl] -8-methyl-6-nonenamide, molecular weight 305, melting point 66 ° C., water solubility: 0.33 g / L (25 ° C.), manufactured by Wako Pure Chemical Industries, Ltd.

(2) Monomer, etc. DVB-570: Trade name, insoluble in water, composition: divinylbenzene (upper limit 60%), ethyl vinylbenzene (upper limit 40%), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. MMA: methyl methacrylate, trade name “Acryester M”, solubility in water: 1.6% by mass, dipole force term δ _p, monomer unit of solubility parameter δ as a monomer _unit : 5.98 [(J / cm ³ ) ^1/2 ] , Hydrogen bond strength term δ _h , monomer unit of solubility parameter δ as a monomer _unit : 9.25 [(J / cm ³ ) ^1/2 ], MAA manufactured by Mitsubishi Rayon Co., Ltd. MAA: methacrylic acid, solubility in water: 8. 9 wt%, claim dipole-dipole force solubility parameter [delta] as a monomer unit _{δ p, 2nd monomer unit: 7.13} [(J / cm 3) 1/2], monomer Hydrogen bonding term solubility parameter [delta] as a unit _{δ h, 2nd monomer unit: 13.03} [(J / cm 3) 1/2], manufactured by Mitsubishi Rayon Co., Ltd. i-BMA: iso- butyl methacrylate, solubility in water : 0.5 g / L (25 ° C.), dipole force term δ _{p, monomer unit of} solubility parameter δ: 3.75 [(J / cm ³ ) ^1/2 ], hydrogen bond strength term δ of solubility parameter δ _{h, monomer unit} : 7.32 [(J / cm ³ ) ^1/2 ], manufactured by Nippon Shokubai Co., Ltd. EGDMA: ethylene glycol dimethacrylate, trade name “light ester EG”, solubility in water: 581 mg / L (25 ° C. ) term dipole-dipole force solubility parameter [delta] as a monomer unit _{δ p, monomer unit: 5.37 [} (J / cm 3) 1/2], Hydrogen bonding term solubility parameter [delta] as Nomar unit _{δ h, monomer: 10.42 [(} J / cm 3) 1/2], Kyoeisha Chemical Co., Ltd. Takenate D-140 N :, trade name, polyisocyanate, Mitsui Chemicals DETA: Diethylenetriamine, manufactured by Wako Pure Chemical Industries, Ltd.

(3) Other components Dilauroyl peroxide: trade name “Perroyl L”, oil-soluble polymerization initiator, manufactured by NOF Corporation DISPERBYK-164: trade name, functional group-modified copolymer for pigment dispersion (molecular weight: 10,000 to 50,000) , Manufactured by Big Chemie PVA-217: trade name “Kuraraypoval 217”, partially saponified polyvinyl alcohol, degree of saponification: 87.0-89.0%, degree of polymerization: 1700, viscosity (4% by weight aqueous solution, 20 ° C.): 22 0.0 to 27.0 mPa · sec, dispersant, Kuraray Metroise 90SH-100: trade name, methylcellulose, viscosity (2% by weight aqueous solution, 20 ° C.) 100 mPa · s, dispersant, Shin-Etsu Chemical Co., Ltd. DBN: Product name “Neopelex No. 6 powder”, sodium dodecylbenzenesulfonate, anionic emulsifier, manufactured by Kao Corporation Perex SS-L: trade name, 50% by weight aqueous solution of sodium alkyldiphenyl ether disulfonate (anionic emulsifier), Persoft EF: trade name, 25% by weight aqueous solution of polyoxyethylene alkyl ether sulfate sodium salt (anion) Emulgen A-90 manufactured by NOF Corporation, trade name, polyoxyethylene distyrenated phenyl ether, nonionic emulsifier, manufactured by Kao Corporation Emulgen A-500: trade name, polyoxyethylene distyrenated phenyl ether, nonion -Based emulsifier, manufactured by Kao Corporation Neocor SW-C: trade name, 70 mass% isopropanol solution of sodium dioctylsulfosuccinate (anionic emulsifier), manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Pronon 208: trade name, polyoxyethylene polyoxypropylene block Polymers, nonionic emulsifier, manufactured by NOF Corporation Noigen EA-177: tradename, polyoxyethylene styrenated phenyl ether, nonionic emulsifier (HLB: 15.6), manufactured by Dai-ichi Kogyo Seiyaku Co.
DK ester F-160: trade name, sucrose fatty acid ester, nonionic emulsifier, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Demol NL: trade name, 41% by weight aqueous solution of β-naphthalenesulfonic acid formaldehyde condensate sodium salt, anionic dispersant New Calgen FS-4 manufactured by Kao Corporation: trade name, β-naphthalenesulfonic acid formaldehyde condensate sodium salt, anionic dispersant, manufactured by Takemoto Yushi Co., Ltd. Rheojic 260H: trade name, sodium polyacrylate, thickener, Toagosei Nisseki Hyzol SAS-296: Brand name, Phenylxylylethane, JX Nippon Mining & Energy Corporation Alkene L: Brand name, alkylbenzene, JX Nippon Mining & Energy Corporation Propylene glycol: Antifreeze, Wako Pure Chemical Industries, Ltd. Nopco 8034-L: Product name, antifoaming agent, manufactured by San Nopco Equipment Used for Dispersion Homo Disper: Trade name “TK Homo Disper Model 2.5”, manufactured by Primex Corporation Homo Mixer: Trade name “TK Homo Mixer Mark 2.5 type”, manufactured by Primex Corporation Bead mill: Product name “Disper” 2. “Mat SL-12C”, manufactured by VMA-GETZMANNGMBH. Measurement of Median Diameter The median diameter of the particles of each of the preparation examples described below is the laser diffraction scattering type particle size distribution measuring apparatus LA-920 (for the particles of Preparation Examples 1 to 3, 8, 10, 11 and 13. The median diameter of the clothianidin in slurry B of Preparation Example 2 and the particles of Preparation Examples 4 to 7, 9 and 12 was measured using a dynamic light scattering particle size analyzer (FPAR-1000, Otsuka Electronics). ).

[Preparation of the first treatment agent and the second treatment agent]
Preparation Example 1
(Production of clothianidin-containing microcapsules (first particles))
(Production method: Interfacial polymerization)
Blending Nisseki Hyzol SAS-296 318g, Alkene L 154g, DISPERBYK-164 48g, mixing them uniformly, adding 480g clothianidin to this, stirring with homodisper, slurry containing clothianidin 48% by mass Liquid A was obtained.

  Next, the obtained slurry liquid A containing 48% by mass of clothianidin was wet pulverized by a bead mill. Then, 213 g of Takenate D-140N was added to 283 g of the slurry liquid A subjected to wet pulverization, and stirred uniformly to obtain slurry liquid B.

  Thereafter, 248 g of the obtained slurry liquid B is added to 492 g of an aqueous solution containing 50.4 g of PVA-217 and 3.6 g of Newkargen FS-4, and a few drops at room temperature with a homomixer so as to form fine droplets. The mixture was stirred for 5 minutes at a rotational speed of 5000 rpm.

  Next, while gently stirring this mixed liquid, 207 g of water and the remaining 248 g of the slurry liquid B were added and stirring was continued. Thereafter, the mixture was stirred with a homomixer at room temperature for several minutes at a rotational speed of 2500 rpm.

  Next, while gently stirring this mixed solution in a thermostat at 75 ° C. for 3 hours, 7.6 g of DETA was dropped, and these were interfacially polymerized so that clothianidin was included in a film made of polyurethane and polyurea. Formulated to obtain microcapsules. The average particle size of the microcapsules was 10 μm.

  Thereafter, 450 g of 0.5% by weight aqueous solution of Rheological 260H, 54 g of propylene glycol, and 93.4 g of water were added thereto to make the total mass 1800 g, and the concentration of clothianidin was adjusted to 7.5% by mass.

Preparation Example 2
(Production of first multi-domain particle (first particle) containing clothianidin)
(Production method: suspension polymerization)
First, 550 g of DVB-570 and 60.5 g of DISPERBYK-164 were stirred and mixed until uniform, and then 385 g of clothianidin was added and stirred and mixed with a homodisper to obtain a slurry containing clothianidin 38.7%. It was. The obtained slurry was put into a bead mill and wet pulverized for 15 minutes to obtain a slurry containing clothianidin 38.7% (slurry B). The median diameter of clothianidin in slurry B was 468 nm.

  Next, 100 g of slurry B and 500 mg of dilauroyl peroxide were charged into a 200 mL beaker, and the dilauroyl peroxide was dissolved in slurry B by stirring at room temperature.

  Separately, 257.5 g of ion-exchanged water, 40 g of 10% aqueous solution of PVA-217 and 1 g of 1% aqueous solution of pronone 208 were charged into a 500 mL beaker and stirred at room temperature to obtain a uniform aqueous solution.

  Next, slurry B containing dilauroyl peroxide was added to a 500 mL beaker and stirred for 5 minutes at a rotation speed of 6000 rpm with a homomixer to disperse slurry B in water to prepare a suspension (aqueous dispersion). did.

  Thereafter, the suspension (aqueous dispersion) is transferred to a 500 mL 4-neck Kolben equipped with a stirrer, reflux condenser, thermometer and nitrogen introduction tube, and heated with stirring in a nitrogen stream to effect suspension polymerization. Carried out.

  The suspension polymerization was started at the time when the temperature reached 55 ° C., and then continuously carried out at 70 ± 1 ° C. for 5 hours and at 80 ± 1 ° C. for 2 hours.

  Thereafter, the suspension after the reaction was cooled to 30 ° C. or lower to obtain a suspension (suspension) of the first multi-domain particles containing clothianidin. The median diameter of the first multidomain particle was 28.2 μm.

  Moreover, as a result of TEM observation about the particle | grains of this suspension, it confirmed that it was the 1st multi domain type particle | grain. Specifically, a suspension (suspension) is freeze-dried, dispersed in a bisphenol liquid epoxy resin, and cured with an amine. This was cut with an ultramicrotome to obtain a cross section, stained with ruthenium tetroxide, and cut into ultrathin sections with an ultramicrotome to prepare a sample. The prepared sample was observed with a transmission electron microscope (model number “H-7100”, manufactured by Hitachi, Ltd.) by TEM. The image processing figure of the TEM photograph of the first multi-domain particle is shown in FIG.

Preparation Example 3
(Production of first compatible particles (first particles) containing etofenprox (Production method: suspension polymerization)
A 200 mL beaker was charged with 40 g of etofenprox, 42 g of MMA, 18 g of EGDMA and 500 mg of dilauroyl peroxide, and stirred at room temperature to prepare a uniform hydrophobic solution.

  Separately, 258.5 g of ion-exchanged water, 40 g of a 10% aqueous solution of PVA-217, and 1 g of a 1% aqueous solution of pronone 208 were placed in a 500 mL beaker and stirred at room temperature to obtain a uniform aqueous solution.

  Next, the hydrophobic solution was added to a 500 mL beaker, and the hydrophobic solution was suspended by stirring with a homomixer at 3000 rpm for 10 minutes.

  Thereafter, the suspension was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, and heated with stirring under a nitrogen stream to carry out suspension polymerization.

  The suspension polymerization was started at the time when the temperature reached 55 ° C., and then continuously carried out at 60 ± 2 ° C. for 1 hour, 70 ± 2 ° C. for 3 hours, and 80 ± 2 ° C. for 2 hours.

  Thereafter, the suspension after the reaction was cooled to 30 ° C. or lower to obtain a suspension of first compatible particles containing etofenprox.

  The median diameter of the first compatible particles was 10.1 μm.

  Moreover, as a result of TEM observation about the particle | grains of this suspension, it confirmed that it was the 1st compatible particle | grain. A TEM photograph of the particles of Preparation Example 3 is shown in FIG. As can be seen from FIG. 3, TEM observation confirmed that the particles had a uniform structure, that is, a homogeneous phase in which etofenprox and the polymer were compatible.

  In addition, as can be seen from FIG. 3, in the TEM photograph of Preparation Example 3, a phase with a high concentration of etofenprox forms a layer close to the surface of the particle, and a phase with a low concentration forms an inner portion thereof. . In each phase, etofenprox and the polymer are compatible.

Preparation Example 4
(Production of second compatible particles (second particles) containing propiconazole and IPBC)
(Production method: Miniemulsion polymerization)
A 200 mL container was charged with 24 g of IPBC, 56 g of propiconazole, 18.8 g of MMA, 1.2 g of EGDMA and 0.5 g of dilauroyl peroxide, and stirred at room temperature to prepare a uniform hydrophobic solution.

  Separately, in a 500 mL beaker, 106.46 g of deionized water, 2.8 g of Pelex SS-L, 40 g of PVA-217 (10%) aqueous solution and 0.24 g of demole NL were charged and stirred at room temperature to obtain a uniform aqueous emulsifier solution. Prepared.

  Subsequently, the hydrophobic solution was added to the emulsifier aqueous solution of a 500 mL beaker, and the hydrophobic solution was emulsified in the emulsifier aqueous solution by stirring with a homomixer at a rotation speed of 12000 rpm for 5 minutes to prepare a mini-emulsion.

  Thereafter, the prepared mini-emulsion was transferred to a 300 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, and a rotation speed of 200 rpm (peripheral speed: 37. The temperature was raised with stirring at 7 m / min) to carry out miniemulsion polymerization.

  The mini-emulsion polymerization was started at the time when the temperature reached 55 ° C., and then continuously performed at 62 ± 2 ° C. for 3 hours and 70 ± 2 ° C. for 2 hours. Subsequently, the temperature of the reaction solution was raised to 80 ± 2 ° C. and aged for 2 hours.

  Then, the emulsion of the 2nd compatible particle | grains containing IPBC and propiconazole was obtained by cooling a reaction liquid to 30 degrees C or less. The median diameter of the second compatible particles was 429 nm.

Preparation Examples 5-7
(Production of second compatible particles (second particles) containing propiconazole and IPBC)
A second compatible particle emulsion containing IPBC and propiconazole was obtained in the same manner as in Preparation Example 4 except that the formulation was changed according to Table 1. The median diameter is listed in Table 1.

Preparation Example 8
(Production of first compatible system particles (first particles) containing propiconazole and IPBC)
(Production method: suspension polymerization)
A 200 mL beaker was charged with 12 g of IPBC, 28 g of propiconazole, 42 g of MMA, 18 g of EGDMA and 500 mg of dilauroyl peroxide, and stirred at room temperature to prepare a uniform hydrophobic solution.

  Separately, 258.5 g of ion-exchanged water, 40 g of a 10% aqueous solution of PVA-217, and 1 g of a 1% aqueous solution of pronone 208 were placed in a 500 mL beaker and stirred at room temperature to obtain a uniform aqueous solution.

  Next, the hydrophobic solution was added to a 500 mL beaker, and the hydrophobic solution was suspended by stirring with a homomixer at 3000 rpm for 10 minutes.

  Thereafter, the suspension was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, and heated with stirring under a nitrogen stream to carry out suspension polymerization.

  The suspension polymerization was started at the time when the temperature reached 55 ° C., and then continuously carried out at 60 ± 2 ° C. for 1 hour, 70 ± 2 ° C. for 3 hours, and 80 ± 2 ° C. for 2 hours.

  Thereafter, the suspension after the reaction was cooled to 30 ° C. or lower to obtain a suspension of first compatible particles containing propiconazole and IPBC.

  The median diameter of the first compatible particles was 9.8 μm.

  Moreover, as a result of TEM observation about the particle | grains of this suspension, it confirmed that it was the 1st compatible particle | grain. A TEM photograph of the particles of Preparation Example 8 is shown in FIG. As can be seen from FIG. 4, TEM observation confirmed that the particles had a uniform structure, that is, a homogeneous phase in which propiconazole and IPBC were compatible with the polymer.

Preparation Example 9
(Production of second compatible particles (second particles) containing IPBC)
(Production method: Miniemulsion polymerization)
A uniform hydrophobic solution was prepared by charging 25 g of IPBC, 75 g of MMA and 0.5 g of dilauroyl peroxide in a 200 mL container and stirring at room temperature.

  Separately, 125.5 g of deionized water, 4.0 g of Neocor SW-C, and 20 g of a 25% by weight aqueous solution of Neugen EA-177 were placed in a 500 mL beaker and stirred at room temperature to prepare a uniform aqueous emulsifier solution.

  Subsequently, the hydrophobic solution was added to the emulsifier aqueous solution of a 500 mL beaker, and the hydrophobic solution was emulsified in the emulsifier aqueous solution by stirring with a homomixer at a rotation speed of 12000 rpm for 5 minutes to prepare a mini-emulsion.

  Thereafter, the prepared mini-emulsion was transferred to a 300 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, and the rotation speed was 125 rpm (circumferential speed 23. The temperature was increased while stirring at 6 m / min) to carry out miniemulsion polymerization.

  The mini-emulsion polymerization was started at the time when the temperature reached 55 ° C., and then continuously carried out at 60 ± 2 ° C. for 1 hour and at 70 ± 2 ° C. for 3.5 hours. Subsequently, the temperature of the reaction solution was raised to 78 ± 2 ° C. and aged at that temperature for 2.5 hours.

  Then, the reaction liquid was cooled to 30 ° C. or lower to obtain an emulsion of second compatible particles containing IPBC. The median diameter of the second compatible particles was 201 nm.

Preparation Example 10
(Production of first compatible particles (first particles) containing IPBC)
(Production method: suspension polymerization)
A homogeneous hydrophobic solution was prepared by charging 40 g of IPBC, 42 g of MMA, 18 g of EGDMA, and 500 mg of dilauroyl peroxide in a 200 mL beaker and stirring at room temperature.

  Separately, 258.5 g of ion-exchanged water, 40 g of a 10% aqueous solution of PVA-217, and 1 g of a 1% aqueous solution of pronone 208 were placed in a 500 mL beaker and stirred at room temperature to obtain a uniform aqueous solution.

  Next, the hydrophobic solution was added to a 500 mL beaker, and the hydrophobic solution was suspended by stirring with a homomixer at 3000 rpm for 10 minutes.

  Thereafter, the suspension was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, and heated with stirring under a nitrogen stream to carry out suspension polymerization.

  The suspension polymerization was started at the time when the temperature reached 55 ° C., and then continuously carried out at 60 ± 2 ° C. for 1 hour, 70 ± 2 ° C. for 3 hours, and 80 ± 2 ° C. for 2 hours.

  Thereafter, the suspension after the reaction was cooled to 30 ° C. or less to obtain a suspension of first compatible particles containing IPBC.

  The median diameter of the first compatible particles was 7.4 μm.

  Moreover, as a result of TEM observation about the particle | grains of this suspension, it confirmed that it was the 1st compatible particle | grain. A TEM photograph of the particles of Preparation Example 10 is shown in FIG. As can be seen from FIG. 5, TEM observation confirmed that the particles had a uniform structure, that is, a homogeneous phase in which IPBC and the polymer were compatible.

Preparation Example 11
(Production of flowable agent (first particle) containing flowable particles of IPBC)
(Production method: wet grinding)
30 g of IPBC, 1.5 g of DK ester F-160, 2 g of methyl cellulose, 0.6 g of Perex SS-L, 0.2 g of Nopco 8034-L were added to 65.7 g of water and mixed with stirring, and then a bead mill (Dynomill, Typ KDL). A, a flowable agent containing 30% IPBC flowable particles was obtained by wet pulverization with a glass bead diameter of 0.5 mm. The median diameter of the IPBC flowable particles was 8.4 μm.

Preparation Example 12
(Production of second compatible system particles (second particles) containing propiconazole)
(Production method: Miniemulsion polymerization)
In a 200 mL container, 45 g of propiconazole, 51.7 g of MMA, 3.3 g of EGDMA and 0.5 g of dilauroyl peroxide were charged and stirred at room temperature to prepare a uniform hydrophobic solution.

  Separately, in a 500 mL beaker, 157.26 g of deionized water, 2.0 g of Neocol SW-C, 40 g of an aqueous solution of PVA-217 (10% by mass) and 0.24 g of Demol NL are stirred and stirred at room temperature to obtain a uniform emulsifier. An aqueous solution was prepared.

  Subsequently, the hydrophobic solution was added to the emulsifier aqueous solution of a 500 mL beaker, and the hydrophobic solution was emulsified in the emulsifier aqueous solution by stirring with a homomixer at a rotation speed of 14,000 rpm for 10 minutes to prepare a mini-emulsion.

  Thereafter, the prepared mini-emulsion was transferred to a 300 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, and a rotation speed of 200 rpm (peripheral speed: 37. The temperature was raised with stirring at 7 m / min) to carry out miniemulsion polymerization.

  The mini-emulsion polymerization was started at the time when the temperature reached 55 ° C., and then continuously carried out at 60 ± 2 ° C. for 3 hours and at 70 ± 2 ° C. for 2 hours.

  Subsequently, the temperature of the reaction solution was raised to 80 ± 2 ° C. and aged for 2 hours.

  Then, the reaction liquid was cooled to 30 ° C. or lower to obtain an emulsion of second compatible particles containing propiconazole. The median diameter of the second compatible particles was 166 nm.

Preparation Example 13
(Production of first multi-domain particle (first particle) containing capsaicin)
A 200 mL container was charged with 20 g of capsaicin, 56 g of i-BMA, 24 g of EGDMA and 0.5 g of dilauroyl peroxide, and stirred at room temperature (25 ° C.) to prepare a uniform hydrophobic solution.

  Separately, a 500 mL beaker was charged with 258.26 g of deionized water, 0.24 g of demole NL, 1 g of 1% aqueous solution of Pronon 208, and 40 g of 10% aqueous solution of PVA-217, and stirred at room temperature to obtain a uniform aqueous solution. Prepared.

  The hydrophobic solution is then added to an aqueous solution in a 500 mL beaker. K. An aqueous dispersion was prepared by dispersing the hydrophobic solution in an aqueous solution by stirring for 5 minutes at a rotation speed of 2000 rpm with a homomixer MARK 2.5 (manufactured by Primix).

  Thereafter, the aqueous dispersion was transferred to a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, and rotated at 100 rpm (circumferential speed 18.9 m) with a 6 cm diameter stirrer under a nitrogen stream. / Min), the temperature of the four-necked flask was raised by a water bath to carry out suspension polymerization (radical polymerization).

  The suspension polymerization was started at the time when the temperature reached 55 ° C., and then continuously carried out at 60 ± 2 ° C. for 1 hour and at 70 ± 2 ° C. for 3 hours.

  Subsequently, the temperature of the water bath was raised, and the temperature of the reaction solution was raised to 80 ± 2 ° C. and aged for 3 hours.

  Thereafter, the reaction liquid was cooled to 30 ° C. or lower to obtain a suspension containing capsaicin and containing first multi-domain particles (first particles) having a median diameter of 40 μm.

  Table 2 shows the preparation method of each preparation example.

[Preparation of wood preservative]
Examples 1-15 and Comparative Examples 1-3
A wood preservative was prepared by blending the first treatment agent and the second treatment agent prepared in each of the preparation examples and water in accordance with the formulation described in Table 3.

[Evaluation of wood preservatives]
(Preservation test)
The wood preservatives of Examples 1-5 and Comparative Examples 1 and 2 were diluted 20 times with pure water, and the wood preservatives of Examples 6-12, 14, 15 and Comparative Example 3 were diluted 10 times with pure water. Then, the wood preservative of Example 13 was diluted 8 times with pure water and used by the Japan Wood Preservation Association to determine the indoor preservative efficacy test method and performance standard for surface treatment wood preservatives (JWPS-FW The antiseptic test was carried out in accordance with “-S.1)”. Further, an antiseptic test (control) in which no wood preservative was used was also carried out as Comparative Example 4. In these antiseptic tests, rot fungi and Kawaratake were used as the test subjects, and the mass reduction rate (%) of the wood was measured, and the suitability / unsuitability was evaluated according to the following criteria. In addition, the mass reduction rate is 3% or less as a prescribed value for passing the wood preservative.

  The results are shown in Table 3.

Conformity: Mass reduction rate is 3% or less Unsuitable: Mass reduction rate exceeds 3%

The numerical values in Table 3 are the number of parts by mass, the upper column indicates the number of parts of each treatment agent, and the lower column indicates the number of parts of the active ingredient. However, in the 2nd processing agent column in Examples 1-6, 15 and comparative example 3, the numerical value of the left column shows the compounding part number of the 2nd processing agent, and the numerical value of the right column is the compounding part number of an active ingredient. Indicates. Moreover, the numerical value of the left column in the 1st processing agent column in Comparative Examples 1-3 shows the compounding part number of a 1st processing agent, and the numerical value of a right column shows the compounding part number of an active ingredient.

[Preparation of wood protective paint]
Examples 16-30 and Comparative Examples 5-7
In accordance with the formulation described in Table 4, while stirring the xyla decor interior fine pinney (trade name, main component: acrylic resin, manufactured by Nippon Envirochemicals) with a disper, Examples 1-14 and Comparative Examples 1-3 Each of the wood preservatives was blended, and further stirred and mixed at room temperature for 30 minutes to prepare each of the wood protective paints of Examples 16 to 30 and Comparative Examples 5 to 7.

[Evaluation of wood protective paint]
(Preservation test)
Using wood protective paint as a stock solution as it is, preserving in accordance with “Indoor Preservation Efficacy Test Method and Performance Standards of Wood Preservatives for Surface Treatment (JWPS-FW-S.1)” established by Japan Wood Preservation Association The test was conducted. For the preservative test, wood was left outdoors (ultraviolet exposure treatment) for 6 months. Moreover, the antiseptic test (control) which apply | coated the xyla decor interior fine pinny which has not added the wood preservative was made into the comparative example 8, and the antiseptic test (no coating) which did not apply | coat a wood protective coating was conducted as the comparative example 9. In these antiseptic tests, the rot fungi as test subjects were Ootake and Kawaratake, and the mass reduction rate (% by mass) of the wood was measured. In addition, 3 mass% or less is considered as the standard value of the pass of a wood protective coating material for the mass reduction rate. The results are shown in Table 4.

Conformity: Mass reduction rate is 3% or less.
Improper: Mass reduction rate exceeds 3%.

(Anti-mold test)
An antifungal test was carried out in accordance with Japan Wood Preservation Association Standard No. 2 using the wood protective paint as it was as a stock solution. For the preservative test, wood was left outdoors (ultraviolet exposure treatment) for 6 months. Moreover, the antifungal test (control) which apply | coated only the xyladecor interior fine which does not add a wood preservative was made into the comparative example 10, and the antiseptic test (no coating) which did not apply | coat a wood protective coating was carried out as the comparative example 11. In these antifungal tests, the fungi to be tested were Aspergillus niger and Penicillium funiculosum. The mass reduction rate (% by mass) of the wood was measured. The evaluation of the mold prevention test was as follows. The results are shown in Table 4.

0 No mold growth was observed on the test specimen (wood).
1 Mold growth is observed only on the side of the specimen.
2 Mold growth is observed in less than 1/3 of the area of the upper surface of the specimen.
3 Mold growth is observed in 1/3 or more of the upper surface area of the test specimen.

  The treating agent can be used for, for example, an aqueous wood preservative, for example, an aqueous paint, such as a building material.

Claims (16)

A first treatment agent in which an active ingredient remains on the surface of the material to be treated;
Containing an active ingredient and a second treatment agent that penetrates into the material to be treated;
The first treatment agent has an average particle diameter of 1 μm or more and contains first particles containing an active ingredient,
The second treating agent has an average particle diameter of less than 1 μm and contains second particles containing an active ingredient.   The ratio of the second treatment agent to the total amount of the first treatment agent and the second treatment agent is 60% by mass or more and 95% by mass or less. Processing agent.   The ratio of the active ingredient contained in the second treating agent to the total amount of the active ingredient contained in the first treating agent and the active ingredient contained in the second treating agent is 55% by mass. Above, it is 95 mass% or less, The processing agent of Claim 1 or 2 characterized by the above-mentioned.   The second particles are prepared by dissolving a hydrophobic active ingredient with a hydrophobic polymerizable vinyl monomer to prepare a hydrophobic solution, and blending water and an emulsifier to prepare an aqueous emulsifier solution. A solution obtained by emulsifying a solution in the aqueous emulsifier solution and polymerizing the polymerizable vinyl monomer by miniemulsion polymerization in the presence of a polymerization initiator. The processing agent as described in any one.   The treatment agent according to any one of claims 1 to 4, wherein the second treatment agent contains an antiseptic and fungicidal agent as an active ingredient.   The treatment agent according to claim 5, wherein the antiseptic / fungal agent contains an organic iodine compound and / or a triazole compound.   The treatment agent according to claim 1, wherein the first particle is a microcapsule in which an active ingredient is encapsulated by a film. The first particles are:
Slurry to prepare a hydrophobic slurry by dispersing an active ingredient that is hydrophobic and substantially insoluble in the polymerizable vinyl monomer in the absence of a solvent, in the hydrophobic polymerizable vinyl monomer. Process,
An aqueous dispersion step of preparing an aqueous dispersion by dispersing the hydrophobic slurry in water; and
The treatment agent according to any one of claims 1 to 6, which is obtained by a production method including a polymerization step of producing a polymer by suspension polymerization of the polymerizable vinyl monomer. The first particles are:
A hydrophobic solution preparation step of preparing a hydrophobic solution by dissolving a hydrophobic active ingredient in a hydrophobic polymerizable vinyl monomer in the absence of a solvent;
An aqueous dispersion step of dispersing the hydrophobic solution in water to prepare an aqueous dispersion; and
The treatment agent according to any one of claims 1 to 6, which is obtained by a production method including a polymerization step of producing a polymer by suspension polymerization of the polymerizable vinyl monomer.   The treatment agent according to claim 9, wherein in the first particle, the hydrophobic active ingredient is compatible with the polymer. The first particles are:
A matrix comprising the polymer;
The treatment agent according to claim 9, wherein the treatment agent has a phase separation structure formed from domains separated from the matrix and composed of the hydrophobic active ingredient.   The said 1st processing agent contains an insecticide and / or a repellent as an active ingredient, The processing agent as described in any one of Claims 1-11 characterized by the above-mentioned.   The treatment agent according to claim 12, wherein the insect repellent contains a neonicotinoid insecticide and / or a pyrethroid insecticide.   The treatment agent according to claim 12, wherein the repellent contains capsaicins.   The wood preservative characterized by including the processing agent as described in any one of Claims 1-14.   A paint comprising the treating agent according to claim 1.