WO2015030213A1 - Particules à libération prolongée et leur procédé de production, matériau de moulage et article moulé - Google Patents

Particules à libération prolongée et leur procédé de production, matériau de moulage et article moulé Download PDF

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Publication number
WO2015030213A1
WO2015030213A1 PCT/JP2014/072837 JP2014072837W WO2015030213A1 WO 2015030213 A1 WO2015030213 A1 WO 2015030213A1 JP 2014072837 W JP2014072837 W JP 2014072837W WO 2015030213 A1 WO2015030213 A1 WO 2015030213A1
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Prior art keywords
release particles
sustained
hydrophobic
vinyl monomer
oil phase
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PCT/JP2014/072837
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English (en)
Japanese (ja)
Inventor
大島　純治
井上　英明
智子 星野
小林　綾子
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日本エンバイロケミカルズ株式会社
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Priority claimed from JP2014174055A external-priority patent/JP6355485B2/ja
Application filed by 日本エンバイロケミカルズ株式会社 filed Critical 日本エンバイロケミカルズ株式会社
Priority to CN201480047961.6A priority Critical patent/CN105764338B/zh
Priority to AU2014312780A priority patent/AU2014312780A1/en
Priority to US14/914,949 priority patent/US20160235068A1/en
Publication of WO2015030213A1 publication Critical patent/WO2015030213A1/fr
Priority to AU2018203982A priority patent/AU2018203982A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers

Definitions

  • the present invention relates to sustained release particles, a production method thereof, a molding material and a molded product, and more particularly, to sustained release particles capable of sustained release of an antibiotic compound, a production method thereof, a molding material and a molded product.
  • Antimicrobial active compounds such as insecticides, insecticides, antproofing agents, fungicides, preservatives, herbicides, algae control agents, repellents, etc. are microencapsulated to gradually release the antibiotics and maintain their efficacy Particles that guarantee sex are known.
  • the particles may require sustained release depending on the purpose and purpose.
  • the microcapsules obtained by the method described in Patent Document 1 have a problem that the above-described requirements cannot be sufficiently satisfied.
  • An object of the present invention is to provide sustained release particles that are excellent in sustained release and robust, a production method thereof, a molding material and a molded product using the sustained release particles.
  • the inventors of the present invention have made extensive studies on the above-mentioned sustained release particles, a production method thereof, a molding material and a molded product using the sustained release particles, and in the absence of a solvent, the hydrophobicity and Oil phase component for preparing an oil phase component containing a hydrophobic slurry by dispersing an antibiotic active compound substantially insoluble in the hydrophobic polymerizable vinyl monomer in the hydrophobic polymerizable vinyl monomer Sustained release by a production method comprising a preparation step, a water dispersion step of dispersing an oil phase component in water to prepare an aqueous dispersion, and a polymerization step of producing a polymer by suspension polymerization of a polymerizable vinyl monomer.
  • the present inventors have found that it is possible to obtain an excellent and robust sustained-release particle, a molding material and a molded product using the same, and have completed the first invention group.
  • the first invention group is (1) In the absence of a solvent, a hydrophobic and substantially insoluble antibiotic active compound with respect to the hydrophobic polymerizable vinyl monomer is dispersed in the hydrophobic polymerizable vinyl monomer, thereby making the hydrophobic
  • the polymerizable vinyl monomer is subjected to suspension polymerization in the presence of a salt of a condensate of aromatic sulfonic acid and formaldehyde, and / or the polymerizable vinyl monomer is (meth) acrylic acid.
  • the sustained-release particles according to (1) above comprising an ester monomer and a (meth) acrylate crosslinkable monomer, (3)
  • the neonicotinoid insecticide includes (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine and 1- (6-chloro-3-pyridylmethyl)-
  • the sustained-release particles according to (3) above which contain at least one selected from the group consisting of N-nitroimidazolidine-2-ylideneamine, (5) It has a two-phase structure formed of a matrix made of a polymer and an antibiotic compound that is substantially insoluble in the monomer for forming the polymer and is dispersed in the matrix.
  • sustained release particles Characterized by sustained release particles, (6) The sustained release particles according to (5) above, wherein both the matrix and the domain are exposed on the surface of the sustained release particles, (7) The sustained release particles according to (5) above, wherein the domain is covered with the matrix, (8) Furthermore, the sustained release particles according to (7) above, wherein the antibiotic compound is attached to the surface of the matrix, (9) The sustained release particles according to any one of (5) to (8) above, wherein the antibiotic compound is a neonicotinoid insecticide, (10) The neonicotinoid insecticide includes (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine and 1- (6-chloro-3-pyridylmethyl)- The sustained release particles according to (9) above, comprising at least one selected from the group consisting of N-nitroimidazolidin-2-ylideneamine, (11) The sustained release particles according to any one of (1) to (10) above, wherein the sustained release particles are prepared as granules
  • a molding material comprising a thermoplastic resin and the sustained-release particles according to any one of (1) to (11) above, (13) A molded product comprising a thermoplastic resin and the sustained release particles according to any one of (1) to (11) above, (14)
  • a hydrophobic and substantially insoluble antibiotic active compound with respect to the hydrophobic polymerizable vinyl monomer is dispersed in the hydrophobic polymerizable vinyl monomer, thereby making the hydrophobic
  • An oil phase component preparation step for preparing an oil phase component containing a slurry, an aqueous dispersion step for preparing an aqueous dispersion by dispersing the oil phase component in water, and suspension polymerization of the polymerizable vinyl monomer,
  • the polymerizable vinyl monomer is subjected to suspension polymerization in the presence of a salt of a condensate of aromatic sul
  • the method for producing sustained-release particles according to (14) above comprising an ester monomer and a (meth) acrylate crosslinkable monomer, (16)
  • the suspension according to (14) or (15) above further comprising a step of blending the suspension obtained by the polymerization step and a solid carrier, drying them, and preparing granules.
  • the method for producing sustained-release particles according to any one of (14) to (16) above, wherein the antibiotic compound is a neonicotinoid insecticide, (18)
  • the neonicotinoid insecticide includes (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine and 1- (6-chloro-3-pyridylmethyl)-
  • the present inventors diligently examined the sustained-release particles of the first invention group, the production method thereof, the molding material and the molded product using the sustained-release particles, and in the absence of a solvent, An oily phase component containing a hydrophobic slurry is dispersed by dispersing an hydrophobic active vinyl compound that is substantially insoluble in the hydrophobic polymerizable vinyl monomer in the hydrophobic polymerizable vinyl monomer.
  • the release of the polymerizable vinyl monomer is controlled by a production method in which a suspension shell polymerization of the polymerizable vinyl monomer and a hydrophobic shell-forming component and a hydrophilic shell-forming component are interfacially polymerized to form a shell covering the suspension polymer.
  • the second invention group is: (1) In the absence of a solvent, a hydrophobic and substantially insoluble antibiotic active compound with respect to the hydrophobic polymerizable vinyl monomer is dispersed in the hydrophobic polymerizable vinyl monomer, thereby making the hydrophobic An oil phase component preparation step for preparing an oil phase component containing a slurry, an aqueous dispersion step for preparing an aqueous dispersion by dispersing the oil phase component in water, and suspension polymerization of the polymerizable vinyl monomer, A polymerization step for forming a coalescence, and at least one of the oil phase component preparation step, the water dispersion step and the polymerization step, a hydrophobic shell-forming component and a hydrophilic shell-forming component are contained, and the polymerization step Then, the polymerizable vinyl monomer is subjected to suspension polymerization, and the hydrophobic shell-forming component and the hydrophilic shell-forming component are interfacially polymerized to coat the suspension polymer.
  • controlled release particles (2) The controlled release particles according to (1) above, characterized in that the interfacial polymerization is started simultaneously with the start of suspension polymerization or before the start of suspension polymerization, (3) The sustained-release particles according to (1) or (2) above, wherein the hydrophobic shell-forming component contains a polyisocyanate, and the hydrophilic shell-forming component contains a polyamine, (4) The sustained release particles according to any one of (1) to (3) above, wherein the antibiotic compound is a neonicotinoid insecticide, (5) The neonicotinoid insecticide includes (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine and 1- (6-chloro-3-pyridylmethyl)- The sustained-release particles according to (4) above, comprising at least one selected from the group consisting of N-nitroimidazolidine-2-ylideneamines, (6) A matrix composed of a polymer, an antibiotic compound which is substantially insoluble in the mono
  • the shell is made of polyurea, the sustained release particles according to (6) above, (8) The sustained release particles according to (6) or (7) above, wherein an antibiotic compound is attached to the surface of the shell, (9) The sustained-release particles according to any one of (6) to (8) above, wherein the antibiotic compound is a neonicotinoid insecticide, (10) The neonicotinoid insecticide includes (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine and 1- (6-chloro-3-pyridylmethyl)- The sustained release particles according to (9) above, comprising at least one selected from the group consisting of N-nitroimidazolidin-2-ylideneamine, (11) The sustained release particles according to any one of (1) to (10) above, wherein the sustained release particles are prepared as granules.
  • a molding material comprising a thermoplastic resin and the sustained-release particles according to any one of (1) to (11) above, (13) A molded product comprising a thermoplastic resin and the sustained release particles according to any one of (1) to (11) above, (14)
  • a hydrophobic and substantially insoluble antibiotic active compound with respect to the hydrophobic polymerizable vinyl monomer is dispersed in the hydrophobic polymerizable vinyl monomer, thereby making the hydrophobic
  • An oil phase component preparation step for preparing an oil phase component containing a slurry, an aqueous dispersion step for preparing an aqueous dispersion by dispersing the oil phase component in water, and suspension polymerization of the polymerizable vinyl monomer,
  • a polymerization step for forming a coalescence, and at least one of the oil phase component preparation step, the water dispersion step and the polymerization step, a hydrophobic shell-forming component and a hydrophilic shell-forming component are contained, and the polymerization step Then, the
  • a method of manufacturing a controlled release particles (15)
  • the interfacial polymerization is started simultaneously with the start of the suspension polymerization or started before the start of the suspension polymerization.
  • the method for producing sustained-release particles according to Item (18) The method for producing sustained-release particles according to any one of (14) to (17) above, wherein the antibiotic compound is a neonicotinoid insecticide, (19)
  • the neonicotinoid insecticide includes (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine and 1- (6-chloro-3-pyridylmethyl)-
  • the method for producing sustained-release particles according to (18) above comprising at least one selected from the group consisting of N-nitroimidazolidine-2-ylideneamine.
  • the sustained-release particles of the first invention group are a hydrophobic polymer that is hydrophobic and substantially insoluble in a hydrophobic polymerizable vinyl monomer in the absence of a solvent.
  • An oil phase component preparation step for preparing an oil phase component containing a hydrophobic slurry by dispersing in a vinyl monomer, an aqueous dispersion step for preparing an aqueous dispersion by dispersing the oil phase component in water, and a polymerizable vinyl Since it is obtained by a production method comprising a polymerization step of producing a polymer by suspension polymerization of a monomer, it is possible to obtain sustained release particles that are excellent in sustained release properties.
  • sustained-release particles of the first invention group sustained-release particles that are robust and excellent in sustained-release properties can be obtained.
  • the sustained-release particles of the first invention group have a two-phase structure formed of a matrix made of a polymer and a domain made of an antibiotic compound and dispersed in the matrix, the antibiotic In addition to excellent sustained release of the active compound and excellent fastness, it is excellent in kneadability with the resin.
  • the molding material of the first invention group contains the above-mentioned sustained release particles, the excellent controlled release property of the antibiotic compound can be imparted to the molded product of the first invention group.
  • the sustained-release particles of the second invention group are hydrophobic, and in the absence of a solvent, a hydrophobic and substantially insoluble antibiotic active compound with respect to a hydrophobic polymerizable vinyl monomer.
  • An oil phase component preparation step for preparing an oil phase component containing a hydrophobic slurry by dispersing in a vinyl monomer, an aqueous dispersion step for preparing an aqueous dispersion by dispersing the oil phase component in water, and a polymerizable vinyl Since it is obtained by a production method comprising a polymerization step of producing a polymer by suspension polymerization of a monomer, it is possible to obtain a sustained-release particle having excellent sustained-release properties and alkali resistance and robustness.
  • sustained-release particles of the second invention group it is possible to obtain sustained-release particles that are robust and excellent in sustained-release properties and alkali resistance.
  • the sustained-release particles of the second invention group are obtained by suspension polymerizing the polymerizable vinyl monomer and interfacially polymerizing the hydrophobic shell-forming component and the hydrophilic shell-forming component. Is formed, the encapsulating rate of the antibiotic compound can be increased, and the alkali resistance of the antibiotic compound is excellent.
  • the sustained-release particles of the second invention group include a matrix made of a polymer and a domain made of an antibiotic compound and dispersed in the matrix. In addition to being excellent in fastness, it is excellent in kneadability with resin.
  • the sustained release particles in the second invention group include a shell covering the matrix, the antibiotic active compound is excellent in sustained release and alkali resistance.
  • the molding material of the second invention group contains the above-mentioned sustained release particles, the excellent controlled release property and the alkali resistance of the antibiotic compound can be imparted to the molded product of the second invention group. .
  • FIG. A1 shows a schematic cross-sectional view of a first embodiment of sustained-release particles of the first invention group.
  • FIG. A2 shows a schematic cross-sectional view of a second embodiment of the first-invented group sustained-release particles (embodiment in which the domains are covered with a matrix and the deposits adhere to the surface of the matrix).
  • FIG. A3 shows a schematic cross-sectional view of a modification of the second embodiment (a mode in which the entire surface of the matrix is exposed).
  • FIG. A4 shows an image processing diagram of an SEM photograph of sustained-release particles of Example A1.
  • FIG. A5 shows an image processing diagram of an SEM photograph of sustained release particles of Example A2.
  • FIG. A6 shows an image processing diagram of the SEM photograph of the sustained release particles of Example A3.
  • FIG. A7 shows an image processing diagram of an SEM photograph of sustained-release particles of Example A4.
  • FIG. A8 shows an image processing diagram of an SEM photograph of sustained-release particles of Example A9.
  • FIG. A9 shows an image processing diagram of an SEM photograph of sustained-release particles of Example A19.
  • FIG. A10 shows the image processing drawing of the SEM photograph of the fracture surface of the strand of Example A20.
  • FIG. A11 shows an image processing diagram of the SEM photograph of the fracture surface of the strand of Example A21.
  • FIG. A12 shows an image processing diagram of a TEM photograph of sustained-release particles of Example A1.
  • FIG. A13 shows an image processing diagram of a TEM photograph of sustained release particles of Example A2.
  • FIG. A14 shows an image processing diagram of a TEM photograph of sustained release particles of Example A3.
  • FIG. B1 shows a schematic cross-sectional view of a third embodiment of the sustained-release particles of the second invention group.
  • FIG. B2 shows a schematic cross-sectional view of a fourth embodiment of sustained-release particles of the second invention group.
  • FIG. B3 shows an image processing diagram of an SEM photograph of the sustained release particles of Example B1.
  • FIG. B4 shows an image processing diagram of an SEM photograph of sustained release particles of Example B2.
  • FIG. B5 shows an image processing diagram of an SEM photograph of sustained release particles of Example B6.
  • FIG. B6 shows an image processing diagram of an SEM photograph of sustained-release particles of Example B30.
  • FIG. B7 shows an image processing diagram of an SEM photograph of sustained-release particles of Example B35.
  • FIG. B8 shows an image processing diagram of a TEM photograph of sustained release particles of Example B2.
  • FIG. B9 shows an image processing diagram of a TEM photograph of sustained release particles of Reference Example B1.
  • FIG. B10 shows an image processing diagram of a TEM photograph of sustained release particles of Reference Example B2.
  • FIG. B11 shows an image processing diagram of a TEM photograph of sustained release particles of Reference Example B3.
  • the method for producing sustained-release particles of the first invention group comprises a hydrophobic and substantially insoluble antibiotic active compound in a hydrophobic polymerizable vinyl monomer in the absence of a solvent.
  • Antibacterial active compounds include insecticides (including ants), insecticides (including ants), sterilization, antibacterial, antiseptic, herbicidal, algae, fungicides and other insecticides (anticides) ), Insecticides (including ant-proofing agents), fungicides, antibacterial agents, antiseptics, herbicides, algae-proofing agents, fungicides, attractants, repellents and rodenticides.
  • antibiotic active compounds such as clothianidin ((E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine), imidacloprid (1 -(6-Chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine), thiacloprid, thiamethoxam ((EZ) -3- (2-chloro-1,3-thiazol-5-ylmethyl) -5-methyl -1,3,5-oxadiazinan-4-ylidene (nitro) amine), neonicotinoid insecticides such as dinotefuran, diamides such as fulbenzamide, chlorantraniliprole, diflubenzuron, teflubenzuron, chlorfluazuron, Insect growth such as tebufenozide, methoxyphenozide, cyromazine Please, acaricides such as clofentezine,
  • 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.
  • 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 thiophanate methyl, carbendazine (MBC), benzimidazole fungicides such as dietofencarb, acid amide fungicides such as isothianyl, sterol biosynthesis inhibitors such as triphorine, 1,2-benzisothiazoline-3- And other synthetic inhibitors such as isothiazolone fungicides such as ON, dichromimidine, fluorimide, captan, chlorothalonil, quinotimeoate, oxolinic acid, benchavaricarb isopropyl, diazofamide, and zinc pyrithione.
  • MBC carbendazine
  • benzimidazole fungicides such as dietofencarb
  • acid amide fungicides such as isothianyl
  • sterol biosynthesis inhibitors such as triphorine
  • other synthetic inhibitors such as isothiazolone fungicides such as ON, dichromimidine,
  • 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), cumyluron, carbylate, and other urea chemicals ethoxysulfuron, halosulfuronmethyl, flazasulfuron , Sulfonylureas such as nicosulfuron, thifensulfuron methyl, imazosulfuron, cyclosulfamuron, flucetosulfuron, trifloxysulfuron sodium salt, triazines such as simazine (CAT), atrazine, triadifram, lenacyl, sibulthrin, terbutrin Drugs, amino acids such as glyphosate, phenylphthalimides such as flumioxazin, triketones such as mesotrione, and other drugs such as quinoclamin and pyriphthalide.
  • DCMU 3- (3,4-dichlorophenyl) -1,1-dimethyl
  • the antibiotic compound is preferably a neonicotinoid insecticide from the viewpoint of species selectivity and safety, and zinc pyritine from the viewpoint of versatility and efficacy, more preferably from the viewpoint of poor solubility, Clothianidin, imidacloprid, and zinc pyrithione are preferable, and clothianidin and imidacloprid are more preferable. Particularly preferred is clothianidin from the viewpoint of safety for mammals.
  • Antibiotic active compounds are substantially hydrophobic and, for example, have very low solubility in water at room temperature (20-30 ° C., more specifically 25 ° C.), more specifically,
  • the solubility at room temperature is 1.5 parts by mass / 100 parts by volume of water (15 g / L) or less, preferably 0.5 parts by volume / 100 parts by mass of water (5 g / L) or less, more preferably 0.1 parts by mass / 100 parts by volume of water (1 g / L) or less.
  • the antibiotic compound is substantially insoluble in the polymerizable vinyl monomer, and specifically, for example, at room temperature (20 to 30 ° C., more specifically 25 ° C.) with respect to the polymerizable vinyl monomer.
  • the solubility is extremely small. Specifically, the solubility at room temperature is, for example, 0.1 parts by mass / (use) polymerizable vinyl monomer (mixture) 100 parts by volume (1 g / L) or less, preferably 0.05. It is 100 parts by mass (0.5 g / L) or less by mass parts / (used) polymerizable vinyl monomer (mixture).
  • the melting point of the antibiotic compound is, for example, 80 ° C. or more, preferably 100 ° C. or more. If the antibiotic compound is a compound that does not contain a metal atom, it is, for example, 300 ° C. or less.
  • polymerizable vinyl monomer examples include (meth) acrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, maleic acid ester monomers, vinyl halides, vinylidene halides, nitrogen-containing vinyl monomers, and crosslinkable monomers. Etc.
  • 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 (i-BMA / i-BA), tert-butyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid alkyl ester in which the alkyl moiety such as n-pentyl, n-hexyl (meth) acrylate and cyclohexyl (meth) acrylate has a linear, branched or cyclic alkyl moiety having 1 to 6 carbon atoms And, for example, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth)
  • (meth) acrylic acid alkyl ester more preferred is a (meth) acrylic acid alkyl ester having an alkyl moiety having 1 to 6 carbon atoms, and particularly preferred is isobutyl methacrylate (i-BMA).
  • aromatic vinyl monomer examples include styrene monomers (monovinylbenzene) such as styrene (vinylbenzene), p-methylstyrene, o-methylstyrene, ⁇ -methylstyrene, and ethylvinylbenzene.
  • styrene monomers such as styrene (vinylbenzene), p-methylstyrene, o-methylstyrene, ⁇ -methylstyrene, and ethylvinylbenzene.
  • styrene and ethyl vinylbenzene are used.
  • vinyl ester monomers examples include vinyl acetate and vinyl propionate.
  • maleate ester monomers examples 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.
  • nitrogen-containing vinyl monomer examples include (meth) acrylonitrile, N-phenylmaleimide, vinylpyridine, and the like.
  • crosslinkable monomer examples include mono- or polyethylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, such as 1,3-propanediol di (meth) acrylate, 1, Alkanediol di (meth) acrylates such as 4-butanediol di (meth) acrylate and 1,5-pentanediol di (meth) acrylate, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ( (Meth) acrylate crosslinkable monomers such as alkane polyol poly (meth) acrylate such as PETA / PETM), for example, allyl (meth) methacrylate, triallyl (iso) cyanurate Le monomers, such as divinyl benzene, aromatic crosslinking monomers such as trivinyl
  • the polymerizable vinyl monomer can be used alone or in combination.
  • the glass transition temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher.
  • the polymerizable vinyl monomer is selected so that
  • the polymerizable vinyl monomer is, for example, substantially hydrophobic, and specifically has, for example, extremely low solubility in water at room temperature. More specifically, the solubility at room temperature is, for example, 10 parts by mass / 100 parts by volume of water (100 g / L) or less, preferably 8 parts by weight / 100 parts by volume of water (80 g / L) or less.
  • the entire polymerizable vinyl monomer that is, a mixture of different types of polymerizable vinyl monomers
  • Oil phase component preparation process In the oil phase component preparation step, an antibiotic compound that is hydrophobic and substantially insoluble in the hydrophobic polymerizable vinyl monomer is dispersed in the hydrophobic polymerizable vinyl monomer in the absence of a solvent. By doing this, an oil phase component containing a hydrophobic slurry is prepared.
  • the polymerizable vinyl monomer and the antibiotic compound described above are blended and stirred without blending a solvent (a hydrophobic organic solvent such as hexane, toluene, ethyl acetate). Thereby, a hydrophobic slurry is prepared. The hydrophobic slurry is included in the oil phase component.
  • a solvent a hydrophobic organic solvent such as hexane, toluene, ethyl acetate
  • 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.
  • 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 antibiotic compound is wet-ground by the dispersion described above.
  • the polymerizable vinyl monomer can be added to the antibiotic compound, or alternatively, the polymerizable vinyl monomer can be divided and added to the antibiotic compound.
  • the polymerizable vinyl monomer is blended separately, first, a part of the polymerizable vinyl monomer is blended with the antibiotic compound, and they are dispersed to prepare a hydrophobic slurry. The remainder of the monomer is blended into the hydrophobic slurry.
  • the blending ratio of the antibiotic compound to the polymerizable vinyl monomer is, for example, 1/99 or more, preferably 10/90, in mass ratio (that is, mass part of antibiotic compound / mass part of polymerizable vinyl monomer). Or more, more preferably 15/85 or more, and for example, 90/10 or less, preferably 75/25 or less, more preferably 70/30 or less, and further preferably 65/35 or less, particularly preferably. Is 60/40 or less.
  • the blending ratio of the antibiotic compound is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, with respect to 100 parts by mass of the polymerizable vinyl monomer.
  • it is 900 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less.
  • the content ratio of the antibiotic compound in the oil phase component is, for example, 1% by mass or more, preferably 10% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably , 70% by mass or less, and more preferably 60% by mass or less.
  • a dispersant in the above-described dispersion, can be blended if necessary.
  • the dispersant include an amphiphilic polymer type dispersant, a nonionic surfactant (first surfactant), and the like.
  • amphiphilic polymer dispersant examples include, for example, EFKA4008, EFKA4009 (urethane-based polymer dispersant manufactured by Ciba Specialty), DISPERBYK-2164, DISPERBYK-164 (above, functional group for pigment dispersion manufactured by Bic Chemie) Modified copolymer), NUOSPERSE 2008, NUOSPERSE FA-196, NUOSPERSE 657 (above made by Elementis), Floren D-90, Polyflow KL-100, Polyflow KL-700 (above made by Kyoeisha Chemical Co., Ltd.), Homogenol L-95 (Kao) Nonionic amphiphilic polymer type dispersants such as those manufactured by Komatsu Ltd.
  • amphiphilic polymer dispersant examples include, for example, Floren G-900 (carboxyl-modified polymer manufactured by Kyoeisha Chemical Co., Ltd.), Disparon DA-234, Disparon DA-325, Disparon DA-375, Disparon DA-550. And anionic amphiphilic polymer type dispersants such as Disparon AQ-330 (polyether phosphate ester salt manufactured by Enomoto Kasei Co., Ltd.). Furthermore, examples of the amphiphilic polymer type dispersant include cationic amphiphilic polymer type dispersants such as NOPCOSPERTH 092 (manufactured by San Nopco).
  • Nonionic surfactants include, for example, amogen CBH (alkylbetaine), amogen SH (alkylamidobetaine), Neugen 100E (polyoxyethylene oleyl ether), Neugen EA73 (polyoxyethylene dodecylphenyl 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) Le) (all manufactured by Kao Corporation), and the like.
  • amogen CBH alkylbetaine
  • amogen SH alkylamidobetaine
  • Neugen 100E polyoxyethylene oleyl ether
  • the dispersant is preferably an amphiphilic polymer dispersant, more preferably a nonionic amphiphilic polymer dispersant, an anionic amphiphilic polymer dispersant, and more preferably.
  • nonionic amphiphilic polymer type dispersants and particularly preferred are functional group-modified copolymer dispersants for pigment dispersion and urethane polymer dispersants.
  • the mixing 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 antibiotic compound. It is.
  • the average particle size of the antibiotic compound in the oil phase component is, for example, 5 ⁇ m or less, preferably 2.5 ⁇ m or less, and for example, 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more.
  • a polymerization initiator is blended together with the preparation of the hydrophobic slurry or after the preparation of the hydrophobic slurry.
  • the polymerization initiator is blended into the prepared hydrophobic slurry.
  • the polymerizable vinyl monomer can be divided and blended with the antibiotic compound. Specifically, a part of the polymerizable vinyl monomer is blended with the antibiotic compound to form a hydrophobic slurry. Then, the polymerization initiator is dissolved in the remainder of the polymerizable vinyl monomer, and this is blended into the prepared hydrophobic slurry.
  • an oil phase component containing a polymerization initiator and a hydrophobic slurry is prepared.
  • polymerization initiator examples include radical polymerization initiators usually used in suspension polymerization, and specific examples include oil-soluble polymerization initiators.
  • oil-soluble polymerization initiator examples include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, diisopropyl
  • Oil-soluble organic peroxides such as peroxydicarbonate and benzoyl peroxide, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 And oil-soluble azo compounds such as' -azobis (2-methylbutyronitrile).
  • Polymerization initiators can be used alone or in combination of two or more.
  • the blending ratio of the polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the polymerizable vinyl monomer. For example, 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 1.0 parts by mass or less.
  • the blending ratio of the polymerization initiator exceeds the above upper limit, the molecular weight of the polymer may be excessively decreased.
  • the blending ratio is less than the above lower limit, the conversion rate is not sufficiently improved, and unreacted polymerization is performed. In some cases, several% or more of the functional vinyl monomer remains.
  • oil phase component and water are mixed and stirred uniformly to disperse (suspend) the oil phase component in water.
  • an aqueous dispersion (suspension) of the oil phase component is obtained.
  • the conditions for water dispersion are not particularly limited, and for example, it may be carried out at room temperature or by heating.
  • a dispersant (second dispersant) and a surfactant (second surfactant) are blended.
  • dispersant examples 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.
  • polyvinyl alcohol (PVA) and tricalcium phosphate are preferable. More preferably, polyvinyl alcohol (PVA) is mentioned.
  • the blending ratio of the dispersant is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the oil phase component. 10 parts by mass or less, preferably 5 parts by mass or less.
  • the surfactant is preferably used in combination with the above-described dispersant (second dispersant) in order to effectively prevent aggregation of particles during radical polymerization.
  • dodecylbenzene Anionic surfactants such as sodium sulfonate, sodium lauryl sulfate, sodium di-2-ethylhexyl sulfosuccinate, sodium dodecyl diphenyl ether disulfonate, sodium nonyl diphenyl ether sulfonate, a salt of a condensate of aromatic sulfonic acid and formaldehyde, such as Nonionic series such as polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene polyoxypropylene block copolymer Surface active agents, and the like.
  • 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 oil phase component. Preferably, it is 0.1 mass part or less.
  • dispersants or the dispersant and the surfactant can be blended, for example, either before or after blending the oil phase component with water, preferably water before blending the oil phase component. Blend in.
  • an aqueous solution of the dispersant or an aqueous solution of the dispersant and the surfactant is prepared.
  • a disperser such as a homomixer, an ultrasonic homogenizer, a pressure homogenizer, a milder, or a porous membrane press-in disperser is used. 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.
  • dispersant second dispersant
  • a dispersant and a surfactant are used in the aqueous dispersion.
  • the droplets of the oil phase component are more stabilized.
  • the blending ratio of water is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, with respect to 100 parts by mass of the oil phase component. It is adjusted to 1900 parts by mass or less, preferably 900 parts by mass or less, more preferably 400 parts by mass or less.
  • a polymerizable vinyl monomer is subjected to suspension polymerization to produce a polymer.
  • the aqueous dispersion is heated to a predetermined temperature.
  • 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 of the polymerizable vinyl monomer that becomes a polymer is only in water-dispersed particles (hydrophobic liquid phase).
  • the aqueous dispersion is heated while stirring, whereby the polymerizable vinyl monomer starts polymerization in the aqueous dispersion particles as it is, and a polymer is formed.
  • Stirring can be performed, for example, with a stirrer having stirring blades.
  • 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 temperature of the aqueous dispersion is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and for example, 100 ° C. or lower, preferably 90 ° C. or lower, more preferably 80 ° C. Heat to below °C.
  • suspension polymerization proceeds in a state where the antibiotic compound 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.
  • the antibiotic compound In suspension polymerization, the antibiotic compound is substantially insoluble with respect to the polymerizable vinyl monomer, and the antibiotic compound is incompatible with the polymerizable vinyl monomer and / or polymer from the start of polymerization to the end of polymerization. The incompatible state is maintained.
  • the aqueous dispersion after polymerization is cooled, for example, by cooling, and filtered through a 100 mesh filter cloth to obtain an aqueous dispersion (suspension) of sustained release particles.
  • the cooling temperature is, for example, room temperature (20 to 30 ° C., more specifically 25 ° C.).
  • the concentration of the antibiotic compound in the obtained sustained-release particles is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and for example, 50% by mass or less.
  • the amount is preferably 40% by mass or less, and more preferably 35% by mass or less.
  • the content ratio of the sustained release particles in the suspension is determined by the blending amount of the oil phase component and water (or an aqueous solution) in which the oil phase component is dispersed, and specifically, for example, 10% by mass or more, Preferably, it is 20 mass% or more, for example, 50 mass% or less, preferably 40 mass% or less.
  • the average particle diameter of the sustained release particles is, for example, 1 ⁇ m or more, preferably 2 ⁇ m or more, and for example, 20 mm or less, preferably 10 mm or less.
  • the average particle diameter is calculated as the median diameter.
  • sustained-release particles produced by the above-described method for producing sustained-release particles have a two-phase structure formed from a matrix described later and domains described later dispersed in the matrix.
  • aqueous dispersion containing the sustained release particles obtained by the above production method
  • other dispersants thickeners, antifreezing agents, preservatives, microbial growth inhibitors
  • Known additives such as a specific gravity adjusting agent can be appropriately blended.
  • the sustained-release particles thus obtained may be used as they are (suspension), that is, as a suspension, or directly as a powder by spray drying.
  • solid-liquid separation is performed by centrifugation, fuller press, etc., and after washing, if necessary, dried by fluid drying, shelf drying, etc., and if necessary, crushed with an atomizer, feather mill, etc., vibrating sieve, etc.
  • sustained release particles for example, a suspension of sustained release particles is mixed and mixed in a solid carrier, and then dried (granulation step). That is, the method for producing sustained-release particles can further include a granulation step in addition to the oil phase component preparation step, the water dispersion step and the polymerization step.
  • the solid carrier examples include pumice, bentonite, clay, kaolin, talc, acid clay, zeolite, vermiculite, perlite, calcium carbonate, silica sand and the like.
  • the solid carrier is preferably pumice.
  • a commercially available product can be used, and specifically, a kagarite series (natural pumice fine granules, manufactured by Kagarite Kogyo Co., Ltd.) is used.
  • the average particle size of the solid carrier is, for example, 100 ⁇ m or more, preferably 300 ⁇ m or more, and for example, 5.00 mm or less, preferably 2.00 mm or less.
  • the ratio of the suspension of sustained release particles is such that the concentration of the antibiotic compound in the resulting granules (solid carrier and sustained release particles) is, for example, 0.01% by mass or more, Preferably, it is adjusted to be 0.05% by mass or more, for example, 2% by mass or less, preferably 1% by mass or less.
  • the blending ratio of the suspension of sustained release particles (including water) is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the solid carrier. More preferably, it is 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass or less.
  • the sustained-release particles of the first invention group are a hydrophobic polymer that is hydrophobic and substantially insoluble in a hydrophobic polymerizable vinyl monomer in the absence of a solvent.
  • An oil phase component preparation step for preparing an oil phase component containing a hydrophobic slurry by dispersing in a vinyl monomer, an aqueous dispersion step for preparing an aqueous dispersion by dispersing the oil phase component in water, and a polymerizable vinyl Since it is obtained by a production method comprising a polymerization step of producing a polymer by suspension polymerization of a monomer, it is possible to obtain sustained release particles that are excellent in sustained release properties.
  • the microcapsules obtained by the method described in Patent Document 1 are obtained only by interfacial polymerization, the dispersion medium (solvent) remains in the microcapsules, and therefore the surface hardness becomes insufficient. There is. As a result, when the microcapsule dispersion undergoes a process in which a high shearing force is applied or is stored for a long period of time, the microcapsules may aggregate to make redispersion difficult.
  • the microcapsules are likely to be blocked, and it may be difficult to take out the microcapsules as dry particles.
  • the sustained-release particles of the first invention group have hydrophobic active compounds that are hydrophobic and substantially insoluble in hydrophobic polymerizable vinyl monomers in the absence of a solvent.
  • robust sustained-release particles can be obtained, and as a result, the obtained sustained-release particles are excellent in redispersibility and blocking resistance.
  • sustained-release particles can be applied to various industrial products, for example, indoor and outdoor paints, rubber, fibers, resins (including plastics), adhesives, joint agents, sealing agents, building materials, caulking. It can be added to the agent, wood treatment agent, soil treatment agent, white water, pigment, printing plate treatment liquid, cooling water, ink, cutting oil, cosmetics, non-woven fabric, spinning oil, leather, etc. in the papermaking process.
  • the added amount of the antibiotic compound in the sustained release particles to these industrial products is, for example, 10 mg / kg to 100 g / kg (product mass).
  • thermoplastic resin a powder formulated from sustained-release particles is blended with a thermoplastic resin.
  • a suspension of sustained-release particles is dried and formulated into a powder.
  • the powder and the thermoplastic resin are melt-kneaded to prepare a kneaded product.
  • the kneaded material In order to prepare the kneaded material, specifically, for example, an extruder or a Banbury mixer is used.
  • the extruder for example, a twin screw extruder or a single screw extruder is used.
  • the kneaded material is a molding material for molding a molded product. Specifically, the kneaded material is once cooled and prepared as a pellet-shaped molding material (kneaded material pellet or master batch). On the other hand, the kneaded product is not taken out as a solid molding material, but can be continuously used as it is in a molten state (melt kneaded product) and subjected to molding described later.
  • the content of the antibiotic compound in the powder agent is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and, for example, 10% by mass or less, preferably, with respect to the thermoplastic resin.
  • a powder agent is mix
  • the content of the antibiotic compound is, for example, 1% by mass or more, preferably, with respect to the thermoplastic resin.
  • the powder is mixed with the thermoplastic resin so as to be 5% by mass or more, for example, 50% by mass or less, and preferably 30% by mass or less, to obtain a master batch.
  • the thermoplastic resin is not particularly limited.
  • polyolefin resin such as polyethylene and polypropylene, polystyrene, polymethyl methacrylate, acrylonitrile / styrene copolymer resin (AS resin), methyl methacrylate / styrene copolymer (MS resin), acrylonitrile / styrene / butadiene copolymer resin (ABS resin), styrene and / or acrylic resins
  • polyethylene terephthalate polyester resins such as polylactic acid, polyamide resins such as 6-nylon, chloride
  • vinyl halide resins such as vinyl resin and vinylidene chloride resin
  • polycarbonate polyphenylene ether
  • polyacetal polyacetal
  • thermoplastic polyurethane thermoplastic polyurethane.
  • thermoplastic resins can be used alone or in combination.
  • the mixture is molded into a molded product from the kneaded product pellets or melt-kneaded product.
  • the molding method for example, injection molding, extrusion molding, inflation molding, pultrusion molding, compression molding, or the like is employed.
  • the powder formulated from sustained-release particles is added to the thermoplastic resin.
  • the powder is not particularly limited as long as it is a resin, and may be added to, for example, a thermosetting resin.
  • a powder can be suitably mixed with a liquid resin such as an epoxy resin or a silicone resin.
  • Such molded articles are used in various applications, for example, building materials such as electric wire cable materials, and electric wire cable coating materials such as gas conduits, and conduit coating materials such as clothing. Used as textile products such as mosquito nets.
  • ⁇ Effect of the molded product of the first invention group> since the sustained-release particles of the powder have a robust two-phase structure formed from a matrix and domains, the powder is not destroyed during kneading and molding, and is dispersed in the molded product or localized on the surface.
  • the molded product to which the above powder is added is excellent in sustained release properties of the antibiotic compound.
  • the above-mentioned molding material contains the above-mentioned sustained-release particles, it is dispersed in the above-mentioned molded product, or localized on the surface, so that the molded product has excellent sustained-release properties of the antibiotic compound. Can be granted.
  • sustained release particles are made into beads with a diameter of 1 mm to 20 mm, and are steadily imparted with antibiotic activity effects such as sterilization to the passing fluid by laying, standing, and fixing in the flow path of fluid (gas, liquid). can do.
  • the sustained-release particles obtained by the above-described method for producing sustained-release particles specifically include the first and second embodiments of the sustained-release particles described below.
  • the sustained-release particles 1 are formed, for example, as spherical particles.
  • the sustained release particles 1 have a two-phase structure formed from a matrix 2 and domains 3 dispersed in the matrix 2.
  • the matrix 2 is made of a polymer obtained from the above-described polymerizable vinyl monomer.
  • Domain 3 consists of the antibiotic compounds described above.
  • the matrix 2 forms a medium or a continuous phase, and a multi-domain structure or a sea-island structure (or a multinuclear structure) in which a plurality of domains 3 are dispersed in an isolated manner is formed. Yes. Further, in the sustained release particles 1, the matrix 2 and the domain 3 are incompatible with each other and form a phase separation structure that separates from each other.
  • the matrix 2 is in a region other than the domain 3 in the sustained release particles 1 and is formed in a shape with the domain 3 removed.
  • the plurality of domains 3 form 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 ⁇ m or more, preferably 0.1 ⁇ m or more, and for example, 20 ⁇ m or less, preferably 10 ⁇ m or less.
  • the domain 3 includes a protrusion 4 that protrudes outward from the inside of the matrix 2.
  • the protrusion 4 is exposed from the surface of the matrix 2. Thereby, both the matrix 2 and the domain 3 are exposed on the surface of the sustained release particles 1.
  • the protrusion 4 has an embedded portion 8 embedded in the surface layer portion of the matrix 2.
  • the protrusions 4 serve to increase the initial sustained release rate of the antibiotic compound in the sustained release particles 1 and remarkably increase the blocking resistance of the sustained release particles 1.
  • the exposure rate of the protrusion 4 with respect to the entire surface of the matrix 2 (that is, the exposure rate of the domain 3) is, for example, 0.1% or more, preferably 1% or more, with respect to the entire surface of the sustained release particles 1. For example, it is 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 sustained release particles 1.
  • a hole 6 is formed on the surface of the sustained-release particle 1 by part of the domain 3 being detached (dropped off) from the matrix 2.
  • the hole 6 is formed so as to correspond to the shape of the antibiotic compound constituting the domain 3.
  • sustained-release particles 1 in the above-described production method of the sustained-release particles 1, particularly in the oil phase component preparation step, as the polymerizable vinyl monomer, a (meth) acrylate monomer and (meth) In the water dispersion step, an acrylate-based crosslinkable monomer is not used, and preferably, a salt of a condensate of aromatic sulfonic acid and formaldehyde is not blended as a surfactant (second surfactant).
  • second surfactant second surfactant
  • a combination of an aromatic vinyl monomer and an aromatic crosslinkable monomer is preferably used as the polymerizable vinyl monomer.
  • the content of the aromatic vinyl monomer is 100 parts by mass in total of the aromatic vinyl monomer and the aromatic crosslinkable monomer.
  • 10 parts by mass or more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less, more preferably, 70 parts by mass or less.
  • a surfactant (second surfactant)
  • a salt of a condensate of aromatic sulfonic acid and formaldehyde is not blended, but preferably a dispersant (second dispersant) is blended.
  • Both the matrix 2 and the domain 3 are exposed on the surface of the sustained release particles 1.
  • the surface of the sustained-release particles 1 is exposed so that the antibiotic compound protrudes outward, and constitutes a protrusion 4.
  • the sustained release particles 1 have a two-phase structure formed from a matrix 2 and a domain 3 and do not have a shell.
  • the blocking resistance can be further improved by the protrusions 4.
  • the antibiotic active compound that forms the exposed protrusions 4 can start the sustained release from the initial stage, and when the protrusions 4 drop off, the antibiotic active compound further releases the initial slow release. Since the release rate is accelerated, the initial sustained release rate of the antibiotic compound can be increased to adjust the sustained release rate of the antibiotic compound.
  • this sustained-release particle 1 is a two-phase formed of a matrix 2 made of a polymer and a domain 3 made of an antibiotic compound and dispersed in the matrix 2. Since it has a structure, it is excellent in sustained release property of the antibiotic compound and excellent in fastness. Therefore, the sustained release particles are excellent in kneadability with the above-described resin.
  • the domain 3 is not exposed on the surface of the sustained release particles 1, and all the domains 3 are included in the matrix 2. That is, in the sustained release particles 1, the antibiotic compound forming domain 3 is covered and protected by the matrix 2.
  • an antibiotic compound is attached to the surface of the matrix 2 in the sustained release particles 1.
  • the deposit 5 made of an antibiotic compound is adhered so as to cover all or part of the entire surface of the matrix 2.
  • the deposit 5 does not have the embedded portion 8 and is in contact with the surface of the matrix 2.
  • attachment 5 is not specifically limited, For example, it is formed in appropriate shapes, such as an indefinite shape, spherical shape, lump shape, and plate shape.
  • the inner surface (contact surface that contacts the surface of the matrix 2) of the deposit 5 forms a concave surface corresponding to the surface (spherical surface) of the matrix 2, specifically, a curved surface that is recessed outward.
  • the deposit 5 is the same size as or smaller than the domain 3, and is, for example, 100% or less, preferably 50% or less with respect to the average value of the maximum length of the domain 3.
  • the average value of the maximum length of the deposit 5 is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less, for example, 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more. It is.
  • the coverage of the deposit 5 on the entire surface of the matrix 2 is, for example, 10% or more, preferably 20% or more, and for example, 100% or less, preferably 90% or less.
  • sustained release particle 1 in the water dispersion process of the manufacturing method of the above-mentioned sustained release particle 1, as surfactant (2nd surfactant), aromatic sulfonic acid and formaldehyde are used.
  • a salt of the condensate is blended and / or, in the oil phase component preparation step, a (meth) acrylic acid ester monomer and a (meth) acrylate crosslinking monomer are blended as the polymerizable vinyl monomer.
  • the second surfactant is preferably used in combination with the second dispersant described above.
  • aromatic sulfonic acid examples include benzene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, naphthalene sulfonic acid and the like.
  • naphthalenesulfonic acid such as ⁇ -naphthalenesulfonic acid and ⁇ -naphthalenesulfonic acid is used.
  • Examples of the cation for forming the salt include a monovalent cation.
  • Examples of the monovalent cation include alkali metal cations such as sodium cation and potassium cation, for example, ammonium cation.
  • alkali metal cations such as sodium cation and potassium cation, for example, ammonium cation.
  • an alkali metal cation is used.
  • the salt of the condensate of aromatic sulfonic acid and formaldehyde include a salt of a condensate of naphthalene sulfonic acid and formaldehyde (naphthalene sulfonic acid formaldehyde condensate sodium salt).
  • naphthalene sulfonic acid formaldehyde condensate sodium salt Commercially available products can be used as the salt of the condensate of aromatic sulfonic acid and formaldehyde.
  • Demol NL ⁇ -naphthalenesulfonic acid formaldehyde condensate sodium salt, 41% aqueous solution, manufactured by Kao Corporation
  • the blending ratio of the salt of the condensate of aromatic sulfonic acid and formaldehyde is, for example, 0.0001 parts by mass or more, preferably 0.001 parts by mass or more, with respect to 100 parts by mass of the hydrophobic slurry.
  • it is 1.0 part by mass or less, preferably 0.2 part by mass or less, and more preferably 0.1 part by mass or less.
  • the content ratio of the (meth) acrylate-based crosslinkable monomer in the polymerizable vinyl monomer is, for example, 10% by mass or more, preferably 30% by mass or more, and, for example, 100% by mass or less.
  • the polymerizable vinyl monomer contains a (meth) acrylate monomer and a (meth) acrylate crosslinkable monomer
  • the polymer of the (meth) acrylate monomer is a (meth) acrylate crosslinkable. It has a crosslinked structure that is crosslinked by a monomer or a polymer thereof.
  • a salt of a condensate of aromatic sulfonic acid and formaldehyde is blended and / or oil in the water dispersion step.
  • (Meth) acrylate monomer and (meth) acrylate crosslinkable monomer are used as polymerizable vinyl monomers in the phase component preparation step, and (meth) acrylate monomer and (meth) acrylate monomer are used in the polymerization step.
  • a crosslinkable monomer is subjected to suspension polymerization. Therefore, it can suppress that the domain 3 which consists of an antibiotic compound is exposed to the surface of the sustained release particle
  • the polymerizable vinyl monomer is subjected to suspension polymerization in the presence of a salt of a condensate of naphthalenesulfonic acid and formaldehyde (preferably sodium salt of formaldehyde condensate of naphthalenesulfonic acid), polymerization is performed. Since the interface between the suspension polymer and the water continuous phase in the process is further stabilized, it is possible to prevent the antibiotic compound from leaking out of the sustained release particles. As a result, the sustained release of the antibiotic compound in the sustained release particles can be adjusted by the blending ratio of the salt of the condensate of naphthalene sulfonic acid and formaldehyde.
  • a salt of a condensate of naphthalenesulfonic acid and formaldehyde preferably sodium salt of formaldehyde condensate of naphthalenesulfonic acid
  • the antibiotic compound particles are dispersed and stabilized in the oil phase. Leakage of the bioactive compound out of the sustained release particles can be suppressed.
  • the sustained release properties of the antibiotic compound in the sustained release particles can be adjusted. .
  • the domain 3 can be covered with the matrix 2 as shown in FIG. Can be attached to the surface of the matrix 2. Therefore, the sustained release particles 1 of the second embodiment are excellent in blocking resistance due to the deposits 5.
  • the attached substance 5 can increase the initial sustained release rate of the antibiotic compound and adjust the sustained release rate of the antibiotic compound.
  • the deposit 5 is attached to the surface of the matrix 2, but the domain 3 is covered with the matrix 2, so the first embodiment including the protrusion 4 is provided.
  • the sustained-release particles 1 are antibiotics derived from the protrusions 4 in the sustained-release particles even when stored in an alkaline aqueous solution, compared to the sustained-release particles 1 of the first embodiment. Reduction of the concentration of the active compound can be suppressed.
  • a hydrophobic and substantially insoluble antibiotic active compound with respect to the hydrophobic polymerizable vinyl monomer is contained in the hydrophobic polymerizable vinyl monomer.
  • the oil phase component preparation step for preparing the oil phase component containing the hydrophobic slurry, the water dispersion step for preparing the aqueous dispersion by dispersing the oil phase component in water, and the polymerizable vinyl monomer are suspended. It has a polymerization step for producing a polymer by suspension polymerization.
  • a hydrophobic shell-forming component and a hydrophilic shell-forming component are contained in at least one of the oil phase component preparation step, the water dispersion step, and the polymerization step.
  • an antibiotic compound is dispersed in the polymerizable vinyl monomer to prepare a hydrophobic slurry, and then the hydrophobic slurry and the hydrophobic shell are prepared.
  • An oil phase component including a hydrophobic slurry and a hydrophobic shell forming component is prepared by blending with the forming component.
  • at least one of the water dispersion step and the polymerization step contains a hydrophilic shell-forming component, and more preferably, the hydrophilic shell-forming component in the polymerization step. Is blended.
  • the antibiotic compound the polymerizable vinyl monomer, the hydrophobic shell-forming component, and the hydrophilic shell-forming component will be sequentially described.
  • Antibacterial active compounds include insecticides (including ants), insecticides (including ants), sterilization, antibacterial, antiseptic, herbicidal, algae, fungicides and other insecticides (anticides) ), Insecticides (including ant-proofing agents), fungicides, antibacterial agents, antiseptics, herbicides, algae-proofing agents, fungicides, attractants, repellents and rodenticides.
  • antibiotic active compounds such as clothianidin ((E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine), imidacloprid (1 -(6-Chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine), thiacloprid, thiamethoxam ((EZ) -3- (2-chloro-1,3-thiazol-5-ylmethyl) -5-methyl -1,3,5-oxadiazinan-4-ylidene (nitro) amine), neonicotinoid insecticides such as dinotefuran, diamides such as fulbenzamide, chlorantraniliprole, diflubenzuron, teflubenzuron, chlorfluazuron, Insect growth such as tebufenozide, methoxyphenozide, cyromazine Please, acaricides such as clofentezine,
  • 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.
  • 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 thiophanate methyl, carbendazine (MBC), benzimidazole fungicides such as dietofencarb, acid amide fungicides such as isothianyl, sterol biosynthesis inhibitors such as triphorine, 1,2-benzisothiazoline-3- And other synthetic inhibitors such as isothiazolone fungicides such as ON, dichromimidine, fluorimide, captan, chlorothalonil, quinotimeoate, oxolinic acid, benchavaricarb isopropyl, diazofamide, and zinc pyrithione.
  • MBC carbendazine
  • benzimidazole fungicides such as dietofencarb
  • acid amide fungicides such as isothianyl
  • sterol biosynthesis inhibitors such as triphorine
  • other synthetic inhibitors such as isothiazolone fungicides such as ON, dichromimidine,
  • 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), cumyluron, carbylate, and other urea chemicals ethoxysulfuron, halosulfuronmethyl, flazasulfuron , Sulfonylureas such as nicosulfuron, thifensulfuron methyl, imazosulfuron, cyclosulfamuron, flucetosulfuron, trifloxysulfuron sodium salt, triazines such as simazine (CAT), atrazine, triadifram, lenacyl, sibulthrin, terbutrin Drugs, amino acids such as glyphosate, phenylphthalimides such as flumioxazin, triketones such as mesotrione, and other drugs such as quinoclamin and pyriphthalide.
  • DCMU 3- (3,4-dichlorophenyl) -1,1-dimethyl
  • the antibiotic compound is preferably a neonicotinoid insecticide from the viewpoint of species selectivity and safety, and zinc pyritine from the viewpoint of versatility and efficacy, more preferably from the viewpoint of poor solubility, Clothianidin, imidacloprid, and zinc pyrithione are preferable, and clothianidin and imidacloprid are more preferable. Particularly preferred is clothianidin from the viewpoint of safety for mammals.
  • Antibiotic active compounds are substantially hydrophobic and, for example, have very low solubility in water at room temperature (20-30 ° C., more specifically 25 ° C.), more specifically,
  • the solubility at room temperature is 1.5 parts by mass / 100 parts by volume of water (15 g / L) or less, preferably 0.5 parts by volume / 100 parts by mass of water (5 g / L) or less, more preferably 0.1 parts by mass / 100 parts by volume of water (1 g / L) or less.
  • the antibiotic compound is substantially insoluble in the polymerizable vinyl monomer, and specifically, for example, at room temperature (20 to 30 ° C., more specifically 25 ° C.) with respect to the polymerizable vinyl monomer.
  • the solubility is extremely small. Specifically, the solubility at room temperature is, for example, 0.1 parts by mass / (use) polymerizable vinyl monomer (mixture) 100 parts by volume (1 g / L) or less, preferably 0.05. It is 100 parts by mass (0.5 g / L) or less by mass parts / (used) polymerizable vinyl monomer (mixture).
  • the melting point of the antibiotic compound is, for example, 80 ° C. or more, preferably 100 ° C. or more. If the antibiotic compound is a compound that does not contain a metal atom, it is, for example, 300 ° C. or less.
  • polymerizable vinyl monomer examples include (meth) acrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, maleic acid ester monomers, vinyl halides, vinylidene halides, nitrogen-containing vinyl monomers, and crosslinkable monomers. Etc.
  • 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 (i-BMA / i-BA), tert-butyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid alkyl ester in which the alkyl moiety such as n-pentyl, n-hexyl (meth) acrylate and cyclohexyl (meth) acrylate has a linear, branched or cyclic alkyl moiety having 1 to 6 carbon atoms And, for example, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth)
  • (meth) acrylic acid alkyl ester more preferred is a (meth) acrylic acid alkyl ester having an alkyl moiety having 1 to 6 carbon atoms, and particularly preferred is isobutyl methacrylate (i-BMA).
  • aromatic vinyl monomer examples include styrene monomers (monovinylbenzene) such as styrene (vinylbenzene), p-methylstyrene, o-methylstyrene, ⁇ -methylstyrene, and ethylvinylbenzene.
  • styrene monomers such as styrene (vinylbenzene), p-methylstyrene, o-methylstyrene, ⁇ -methylstyrene, and ethylvinylbenzene.
  • vinyl ester monomers examples include vinyl acetate and vinyl propionate.
  • maleate ester monomers examples 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.
  • nitrogen-containing vinyl monomer examples include (meth) acrylonitrile, N-phenylmaleimide, vinylpyridine, and the like.
  • crosslinkable monomer examples include mono- or polyethylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, such as 1,3-propanediol di (meth) acrylate, 1, Alkanediol di (meth) acrylates such as 4-butanediol di (meth) acrylate and 1,5-pentanediol di (meth) acrylate, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ( (Meth) acrylate crosslinkable monomers such as alkane polyol poly (meth) acrylate such as PETA / PETM), for example, allyl (meth) methacrylate, triallyl (iso) cyanurate Le monomers, such as divinyl benzene, aromatic crosslinking monomers such as trivinyl
  • the polymerizable vinyl monomer can be used alone or in combination.
  • Preferred examples of the polymerizable vinyl monomer include a combination of a (meth) acrylic acid ester monomer and a crosslinkable monomer, and a combination of an aromatic vinyl monomer and a crosslinkable monomer.
  • the content of the (meth) acrylic acid ester monomer is crosslinkable with the (meth) acrylic acid ester monomer.
  • 10 parts by mass or more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and, for example, 90 parts by mass or less, preferably 80 parts by mass with respect to 100 parts by mass of the total amount of monomers. It is 70 parts by mass or less, more preferably 70 parts by mass or less.
  • the blending ratio of the aromatic vinyl monomer is, for example, relative to 100 parts by mass of the total amount of the aromatic vinyl monomer and the crosslinkable monomer. 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less, more preferably 70 parts by mass or less. It is.
  • the glass transition temperature is, for example, 30 ° C. or higher, and preferably 50 ° C. or higher.
  • the polymerizable vinyl monomer is selected so as to have this glass transition temperature.
  • the polymerizable vinyl monomer is, for example, substantially hydrophobic, and specifically has, for example, extremely low solubility in water at room temperature. More specifically, the solubility at room temperature is, for example, 10 parts by mass / 100 parts by volume of water (100 g / L) or less, preferably 8 parts by weight / 100 parts by volume of water (80 g / L) or less.
  • the entire polymerizable vinyl monomer that is, a mixture of different types of polymerizable vinyl monomers
  • hydrophobic shell forming component and hydrophilic shell forming component are two different components that react with each other by polyaddition or polycondensation (condensation polymerization).
  • the hydrophobic shell-forming component is, for example, substantially hydrophobic and specifically has a very low solubility in water at room temperature. More specifically, for example, the solubility at room temperature is 1 part by weight / water. 100 parts by volume (10 g / L) or less, preferably 0.5 parts by weight / 100 parts by volume of water (5 g / L) or less, more preferably 0.1 parts by weight / 100 parts by volume of water (1 g / L) or less. It is.
  • the hydrophobic shell-forming component is an oil-soluble compound that forms a shell by polyaddition or polycondensation with a hydrophilic shell-forming component, and examples thereof include polyisocyanate, polycarboxylic acid chloride, and polysulfonic acid chloride.
  • polyisocyanate examples include aromatic polyisocyanates (aromatic diisocyanates) such as diphenylmethane diisocyanate and toluene diisocyanate, aliphatic polyisocyanates (aliphatic diisocyanates) such as hexamethylene diisocyanate, for example, isophorone diisocyanate (IPDI), hydrogen Aliphatic polyisocyanates (alicyclic diisocyanates) such as added xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate, for example, araliphatic polyisocyanates (araliphatic diisocyanate) such as xylylene diisocyanate and tetramethyl xylylene diisocyanate, etc. It is done.
  • aromatic polyisocyanates aromatic diisocyanates
  • aliphatic polyisocyanates such as hexamethylene diisocyanate
  • multimers of the above-described polyisocyanates are also exemplified, and specific examples include dimers, trimers (isocyanurate group-containing polyisocyanates, cyclic trimers), pentamers, and heptamers.
  • a trimer specifically, a trimer of IPDI is used.
  • modified polyisocyanate (excluding multimers) is also exemplified, for example, Polyol-modified polyisocyanates such as IPDI adducts of trimethylolpropane.
  • polycarboxylic acid chloride examples include sebacic acid dichloride, adipic acid dichloride, azelaic acid dichloride, terephthalic acid dichloride, and trimesic acid dichloride.
  • polysulfonic acid chloride examples include benzenesulfonyl dichloride.
  • Hydrophobic shell forming components can be used alone or in combination.
  • hydrophobic shell-forming component examples include polyisocyanate, more preferably, a cyclic trimer of diisocyanate and an adduct of trimethylolpropane.
  • the hydrophilic shell forming component is a water-soluble compound present in the aqueous phase before interfacial polymerization.
  • the hydrophilic shell-forming component is an active hydrogen group-containing compound, and such an active hydrogen group-containing compound is, for example, a compound having an active hydrogen group such as an amino group or a hydroxyl group. , Polyamine, polyol, water and the like.
  • polyamines examples include diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diaminotoluene, phenylenediamine, and piperazine, for example, polyamines having a valence of 3 or more such as diethylenetriamine, triethylenetetramine, tetraethylene, and pentaminepentaethylenehexamine. Etc.
  • diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diaminotoluene, phenylenediamine, and piperazine
  • polyamines having a valence of 3 or more such as diethylenetriamine, triethylenetetramine, tetraethylene, and pentaminepentaethylenehexamine.
  • Etc Preferably, trivalent or higher polyamine, more preferably diethylenetriamine is used.
  • polystyrene resin examples include ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexane dimethanol, polyethylene glycol, polypropylene glycol, etc.
  • Diols such as triols such as glycerin and trimethylolpropane, and tetraols such as pentaerythritol.
  • the hydrophilic shell forming component can be used alone or in combination.
  • hydrophilic shell forming component polyamines and polyols are preferable, and polyamines are more preferable.
  • Oil phase component preparation process In the oil phase component preparation step, an antibiotic compound that is hydrophobic and substantially insoluble in the hydrophobic polymerizable vinyl monomer is dispersed in the hydrophobic polymerizable vinyl monomer in the absence of a solvent. Then, a hydrophobic slurry is prepared, and then the hydrophobic slurry and the hydrophobic shell forming component are blended to prepare an oil phase component including the hydrophobic slurry and the hydrophobic shell forming component.
  • the polymerizable vinyl monomer and the antibiotic compound are mixed, and the mixture is stirred without adding a solvent (a hydrophobic organic solvent such as hexane, toluene, ethyl acetate). Thereby, a hydrophobic slurry is prepared. The hydrophobic slurry is included in the oil phase component.
  • a solvent a hydrophobic organic solvent such as hexane, toluene, ethyl acetate
  • 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.
  • 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 antibiotic compound is wet-ground by the dispersion described above.
  • the blending ratio of the antibiotic compound to the polymerizable vinyl monomer is, for example, 1/99 or more, preferably 10/90, in mass ratio (that is, mass part of antibiotic compound / mass part of polymerizable vinyl monomer). Or more, more preferably 15/85 or more, and for example, 90/10 or less, preferably 75/25 or less, more preferably 70/30 or less, and further preferably 65/35 or less, particularly preferably. Is 60/40 or less.
  • the blending ratio of the antibiotic compound is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, with respect to 100 parts by mass of the polymerizable vinyl monomer.
  • it is 900 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less.
  • a dispersant (first dispersant) can be blended if necessary.
  • the dispersant include an amphiphilic polymer type dispersant, a nonionic surfactant (first surfactant), and the like.
  • amphiphilic polymer dispersant examples include, for example, EFKA4008, EFKA4009 (urethane-based polymer dispersant manufactured by Ciba Specialty), DISPERBYK-2164, DISPERBYK-164 (above, functional group for pigment dispersion manufactured by Bic Chemie) Modified copolymer), NUOSPERSE 2008, NUOSPERSE FA-196, NUOSPERSE 657 (above made by Elementis), Floren D-90, Polyflow KL-100, Polyflow KL-700 (above made by Kyoeisha Chemical Co., Ltd.), Homogenol L-95 (Kao) Nonionic amphiphilic polymer type dispersants such as those manufactured by Komatsu Ltd.
  • amphiphilic polymer dispersant examples include, for example, Floren G-900 (carboxyl-modified polymer manufactured by Kyoeisha Chemical Co., Ltd.), Disparon DA-234, Disparon DA-325, Disparon DA-375, Disparon DA-550. And anionic amphiphilic polymer type dispersants such as Disparon AQ-330 (polyether phosphate ester salt manufactured by Enomoto Kasei Co., Ltd.). Furthermore, examples of the amphiphilic polymer type dispersant include cationic amphiphilic polymer type dispersants such as NOPCOSPERTH 092 (manufactured by San Nopco).
  • Nonionic surfactants include, for example, amogen CBH (alkylbetaine), amogen SH (alkylamidobetaine), Neugen 100E (polyoxyethylene oleyl ether), Neugen EA73 (polyoxyethylene dodecylphenyl 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) Le) (all manufactured by Kao Corporation), and the like.
  • amogen CBH alkylbetaine
  • amogen SH alkylamidobetaine
  • Neugen 100E polyoxyethylene oleyl ether
  • the dispersant is preferably an amphiphilic polymer dispersant, more preferably a nonionic amphiphilic polymer dispersant, an anionic amphiphilic polymer dispersant, and more preferably.
  • nonionic amphiphilic polymer type dispersants and particularly preferred are functional group-modified copolymer dispersants for pigment dispersion and urethane polymer dispersants.
  • the mixing 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 antibiotic compound. It is.
  • the hydrophobic slurry and the hydrophobic shell forming component are blended.
  • the hydrophobic shell forming component is blended in the hydrophobic slurry.
  • the hydrophobic shell forming component is blended with the polymerization initiator in the hydrophobic slurry.
  • polymerization initiator examples include radical polymerization initiators usually used in suspension polymerization, and specific examples include oil-soluble polymerization initiators.
  • oil-soluble polymerization initiator examples include dilauroyl peroxide (10 hour half-life temperature T 1/2 : 61.6 ° C.), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (10-hour half-temperature T 1/2 : 65.3 ° C.), t-hexylperoxy-2-ethylhexanoate (10-hour half-temperature T 1/2 : 69.9 ° C.), diisopropyl peroxydicarbonate ( 10 hours half-life temperature T 1/2: 40.5 °C), benzoyl peroxide (10 hours half-life temperature T 1/2: 73.6 °C) oil-soluble organic peroxides such as, for example, 2,2' Bisisobutyronitrile (10 hour half temperature T 1/2 : 60 ° C.), 2,2′-azobis (2,4-dimethylvaleronitrile) (10 hour half temperature T 1/2 : 51 ° C.), 2, 2'-azobis 2-methylbutyronit
  • 10-hour half-life temperature T1 / 2 of a polymerization initiator is 40 degreeC or more, for example, Preferably, it is 50 or more, for example, is 90 degrees C or less, Preferably, it is 80 degrees C or less.
  • the 10-hour half-life temperature T 1/2 of the polymerization initiator is the temperature of the 10-hour value in the graph obtained by plotting the concentration half-life at several arbitrary temperatures.
  • Polymerization initiators can be used alone or in combination of two or more.
  • the blending ratio of the polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the polymerizable vinyl monomer. For example, 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2.0 parts by mass or less.
  • the blending ratio of the polymerization initiator exceeds the above upper limit, the molecular weight of the polymer may be excessively decreased.
  • the blending ratio is less than the above lower limit, the conversion rate is not sufficiently improved, and unreacted polymerization is performed. In some cases, several% or more of the functional vinyl monomer remains.
  • the polymerizable vinyl monomer can be divided and blended. In that case, first, a part of the polymerizable vinyl monomer is blended with the antibiotic compound and dispersed to prepare a hydrophobic slurry. Thereafter, the polymerization initiator and the hydrophobic shell-forming component are dissolved in the remainder of the polymerizable vinyl monomer, and this is blended into the hydrophobic slurry.
  • an oil phase component containing a polymerization initiator, a hydrophobic shell forming component and a hydrophobic slurry is prepared.
  • the blending ratio of the hydrophobic shell-forming component is, for example, 2 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer.
  • it is 100 parts by mass or less, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 60 parts by mass or less.
  • the blending ratio of the hydrophobic shell-forming component is, for example, 1% by mass or more, preferably 2% by mass or more, and for example, 60% by mass or less, preferably 40% by mass with respect to the oil phase component. % Or less.
  • the content ratio of the antibiotic compound in the oil phase component is, for example, 1% by mass or more, preferably 10% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less. Preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.
  • the content ratio of the polymerizable vinyl monomer in the oil phase component is, for example, 10% by mass or more, preferably 30% by mass or more, preferably 50% by mass or more, and for example, 90% by mass or less, preferably It is 80 mass% or less, More preferably, it is 70 mass% or less.
  • the average particle size of the antibiotic compound in the oil phase component is, for example, 5 ⁇ m or less, preferably 2.5 ⁇ m or less, and for example, 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more.
  • the hydrophobic shell forming component and the polymerization initiator are blended with respect to the hydrophobic slurry.
  • the hydrophobic shell forming component and the polymerization initiator are prepared in the hydrophobic slurry. It can also be blended with antibiotic active compounds and polymerizable vinyl monomers.
  • the hydrophobic shell forming component is first blended with the antibiotic compound and the polymerizable vinyl monomer, and then they are dispersed to prepare a hydrophobic slurry. Thereby, an oil phase component containing an antibiotic compound, a polymerizable vinyl monomer, a hydrophobic shell forming component and a polymerization initiator is prepared at a time.
  • oil phase component and water are mixed and stirred uniformly to disperse (suspend) the oil phase component in water.
  • an aqueous dispersion (suspension) of the oil phase component is obtained.
  • the conditions for water dispersion are not particularly limited, and may be carried out, for example, at room temperature or by heating.
  • a dispersant (second dispersant) and a surfactant (second surfactant) are blended.
  • dispersant examples 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.
  • polyvinyl alcohol (PVA) and tricalcium phosphate are preferable. More preferably, polyvinyl alcohol (PVA) is mentioned.
  • the blending ratio of the dispersant is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the oil phase component. 10 parts by mass or less, preferably 5 parts by mass or less.
  • the surfactant (second surfactant) is preferably used in combination with the above-described dispersant (second dispersant) in order to effectively prevent aggregation of particles during radical polymerization.
  • Anionic surfactants such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium di-2-ethylhexyl sulfosuccinate, sodium dodecyl diphenyl ether disulfonate, sodium nonyl diphenyl ether sulfonate, and salts of condensation products of aromatic sulfonic acid and formaldehyde
  • Nonionic agents such as polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene polyoxypropylene block copolymer System surfactant and the like.
  • Surfactants can be used alone or in combination.
  • a combination of a nonionic surfactant and an anionic surfactant is used, and more preferably a combination of a polyoxyethylene polyoxypropylene block copolymer and a salt of a condensate of aromatic sulfonic acid and formaldehyde Is mentioned.
  • aromatic sulfonic acid examples include benzene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, naphthalene sulfonic acid and the like.
  • naphthalenesulfonic acid such as ⁇ -naphthalenesulfonic acid and ⁇ -naphthalenesulfonic acid is used.
  • Examples of the cation for forming a salt include monovalent alkali metal cations such as sodium cation and potassium cation, for example, ammonium cation. Preferably, a monovalent alkali metal cation is used.
  • the salt of the condensate of aromatic sulfonic acid and formaldehyde include a salt of a condensate of naphthalene sulfonic acid and formaldehyde (naphthalene sulfonic acid formaldehyde condensate sodium salt).
  • naphthalene sulfonic acid formaldehyde condensate sodium salt Commercially available products can be used as the salt of the condensate of aromatic sulfonic acid and formaldehyde.
  • Demol NL ⁇ -naphthalenesulfonic acid formaldehyde condensate sodium salt, 41% aqueous solution, manufactured by Kao Corporation
  • 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 oil phase component. Preferably, it is 0.1 mass part or less.
  • the surfactant is a combination of a nonionic surfactant and an anionic surfactant
  • the blending ratio of each of the nonionic surfactant and the anionic surfactant is 100 parts by mass of the oil phase component.
  • it is 0.0001 mass part or more, for example, Preferably, it is 0.001 mass part or more, for example, is 1.0 mass part or less, Preferably, it is 0.1 mass part or less.
  • the dispersant or the dispersant and the surfactant can be blended, for example, either before or after blending the oil phase component and water, and preferably in the water before blending with the oil phase component. Blend.
  • an aqueous solution of the dispersant or an aqueous solution of the dispersant and the surfactant is prepared.
  • a disperser such as a homomixer, an ultrasonic homogenizer, a pressure homogenizer, a milder, or a porous membrane press-in disperser is used. 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.
  • dispersant second dispersant
  • a dispersant and a surfactant are used in the aqueous dispersion.
  • the droplets of the oil phase component are more stabilized.
  • the blending ratio of water is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, with respect to 100 parts by mass of the oil phase component. It is adjusted to 1900 parts by mass or less, preferably 900 parts by mass or less, more preferably 400 parts by mass or less.
  • the polymerizable vinyl monomer is subjected to suspension polymerization, and the hydrophobic shell-forming component and the hydrophilic shell-forming component are interfacially polymerized to form a shell that covers the suspension polymer. That is, the shell is formed so as to cover a polymer obtained by suspension polymerization, that is, a suspension polymer.
  • a polymerizable vinyl monomer is subjected to suspension polymerization to produce a polymer.
  • the aqueous dispersion is heated to a predetermined temperature.
  • 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 of the polymerizable vinyl monomer that becomes a polymer is only in water-dispersed particles (hydrophobic liquid phase).
  • the aqueous dispersion is heated while stirring, whereby the polymerizable vinyl monomer starts polymerization in the aqueous dispersion particles as it is, and a polymer is formed.
  • Stirring can be performed, for example, with a stirrer having stirring blades.
  • 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 temperature of the aqueous dispersion is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and for example, 100 ° C. or lower, preferably 90 ° C. or lower, more preferably 80 ° C. Heat to below °C.
  • suspension polymerization proceeds in a state where the antibiotic compound 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.
  • the antibiotic compound In suspension polymerization, the antibiotic compound is substantially insoluble with respect to the polymerizable vinyl monomer, and the antibiotic compound is incompatible with the polymerizable vinyl monomer and / or polymer from the start of polymerization to the end of polymerization. The incompatible state is maintained.
  • suspension polymerization a polymer prepared from a polymerizable vinyl monomer is produced as a suspension polymer.
  • the hydrophilic shell forming component is contained in the aqueous dispersion containing the hydrophobic shell forming component, and the temperature of the aqueous dispersion is raised.
  • the hydrophilic shell-forming component is blended with the aqueous dispersion containing the hydrophobic shell-forming component, and the aqueous dispersion is mixed with the temperature at which suspension polymerization starts (specifically, the polymerization initiator The temperature is raised to a temperature equal to or higher than the decomposition temperature.
  • the temperature at which the interfacial polymerization starts (starting temperature) T ip is not particularly limited, and is, for example, 0 ° C. or higher, preferably 10 ° C. or higher, and, for example, 100 ° C. or lower, preferably 80 ° C. or lower. .
  • the reaction is accelerated when the temperature is, for example, 25 ° C. or higher, preferably 40 ° C. or higher, and 100 ° C. or lower, preferably 80 ° C. or lower.
  • the temperature (starting temperature) T i at which suspension polymerization starts is, for example, in the relationship of the following formula (1) with the 10 hour half-life temperature T 1/2 of the polymerization initiator described above.
  • T 1/2 ⁇ 10 ⁇ T i ⁇ T 1/2 +10 (1)
  • T i represents the initiation temperature of suspension polymerization
  • T 1/2 represents the 10-hour half-life temperature of the polymerization initiator.
  • the temperature at which suspension polymerization starts is, for example, 55 ° C. or higher, preferably 60 ° C. or higher, and for example, 100 ° C. or lower, preferably 80 ° C. or lower.
  • the suspension polymerization start temperature T i is set higher than, for example, the interfacial polymerization start temperature T ip .
  • the suspension polymerization start temperature T i is set to, for example, 5 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher, compared to the interfacial polymerization start temperature T ip.
  • the temperature is set higher by 100 ° C. or less.
  • Examples of the method for starting interfacial polymerization and suspension polymerization include (1) a method of starting interfacial polymerization simultaneously with the start of suspension polymerization, (2) a method of starting interfacial polymerization before the start of suspension polymerization, (3) The method of starting interfacial polymerization after the start of suspension polymerization is mentioned.
  • the temperature of an aqueous dispersion containing an oil phase component containing a hydrophobic shell-forming component is raised to a temperature higher than the temperature at which suspension polymerization starts.
  • the hydrophilic shell-forming component is added to the aqueous dispersion.
  • the hydrophilic shell-forming component is changed to the oil phase containing the hydrophobic shell-forming component. It mix
  • the aqueous dispersion is heated to below the temperature at which suspension polymerization starts, and then The aqueous dispersion can also be heated to a temperature at which suspension polymerization starts.
  • the aqueous dispersion is heated so that the temperature is, for example, less than 55 ° C., preferably less than 50 ° C. Thereby, the interfacial polymerization can be sufficiently promoted before the suspension polymerization is started.
  • the aqueous dispersion is heated to a temperature higher than the temperature at which suspension polymerization starts, and then the hydrophilic shell-forming component is converted into the aqueous dispersion.
  • the time from when the aqueous dispersion is heated to a temperature above the temperature at which suspension polymerization starts until the hydrophilic shell-forming component is blended with the aqueous dispersion is, for example, 0.5 hours or more, It is preferably 1 hour or longer, and for example, 8 hours or shorter, preferably 5 hours or shorter.
  • the method (1) or (2) can prevent the antibiotic compound from dropping from the matrix (described later), and thus the antibiotic can be formed while forming a shell.
  • the active compound can be kept dispersed in the matrix. That is, in the sustained release particles, the shell can surely encapsulate the antibiotic compound in the matrix. Therefore, the alkali resistance of the antibiotic compound in the sustained release particles can be improved.
  • the shell can be formed so as to cover the droplets of the oil phase component, and is thus included in the suspension polymerization. It is possible to control the movement of the antibiotic compound from the suspension polymer to the aqueous phase interface (ie, the interface between the suspension polymer and the water continuous phase).
  • the mixing ratio of the hydrophilic shell forming component is the active hydrogen group (hydrophilic shell forming component of the hydrophilic shell forming component) of the isocyanate group of the hydrophobic shell forming component.
  • the equivalent ratio (isocyanate group / amino group) to amino group) is, for example, 0.4 or more, preferably 0.6 or more, and for example, 1.2 or less. The ratio is preferably 1.0 or less.
  • the hydrophilic shell forming component is blended in the aqueous dispersion containing the hydrophobic shell forming component.
  • the hydrophilic shell forming component is water
  • the hydrophilic shell forming component is separately provided. It is also possible to use the water contained in the aqueous dispersion as a hydrophilic shell forming component without intermixing the forming component with the aqueous dispersion and to interfacially polymerize the hydrophilic shell forming component and the hydrophobic shell forming component. it can.
  • a polyaddition catalyst such as dibutyltin dilaurate can be used.
  • the hydrophobic shell-forming component in the oil phase component (oil phase) and the hydrophilic shell-forming component in the aqueous phase undergo interfacial polymerization on the surface of the water-dispersed particles.
  • the polymerization time for the interfacial polymerization depends on the temperature of the suspension polymerization, but can be confirmed by lowering the pH of the polymerization reaction solution (reaching the neutralization point).
  • the time for completing the interfacial polymerization is, for example, 2 to 4 hours.
  • a shell that covers the oil phase component droplets can be preferably formed before or simultaneously with the start of the suspension polymerization.
  • the antibiotic compound contained in the suspension polymerization moves from the suspension polymer to the aqueous phase interface (interface between the suspension polymer and the water continuous phase).
  • a shell made of a polymer of a hydrophobic shell-forming component and a hydrophilic shell-forming component is formed on the surface of the suspension polymer obtained by interfacial polymerization of the hydrophobic shell-forming component and the hydrophilic shell-forming component.
  • the aqueous dispersion after the reaction is cooled by, for example, cooling, and filtered through a 100 mesh (mesh) filter cloth to obtain an aqueous dispersion of sustained release particles ( Suspension).
  • the cooling temperature is, for example, room temperature (20 to 30 ° C., more specifically 25 ° C.).
  • the concentration of the antibiotic compound in the obtained sustained-release particles is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and for example, 50% by mass or less.
  • the amount is preferably 40% by mass or less, and more preferably 35% by mass or less.
  • the content ratio of the sustained release particles in the aqueous dispersion is determined by the blending amount of the oil phase component and the water (or aqueous solution) in which the oil phase component is dispersed. Specifically, for example, It is 10 mass% or more, Preferably, it is 20 mass% or more, for example, is 50 mass% or less, Preferably, it is 40 mass% or less.
  • the concentration of the shell in the sustained release particles is, for example, 1% by mass or more, preferably 2% by mass or more, and for example, 50% by mass or less, preferably 40% by mass or less.
  • the average particle diameter of the sustained release particles is, for example, 1 ⁇ m or more, preferably 2 ⁇ m or more, and for example, 20 mm or less, preferably 10 mm or less.
  • the average particle diameter is calculated as the median diameter.
  • sustained-release particles of the second invention group are hydrophobic, and in the absence of a solvent, a hydrophobic and substantially insoluble antibiotic active compound with respect to a hydrophobic polymerizable vinyl monomer.
  • the microcapsules obtained by the method described in Patent Document 1 are obtained only by interfacial polymerization, the dispersion medium (solvent) remains in the microcapsules, and therefore the surface hardness becomes insufficient. There is. As a result, when the microcapsule dispersion undergoes a process in which a high shearing force is applied or is stored for a long period of time, the microcapsules may aggregate to make redispersion difficult.
  • the microcapsules are likely to be blocked, and it may be difficult to take out the microcapsules as dry particles.
  • the sustained-release particles of the second invention group are hydrophobic, and in the absence of a solvent, the hydrophobic active vinyl compound that is substantially insoluble with respect to the hydrophobic polymerizable vinyl monomer, Hydrophobic slurry dispersed in a polymerizable vinyl monomer, an oil phase component preparation step for preparing an oil phase component containing a hydrophobic shell-forming component, and an aqueous dispersion for preparing an aqueous dispersion by dispersing the oil phase component in water Process and polymerization to form a polymer that becomes a core by interfacial polymerization of a hydrophobic shell-forming component and a hydrophilic shell-forming component to form a polymer that becomes a shell, and suspension polymerization of a polymerizable vinyl monomer Since it is obtained by a production method comprising a step, it is possible to obtain a robust sustained-release particle by preventing a decrease in surface hardness of the sustained-release particle due to the presence of the solvent in the above
  • a shell that coats the suspension-polymerized suspension polymer is formed, so that the inclusion rate of the antibiotic compound (of the antibiotic compound in the sustained-release particles) Concentration) can be increased, and the sustained release and alkali resistance of the antibiotic compound are excellent.
  • the sustained release property of the sustained release particles and the alkali resistance of the antibiotic compound in the sustained release particles are related to each other. Specifically, the alkali resistance of the antibiotic compound in the sustained release particles is When is improved, the sustained release property of the sustained release particles is improved.
  • the shell is made of polyurea, so that the sustained-release particles are excellent in melt miscibility with the thermoplastic urethane resin. It becomes.
  • sustained-release particles can be applied to various industrial products, for example, indoor and outdoor paints, rubber, fibers, resins (including plastics), adhesives, joint agents, sealing agents, building materials, caulking. It can be added to the agent, wood treatment agent, soil treatment agent, white water, pigment, printing plate treatment liquid, cooling water, ink, cutting oil, cosmetics, non-woven fabric, spinning oil, leather, etc. in the papermaking process.
  • the added amount of the antibiotic compound in the sustained release particles to these industrial products is, for example, 10 mg / kg to 100 g / kg (product mass).
  • thermoplastic resin a powder formulated from sustained-release particles is blended with a thermoplastic resin.
  • a suspension of sustained-release particles is dried and formulated into a powder.
  • the powder and the thermoplastic resin are melt-kneaded to prepare a kneaded product.
  • the kneaded material In order to prepare the kneaded material, specifically, for example, an extruder or a Banbury mixer is used.
  • the extruder for example, a twin screw extruder or a single screw extruder is used.
  • the kneaded material is a molding material for molding a molded product. Specifically, the kneaded material is once cooled and prepared as a pellet-shaped molding material (kneaded material pellet or master batch). On the other hand, the kneaded product is not taken out as a solid molding material, but can be continuously used as it is in a molten state (melt kneaded product) and subjected to molding described later.
  • the content of the antibiotic compound in the powder agent is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and, for example, 10% by mass or less, preferably, with respect to the thermoplastic resin.
  • a powder agent is mix
  • the content of the antibiotic compound is, for example, 1% by mass or more, preferably, with respect to the thermoplastic resin.
  • the powder is mixed with the thermoplastic resin so as to be 5% by mass or more, for example, 50% by mass or less, and preferably 30% by mass or less, to obtain a master batch.
  • the thermoplastic resin is not particularly limited.
  • polyolefin resin such as polyethylene and polypropylene, polystyrene, polymethyl methacrylate, acrylonitrile / styrene copolymer resin (AS resin), methyl methacrylate / styrene copolymer (MS resin), acrylonitrile / styrene / butadiene copolymer resin (ABS resin), styrene and / or acrylic resins, polyethylene terephthalate, polyester resins such as polylactic acid, polyamide resins such as 6-nylon, chloride Examples thereof include vinyl halide resins such as vinyl resin and vinylidene chloride resin, polycarbonate, polyphenylene ether, polyacetal, and thermoplastic polyurethane.
  • polyolefin resin, vinyl chloride resin, and thermoplastic polyurethane are used.
  • the mixture is molded into a molded product from the kneaded product pellets or melt-kneaded product.
  • the molding method for example, injection molding, extrusion molding, inflation molding, pultrusion molding, compression molding, or the like is employed.
  • the powder formulated from sustained-release particles is added to the thermoplastic resin.
  • the powder is not particularly limited as long as it is a resin, and may be added to, for example, a thermosetting resin.
  • a powder can be suitably mixed with a liquid resin such as an epoxy resin or a silicone resin.
  • Such molded articles are used in various applications, for example, building materials such as electric wire cable materials, and electric wire cable coating materials such as gas conduits, and conduit coating materials such as clothing. Used as textile products such as mosquito nets.
  • sustained-release particles obtained by the above-described method for producing sustained-release particles of the second invention group specifically include the following third and fourth embodiments of sustained-release particles. It is out.
  • the sustained release particles 1 are formed, for example, as spherical particles as shown in the cross-sectional view of FIG. B1.
  • the sustained release particles 1 include a matrix 2, a domain 3 dispersed in the matrix 2, and a shell 7 that covers the matrix 2.
  • the matrix 2 is made of a polymer prepared from the above-described polymerizable vinyl monomer. Domain 3 consists of the antibiotic compounds described above.
  • the shell 7 is made of a polymer prepared from the above-described hydrophobic shell-forming component and hydrophilic shell-forming component.
  • a matrix 2 forms a medium or a continuous phase, and a multi-domain structure or a sea-island structure (or a multinuclear structure) in which a plurality of domains 3 are dispersed in the matrix 2 is formed.
  • the matrix 2 and the domain 3 are incompatible with each other and form a phase separation structure or a two-phase structure that separate from each other.
  • the matrix 2 and the domain 3 form a core for the shell 7 described later.
  • the plurality of domains 3 form 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 ⁇ m or more, preferably 0.1 ⁇ m or more, and for example, 20 ⁇ m or less, preferably 10 ⁇ m or less.
  • the shell 7 is formed on the surface of the matrix 2 (polymer obtained by suspension polymerization of the polymerizable vinyl monomer described above). Specifically, the shell 7 covers, for example, at least a part of the surface of the matrix 2, preferably the entire surface of the matrix 2. That is, the shell 7 forms a core-shell structure together with the core composed of the matrix 2 and the domain 3.
  • the shell 7 is composed of a polymer prepared from a hydrophobic shell-forming component and a hydrophilic shell-forming component. Specifically, the outermost layer (outermost surface) is substantially The concentration of the polymer prepared from the hydrophobic shell-forming component and the hydrophilic shell-forming component with respect to the matrix 2 (polymer) in the direction from the outermost layer (outermost surface) to the inside. Is configured to be thin. Thereby, the shell 7 is located (unevenly distributed) on the surface layer of the matrix 2 so as to surround the domain 3.
  • grains is less than 30 mass%, for example An antibiotic compound is blended so that
  • the sustained-release particles 1 of the third embodiment include a matrix 2 made of a polymer of a polymerizable vinyl monomer and a domain 3 made of an antibiotic compound, and the domain 3 dispersed in the matrix 2, In addition to excellent sustained release properties of the antibiotic compound, it is excellent in fastness and excellent in kneading with a resin.
  • the domain 3 includes a protrusion 4 that protrudes outward from the inside of the matrix 2.
  • the protrusion 4 is exposed from the surface of the matrix 2.
  • both the matrix 2 and the domain 3 are exposed on the surface of the sustained release particles 1.
  • the protrusion 4 has an embedded portion 8 embedded in the surface layer portion of the matrix 2.
  • the sustained release particles 1 have a two-phase structure formed from a matrix 2 and a domain 3 and do not have a shell 7.
  • the sustained release particles 1 shown in FIG. B9 are produced by the production method described above except that the hydrophobic shell-forming component and the hydrophilic shell-forming component are not blended and interfacial polymerization is not performed.
  • the sustained-release particles 1 of the third embodiment shown in FIG. B1 are different from the sustained-release particles 1 of the reference form of FIG. B9 and have no protrusions 4 and the suspension polymer is covered with the shell 7. Therefore, it has excellent long-term sustained release.
  • the domain 3 (antibiotic active compound) of the sustained release particles 1 can be protected by the shell 7 as shown in FIG. B1. Therefore, the sustained release particles 1 of the third embodiment are superior to the sustained release particles 1 of the reference embodiment in the sustained release properties and alkali resistance of the antibiotic compound.
  • the deposit 5 made of an antibiotic compound is attached to the surface of the shell 7.
  • the shape of the deposit 5 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 inner surface (contact surface that contacts the surface of the shell 7) of the deposit 5 forms a concave surface corresponding to the surface (spherical surface) of the shell 7, specifically, a curved surface that is recessed outward.
  • the deposit 5 is the same size as or smaller than the domain 3, and is, for example, 100% or less, preferably 50% or less with respect to the average value of the maximum length of the domain 3.
  • the average value of the maximum length of the deposit 5 is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less, for example, 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more. It is.
  • the coverage of the deposit 5 on the entire surface of the shell 7 is, for example, 10% or more, preferably 20% or more, and for example, 100% or less, preferably 90% or less.
  • the concentration of the antibiotic compound in the sustained release particles is, for example, more than 28% by mass, Preferably, the antibiotic compound is blended so as to be 30% by mass or more, more preferably 35% by mass.
  • the anti-blocking property can be further improved by the deposit 5.
  • the second invention group can include both the sustained release particles of the third embodiment and the sustained release particles of the fourth embodiment, and in that case, on a mass basis, Their blending ratio (sustained release particles of the third embodiment / sustained release particles of the fourth embodiment) is, for example, 1/99 or more, further 10/90 or more, and for example, 99 / 1 or less, and further 90/10 or less.
  • Example A corresponding to the first invention group, etc.
  • the numerical values of Preparation Example A and Example A shown below are the numerical values described in the above-mentioned “Mode for Carrying Out the Invention” column (that is, the upper limit). Value or lower limit value). Further, in Preparation Example A, Example A and Comparative Example A, units such as% mean mass% unless otherwise specified.
  • Clothianidin (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine, molecular weight 250, melting point 177 ° C., solubility in water: 0.33 g / L, manufactured by Sumitomo Chemical Co., Ltd.
  • Imidacloprid 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine, molecular weight 256, melting point 144 ° C., solubility in water: 0.48 g / L, manufactured by Maruzen EGDMA: ethylene glycol dimethacrylate Product name “Light Ester EG”, insoluble in water, Kyoeisha Chemical Co., Ltd.
  • i-BMA Isobutyl methacrylate, water solubility: 0.6 g / L, Nippon Shokubai Co., Ltd.
  • DVB-570 Product name, insoluble in water , Composition: Divinylbenzene (upper limit 60%), Ethylvinylbenzene (upper limit 40%), Nippon Steel & Sumikin Chemical Co., Ltd.
  • Styrene To water Solubility: 0.3 g / L, Wako Special Grade Reagent, manufactured by Wako Pure Chemical Industries, Ltd.
  • DISPERBYK-164 trade name, functional group-modified copolymer for pigment dispersion (tertiary amine-containing polyester-modified polyurethane polymer, molecular weight 10,000 to 50,000) Butyl acetate solution, solid concentration 60%, Big Chemie's Parroyl L: trade name, dilauroyl peroxide, NOF Corporation Perhexyl O: trade name, t-hexylperoxy-2-ethylhexanoate, NOF Pronon 208: trade name, polyoxyethylene polyoxypropylene block copolymer, NOF Corporation PVA-217: trade name “Kuraray Poval 217”, partially saponified polyvinyl alcohol, Kuraray Co., Ltd.
  • the average particle size of clothianidin in Slurry A was 1.38 ⁇ m as a result of measurement with a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
  • Preparation Example A2 (Preparation of clothianidin slurry (slurry B)) DVB-570 7200g and DISPERBYK-164 804g are uniformly distributed in a batch type media disperser (batch type bead mill, trade name “AD mill (AD-5), zirconia bead diameter 1.5 mm”, manufactured by Asada Tekko Co., Ltd.) Then, 3996 g of clothianidin was added and wet-pulverized for 150 minutes to obtain a slurry containing 33.3% clothianidin (hydrophobic slurry, hereinafter referred to as “slurry B”).
  • slurry B hydrophobic slurry
  • the average particle diameter of clothianidin in the slurry B was 0.45 ⁇ m as a result of measurement with a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
  • Preparation Examples A3 to A8 (Preparation of clothianidin slurry (slurries C to H)) A clothianidin slurry (hydrophobic slurry, hereinafter referred to as “slurries C to H”) was obtained in the same manner as in Preparation Example A1, except that the formulation was changed to the formulation shown in Table A1.
  • Preparation Example A9 (Preparation of imidacloprid slurry (slurry I)) An imidacloprid slurry (hydrophobic slurry, hereinafter referred to as “slurry I”) was obtained in the same manner as in Preparation Example A1, except that the formulation was changed to the formulation shown in Table A1.
  • Example A1 (Synthesis of clothianidin-containing sustained release particles: corresponding to the first embodiment)
  • slurry B prepared in Preparation Example A2
  • Parroyl L were charged and stirred at room temperature to dissolve Parroyl L in Slurry B.
  • an oil phase component containing Parroyl L and Slurry B was prepared.
  • the oil phase component was added to a 500 mL beaker (2).
  • K The oil phase component was dispersed in water by stirring with a homomixer MARK 2.5 type (manufactured by Primix) at a rotational speed of 6000 rpm for 5 minutes to prepare a suspension (aqueous dispersion).
  • suspension aqueous dispersion
  • 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.
  • 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.
  • suspension after the reaction was cooled to 30 ° C. or less to obtain a suspension (suspension) of sustained release particles containing clothianidin and having a median diameter of 28.2 ⁇ m.
  • the median diameter of the sustained release particles was measured with a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.). The measurement of the median diameter is the same for the following examples and comparative examples.
  • Example A2 Synthesis of clothianidin-containing sustained release particles: corresponding to the second embodiment
  • 100 g of slurry B prepared in Preparation Example A2 and 0.5 g of Parroyl L were charged and stirred at room temperature to dissolve Parroyl L in Slurry B.
  • an oil phase component containing Parroyl L and Slurry B was prepared.
  • the oil phase component was added to a 500 mL beaker (2).
  • K The oil phase component was dispersed in water by stirring with a homomixer MARK 2.5 type (manufactured by Primix) at a rotational speed of 6000 rpm for 5 minutes to prepare a suspension (aqueous dispersion).
  • suspension polymerization was carried out under the same conditions as in Example A1 to obtain a suspension (suspension) of sustained release particles containing clothianidin and having a median diameter of 24.5 ⁇ m.
  • Example A3 Synthesis of clothianidin-containing sustained release particles: corresponding to the second embodiment
  • 100 g of slurry A prepared in Preparation Example A1 and 0.5 g of Parroyl L were charged and stirred at room temperature to dissolve Parroyl L in Slurry A.
  • an oil phase component containing Parroyl L and Slurry A was prepared.
  • the oil phase component was added to a 500 mL beaker (2). K.
  • the oil phase component was dispersed by stirring for 5 minutes at a rotation speed of 3000 rpm with a homomixer MARK 2.5 type (manufactured by Primix) to prepare a suspension (aqueous dispersion).
  • suspension polymerization was carried out under the same conditions as in Example A1 to obtain a suspension (suspension) of sustained-release particles containing clothianidin and having a median diameter of 43.5 ⁇ m.
  • Example A4 (Synthesis of clothianidin-containing sustained release particles: corresponding to the second embodiment) A 200 mL beaker (1) is charged with 50 g of slurry A prepared in Preparation Example A1, 25 g of i-BMA, 25 g of EGDMA, and 0.5 g of Parroyl L, and stirred at room temperature, whereby i-BMA, EGDMA and Parroyl L are mixed. Dissolved in slurry A. Thus, an oil phase component containing i-BMA, EGDMA, Parroyl L and slurry A was prepared.
  • the oil phase component was added to a 500 mL beaker (2). K.
  • the oil phase component was dispersed by stirring for 5 minutes at a rotation speed of 5000 rpm with a homomixer MARK 2.5 type (manufactured by Primix) to prepare a suspension (aqueous dispersion).
  • suspension polymerization was carried out under the same conditions as in Example A1 to obtain a suspension (suspension) of sustained-release particles containing clothianidin and having a median diameter of 9.3 ⁇ m.
  • a suspension (suspension) of sustained-release particles containing clothianidin was obtained in the same manner as in Example A4, except that the formulation was changed according to the descriptions in Table A2 and Table A3.
  • the average particle diameters of the sustained release particles in the suspension are shown in Table A2 and Table A3.
  • Example A9 Synthesis of clothianidin-containing sustained release particles: corresponding to the second embodiment
  • a 200 mL beaker (1) is charged with 50 g of slurry C prepared in Preparation Example A1, 25 g of styrene, 25 g of EGDMA, and 0.5 g of Parroyl L, and stirred at room temperature, whereby styrene, EDGMA and Parroyl L are added to Slurry C. Dissolved.
  • an oil phase component containing styrene, EDGMA, Parroyl L and slurry C was prepared.
  • the oil phase component was added to a 500 mL beaker (2). K.
  • the oil phase component was dispersed by stirring for 5 minutes at a rotation speed of 5000 rpm with a homomixer MARK 2.5 type (manufactured by Primix) to prepare a suspension (aqueous dispersion).
  • suspension polymerization was carried out under the same conditions as in Example A1, and a suspension (suspension agent) of sustained-release particles containing clothianidin and having a median diameter of 14.5 ⁇ m was obtained.
  • Example A10 to Example A12, Example A14, Example A17, Example A18 Synthesis of clothianidin-containing sustained release particles: corresponding to the second embodiment
  • a suspension (suspension) of sustained-release particles containing clothianidin was obtained in the same manner as in Example A9, except that the formulation was changed according to the description in Table A3.
  • Each average particle diameter of the sustained release particles in the suspension is shown in Table A3.
  • Example A19 (synthesis of imidacloprid-containing sustained release particles: corresponding to the second embodiment)
  • a suspension (suspension) of sustained-release particles containing imidacloprid was obtained in the same manner as in Example A4 except that the formulation was changed according to the description in Table A3.
  • the average particle size of the sustained release particles in the suspension is shown in Table A3.
  • “1” in the polymerization conditions column means that the temperature of the suspension in the polymerization process was adjusted to “70 ⁇ 1 ° C. for 5 hours, 80 ⁇ 1 ° C. for 2 hours”, “2” Means that the temperature of the suspension in the polymerization process was adjusted to “80 ⁇ 1 ° C. for 3 hours, 85 ⁇ 1 ° C. for 3 hours”.
  • “1” in the form column of the sustained release particles has the structure of the first embodiment shown in FIG. A1, and “2” has the structure of the second embodiment shown in FIG. A2. Show.
  • Example A20 Keratin and molding of powder of sustained release particles and thermoplastic resin
  • the suspension of sustained-release particles produced in Example A1 was filtered through a 100-mesh filter cloth and dried at room temperature for 1 day to obtain sustained-release particle powder (powder).
  • the obtained sustained-release particle powder (powder) and high-density polyethylene (HDPE) Hi-Zex 6300M were 0.25% clothianidin with respect to HDPE.
  • Example A21 (kneading and molding of the powder of Example A3 and polyethylene) A strip shape treatment was carried out in the same manner as in Example A20 except that the suspension of sustained release particles prepared in Example A3 was used instead of the suspension of sustained release particles prepared in Example A1. A molded product was obtained.
  • Example A22 Suspension of sustained release particles prepared in Example A1 (clothianidin concentration: 8.3% by mass) with respect to 100 parts by mass of Kagalite 2 (manufactured by Kagalite Kogyo Co., Ltd., fine particles of pumice, particle size of 425 to 1400 ⁇ m) 1 Then, 2 parts by mass were blended and then dried to obtain clothianidin granules. The clothianidin concentration in the granules was about 0.1% by mass.
  • Example A23 Instead of the sustained-release particle suspension prepared in Example A1, 1.2 parts by mass of the sustained-release particle suspension prepared in Example A3 (clothianidin concentration 8.3 mass%) was added. Were processed in the same manner as in Example A22 to obtain clothianidin granules. The clothianidin concentration in the granules was about 0.1% by mass.
  • Comparative Example A1 (kneading of clothianidin microcapsule suspension with polyethylene) Instead of the sustained-release particle powder (powder) prepared from Example A1, a sample obtained by drying and crushing a clothianidin microcapsule suspension “Xyramon MC” manufactured by Nihon Enviro Chemicals Co., Ltd. for 1 day at room temperature. In the same manner as in Example A6, the capsule was broken during melt-kneading, the solvent was atomized, and kneading could not be performed.
  • Example A1 to Example A4 Example A9 and Example A19 was dropped on a sample stage, and then water was distilled off. Thereafter, the obtained sustained-release particles were observed with an SEM using a scanning electron microscope Hitachi TM-3000 (manufactured by Hitachi High-Technologies Corporation). SEM images of the sustained release particles obtained in Examples A1 to A4, Example A9, and Example A19 are shown in FIGS. A4 to A9, respectively.
  • Example A20 and Example A21 were immersed in liquid nitrogen, and the fractured surface that was brittle fractured was observed with a scanning electron microscope Hitachi TM-3000 (manufactured by Hitachi High-Technologies Corporation) by SEM.
  • Cross-sectional SEM images of Example A20 and Example A21 are shown in FIGS. A10 and A11, respectively.
  • FIGS. A12 to A14 Image processing diagrams of the TEM photographs of Example A1 to Example A3 are shown in FIGS. A12 to A14, respectively.
  • the blank indicated by reference numeral 3 is a trace of clothianidin dissolved and dropped in the process of recovering the cut-out ultrathin section floating on water, and represents the shape of clothianidin domain. .
  • sustained-release particles produced in Examples A1 to A3 was filtered through a 100-mesh filter cloth and dried at room temperature for 1 day to obtain sustained-release particle powder (powder). These powders were diluted 1000 times with deionized water, of which 6.3 mL was weighed into a glass bottle, and 2 mL of saturated calcium hydroxide solution was added to prepare a test solution. This test solution was allowed to stand at a constant temperature of 40 ° C.
  • Example A4 The results are shown in Table A4.
  • the suspension containing the sustained-release particles of Examples A1 to A3 had a high clothianidin residual ratio of 91 to 93% on the first day after the start of the test. On the 7th day, all were 12 to 16%, which was lower than 1 day after the start of the test, but it was found that it was still at a practical level when the control was 7%.
  • the sustained release particles of Example A2 and Example A3 corresponding to the second embodiment are the sustained release of Example A1 corresponding to the first embodiment on both the first and seventh days after the start of the test. It can also be seen that the alkali resistance is superior compared to the particles.
  • Example A5 The results are shown in Table A5.
  • the granules of Example A22 and Example A23 containing the sustained release particles of Example A1 and Example A3 have a clothianidin residual ratio of 90-92 on the first day after the start of the test. 7% after the start of the test, all decreased to 11-15% compared to 1 day after the start of the test. However, considering that the control is 7%, it is still at a practical level. I understand.
  • the granule of Example A23 containing the sustained release particles of Example A3 corresponding to the second embodiment is an example corresponding to the first embodiment on both the 1st and 7th days after the start of the test.
  • the antibiotic resistance of the antibiotic compound is superior to the granules of Example A22 containing the sustained release particles of A1. 4). Mold prevention test of molded article Silica sand poured to have a moisture content of 8% (optimum moisture content of termite activity) was filled in a plastic container, and then the surface of the quartz sand was Example A20 and Example A21. A strip-shaped molded product was installed.
  • Example A20 and Example A21 a remarkable ant killing effect was recognized.
  • Example B corresponding to the second invention group, etc.
  • the numerical values of Preparation Example B, Example B and Reference Example B shown below are those described in the above-mentioned “Mode for Carrying Out the Invention” column. (That is, an upper limit value or a lower limit value) can be substituted. Further, in Preparation Example B, Example B, and Reference Example B, units such as% mean mass% unless otherwise specified.
  • Clothianidin (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine, molecular weight 250, melting point 177 ° C., solubility in water: 0.33 g / L, manufactured by Sumitomo Chemical Co., Ltd.
  • Imidacloprid 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine, molecular weight 256, melting point 144 ° C., solubility in water: 0.48 g / L, manufactured by Maruzen EGDMA: ethylene glycol dimethacrylate Product name “Light Ester EG”, insoluble in water, Kyoeisha Chemical Co., Ltd.
  • i-BMA Isobutyl methacrylate, water solubility: 0.6 g / L, Nippon Shokubai Co., Ltd.
  • DVB-570 Product name, insoluble in water , Composition: Divinylbenzene (upper limit 60%), Ethylvinylbenzene (upper limit 40%), Nippon Steel & Sumikin Chemical Co., Ltd.
  • Styrene To water Solubility: 0.3 g / L, Wako Special Grade Reagent, manufactured by Wako Pure Chemical Industries, Ltd.
  • DISPERBYK-164 trade name, functional group-modified copolymer for pigment dispersion (tertiary amine-containing polyester-modified polyurethane polymer, molecular weight 10,000 to 50,000) Butyl acetate solution, solid content concentration 60%, Big Chemie's Parroyl L: trade name, dilauroyl peroxide, 10 hour half-life T 1/2 : 61.6 ° C, NOF Pronon 208: trade name, poly Oxyethylene polyoxypropylene block copolymer, NOF Corporation PVA-217: Trade name “Kuraray Poval 217”, partially saponified polyvinyl alcohol, Kuraray Co., Ltd.
  • DEMAL NL trade name, ⁇ -naphthalenesulfonic acid formaldehyde condensate 41 sodium salt % Aqueous solution, Kao Corporation T-1890: Trade name “VESTANA” T 1890/100 ", cyclic trimer form of isophorone diisocyanate (IPDI), solubility in water: 0.02 g / L, manufactured by Evonik Industries, Inc.
  • DETA diethylenetriamine, Wako primary reagent, manufactured by Wako Pure Chemical Industries, Ltd.
  • the average particle size of clothianidin in Slurry A was 1.38 ⁇ m as a result of measurement with a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
  • Preparation Example B2 (Preparation of clothianidin slurry (slurry B)) DVB-570 7200g and DISPERBYK-164 804g are uniformly distributed in a batch type media disperser (batch type bead mill, trade name “AD mill (AD-5), zirconia bead diameter 1.5 mm”, manufactured by Asada Tekko Co., Ltd.) Then, 3996 g of clothianidin was added and wet-pulverized for 150 minutes to obtain a slurry containing 33.3% clothianidin (hydrophobic slurry, hereinafter referred to as “slurry B”).
  • slurry B a slurry containing 33.3% clothianidin (hydrophobic slurry, hereinafter referred to as “slurry B”).
  • the average particle diameter of clothianidin in the slurry B was 0.45 ⁇ m as a result of measurement with a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
  • Preparation Examples B3 to B8 (Preparation of clothianidin slurry (slurries C to H)) A clothianidin slurry (hydrophobic slurry, hereinafter referred to as “slurries C to H”) was obtained in the same manner as in Preparation Example B1, except that the formulation was changed to the formulation shown in Table B1.
  • Table B1 shows the average particle diameter of clothianidin in each of the slurries C to H.
  • Preparation Example B9 (Preparation of imidacloprid slurry (slurry I)) An imidacloprid slurry (hydrophobic slurry, hereinafter referred to as “slurry I”) was obtained in the same manner as in Preparation Example B1, except that the formulation was changed to the formulation described in Table B1.
  • Example B1 (Water dispersion process and polymerization process)
  • Example B2 (Synthesis of polyurea coating / clothianidin-containing sustained release particles: corresponding to the third embodiment)
  • a 200 mL beaker (1) 85 g of the slurry B prepared in Preparation Example B2 is charged with 15 g of T-1890 and 0.5 g of Parroyl L, and stirred at room temperature, whereby T-1890 and Parroyl L are added to the slurry B. Dissolved in.
  • an oil phase component containing T-1890, Parroyl L and Slurry B was prepared.
  • the oil phase component was added to a 500 mL beaker (2). K.
  • the oil phase component was dispersed by stirring with a homomixer MARK 2.5 type (manufactured by PRIMIX Co., Ltd.) at a rotation speed of 6000 rpm for 5 minutes to prepare a suspension (aqueous dispersion).
  • the suspension (aqueous dispersion) was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, and stirred under a nitrogen stream.
  • Interfacial polymerization was started when a 10% by mass aqueous solution of diethylenetriamine was added, and suspension polymerization was started when 55 ° C. was reached, which is the temperature during the temperature increase of the suspension to 70 ° C.
  • clothianidin was dispersed in a matrix formed by suspension polymerization, and a suspension (suspension agent) of sustained-release particles in which the matrix was coated with polyurea was obtained.
  • the suspension after the reaction is cooled to 30 ° C. or lower, so that clothianidin is dispersed in the matrix, and the matrix is a suspension of sustained release particles (suspension) coated with polyurea formed by interfacial polymerization. A suspension was obtained.
  • the median diameter of the sustained release particles in the suspension was measured with a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.). The results are listed in Table B2. The measurement of the median diameter is the same for the following Examples, Reference Examples and Comparative Examples, and the results are shown in Tables B2 to B6.
  • Example B2 (Synthesis of polyurea-coated / clothianidin-containing sustained release particles: corresponding to the third embodiment)
  • a 200 mL beaker (1) 50 g of slurry A prepared in Preparation Example B1 was charged with 17.5 g of i-BMA, 17.5 g of EGDMA, 15 g of T-1890, and 0.5 g of Parroyl L, and stirred at room temperature.
  • I-BMA, EGDMA, T-1890 and Parroyl L were dissolved in slurry A.
  • an oil phase component containing i-BMA, EGDMA, T-1890, Parroyl L and Slurry A was prepared.
  • the oil phase component was added to a 500 mL beaker (2). K.
  • the oil phase component was dispersed by stirring for 5 minutes at a rotation speed of 5000 rpm with a homomixer MARK 2.5 type (manufactured by Primix) to prepare a suspension (aqueous dispersion).
  • the suspension (aqueous dispersion) was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, and stirred under a nitrogen stream.
  • Interfacial polymerization was started when a 10% by mass aqueous solution of diethylenetriamine was added, and suspension polymerization was started when 55 ° C. was reached, which is the temperature during the temperature increase of the suspension to 70 ° C.
  • clothianidin was dispersed in a matrix formed by suspension polymerization, and a suspension (suspension) of sustained-release particles in which the matrix was coated with polyurea formed by interfacial polymerization was obtained.
  • suspension after the reaction was cooled to 30 ° C. or less to obtain a suspension (suspension) of sustained release particles in which clothianidin was dispersed in the matrix and the matrix was coated with polyurea.
  • Example B3 Synthesis of polyurea-coated / clothianidin-containing sustained release particles: corresponding to the third embodiment
  • the suspension was treated in the same manner as in Example B2 so that clothianidin was dispersed in the matrix and the matrix was coated with polyurea. A suspension was obtained.
  • the suspension is heated to 60 ° C. and maintained at the same temperature for 1 hour, and then the suspension is heated to 70 ° C. and maintained at the same temperature for 2 hours. The suspension was then heated to 80 ° C. and maintained at that temperature for 1 hour.
  • Interfacial polymerization was started when a 10% by mass aqueous solution of diethylenetriamine was added, and suspension polymerization was started when 55 ° C. was reached, which is the temperature during the heating of the suspension to 60 ° C.
  • Example B4 (Synthesis of polyurea coating / clothianidin-containing sustained release particles: corresponding to the third embodiment) Except having changed polymerization conditions as follows, it processed similarly to Example B2, and obtained the suspension (suspension agent) of the sustained release particle
  • the suspension was heated to 50 ° C. and maintained at the same temperature for 2 hours, and then the suspension was heated to 60 ° C. and maintained at the same temperature for 1 hour. Subsequently, the suspension was heated to 70 ° C. and maintained at the same temperature for 2 hours, and then the suspension was heated to 80 ° C. and maintained at the same temperature for 1 hour.
  • Interfacial polymerization starts when a 10% by mass aqueous solution of diethylenetriamine is added, and suspension polymerization reaches 55 ° C., which is the temperature after the start of interfacial polymerization and during the heating of the suspension to 60 ° C. Started at the time.
  • Example B5 (Synthesis of polyurea-coated / clothianidin-containing sustained release particles: corresponding to the third embodiment) Except having changed polymerization conditions as follows, it processed similarly to Example B2, and obtained the suspension (suspension agent) of the sustained release particle
  • the suspension was heated to 60 ° C. and maintained at the same temperature for 1 hour. Thereafter, an aqueous solution of diethylenetriamine is added. Immediately after that, the suspension is heated to 70 ° C. and maintained at the same temperature for 2 hours, and then the suspension is heated to 80 ° C. and heated to 1 at the same temperature. Maintained for hours.
  • the suspension polymerization starts when reaching 55 ° C., which is the temperature during the temperature increase of the suspension to 60 ° C.
  • the interfacial polymerization is after the start of the suspension polymerization and is a 10% by mass aqueous solution of diethylenetriamine. It started when I put in.
  • Example B10 to Example B13, Example B19 to Example B23, Example B27, Example B28, Example B31, and Example B32 Polyurea coating / Synthesis of clothianidin-containing sustained release particles
  • Example B28: corresponding to the fourth embodiment A suspension (suspension) of sustained-release particles coated with polyurea and containing clothianidin was processed in the same manner as in Example B2, except that the formulation was changed as described in Tables B3 to B5. It was.
  • Example B6 Synthesis of polyurea-coated / clothianidin-containing sustained release particles: corresponding to the third embodiment
  • a 200 mL beaker (1) 50 g of slurry C prepared in Preparation Example B3 was charged with 17.5 g of styrene, 17.5 g of EGDMA, 15 g of T-1890, and 0.5 g of Parroyl L, and stirred at room temperature.
  • Styrene, EGDMA, T-1890 and Parroyl L were dissolved in slurry C.
  • an oil phase component containing styrene, EGDMA, T-1890, Parroyl L and slurry C was prepared.
  • an oil phase component in which styrene, EGDMA, T-1890 and Parroyl L are dissolved is added to a 500 mL beaker (2).
  • the oil phase component was dispersed by stirring for 5 minutes at a rotation speed of 5000 rpm with a homomixer MARK 2.5 type (manufactured by Primix) to prepare a suspension (aqueous dispersion).
  • the suspension (aqueous dispersion) was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, and stirred under a nitrogen stream.
  • Interfacial polymerization was started when a 10% by mass aqueous solution of diethylenetriamine was added, and suspension polymerization was started when 55 ° C. was reached, which is the temperature during the temperature increase of the suspension to 70 ° C.
  • clothianidin was dispersed in a matrix formed by suspension polymerization, and a suspension (suspension agent) of sustained-release particles in which the matrix was coated with polyurea formed by interfacial polymerization was obtained.
  • suspension after the reaction was cooled to 30 ° C. or less to obtain a suspension (suspension) of sustained release particles in which clothianidin was dispersed in the matrix and the matrix was coated with polyurea.
  • Example B7 to Example B9, Example B14 to Example B18, Example B24 to Example B26, Example B29, Example B30, Example B33, Example B34 (Polyurea coating / Synthesis of clothianidin-containing sustained release particles) (Example B7 to Example B9, Example B14 to Example B18, Example B24 to Example B26, Example B33, and Example B34: corresponding to the third embodiment)
  • Example B35 (synthesis of imidacloprid-containing sustained release particles: corresponding to the third embodiment) A suspension (suspension) of sustained-release particles containing imidacloprid was obtained in the same manner as in Example B2, except that the formulation was changed according to the description in Table B5.
  • Reference Example B1 Synthesis of clothianidin-containing sustained release particles: corresponding to reference form
  • 100 g of slurry B prepared in Preparation Example B2 and 0.5 g of Parroyl L were charged and stirred at room temperature to dissolve Parroyl L in Slurry B.
  • an oil phase component containing Parroyl L and Slurry B was prepared.
  • an oil phase component containing Parroyl L was added to a 500 mL beaker (2).
  • K The oil phase component was dispersed in water by stirring with a homomixer MARK 2.5 type (manufactured by Primix) at a rotational speed of 6000 rpm for 5 minutes to prepare a suspension (aqueous dispersion).
  • suspension aqueous dispersion
  • 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.
  • 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.
  • suspension after the reaction was cooled to 30 ° C. or lower to obtain a suspension (suspension agent) of sustained-release particles containing clothianidin.
  • Reference Example B2 Synthesis of clothianidin-containing sustained release particles: corresponding to reference form
  • 100 g of slurry B prepared in Preparation Example B2 and 0.5 g of Parroyl L were charged and stirred at room temperature to dissolve Parroyl L in Slurry B.
  • an oil phase component containing Parroyl L and Slurry B was prepared.
  • the oil phase component was added to a 500 mL beaker (2).
  • K The oil phase component was dispersed in water by stirring with a homomixer MARK 2.5 type (manufactured by Primix) at a rotational speed of 6000 rpm for 5 minutes to prepare a suspension (aqueous dispersion).
  • suspension polymerization was carried out under the same conditions as in Reference Example B1 to obtain a suspension (suspension) of sustained release particles containing clothianidin.
  • Reference Example B3 Synthesis of clothianidin-containing sustained release particles: corresponding to reference form
  • 100 g of the slurry A prepared in Preparation Example B1 and 0.5 g of Parroyl L were charged and stirred at room temperature to dissolve Parroyl L in the slurry A.
  • an oil phase component containing Parroyl L and Slurry A was prepared.
  • the oil phase component was added to a 500 mL beaker (2). K.
  • the oil phase component was dispersed by stirring with a homomixer MARK 2.5 type (manufactured by PRIMIX Co., Ltd.) at a rotation speed of 6000 rpm for 5 minutes to prepare a suspension (aqueous dispersion).
  • suspension polymerization was carried out under the same conditions as in Reference Example B1 to obtain a suspension (suspension) of sustained release particles containing clothianidin.
  • “1” in the polymerization condition column indicates that immediately after the diethylenetriamine aqueous solution was added to the suspension, the suspension was heated to 70 ° C. and maintained at the same temperature for 5 hours. This shows that the suspension was heated to 80 ° C. and maintained at the same temperature for 2 hours.
  • Example B36 Keratin and molding of powder of sustained release particles and thermoplastic resin
  • the suspension of sustained-release particles prepared in Example B1 was filtered through a 100-mesh filter cloth and dried at room temperature for 1 day to obtain sustained-release particle powder (powder).
  • the obtained sustained-release particle powder (powder) and high-density polyethylene (HDPE) Hi-Zex 6300M were 0.25% clothianidin with respect to HDPE.
  • Example B37 (kneading and molding of the powder of Example B27 and polyethylene) A strip-shaped treatment was carried out in the same manner as in Example B36, except that the sustained-release particle suspension prepared in Example B27 was used instead of the sustained-release particle suspension prepared in Example B1. A molded product was obtained.
  • Reference Example B4 (kneading and molding of the powder of Reference Example B1 and polyethylene) A strip-shaped treatment was carried out in the same manner as in Example B36 except that the suspension of sustained release particles prepared in Reference Example B1 was used instead of the suspension of sustained release particles prepared in Example B1. A molded product was obtained.
  • Reference Example B5 (kneading and molding of the powder of Reference Example B3 and polyethylene) A strip type treatment was carried out in the same manner as in Example B36, except that the suspension of sustained release particles prepared in Example B3 was used instead of the suspension of sustained release particles prepared in Example B1. A molded product was obtained.
  • Example B38 Suspension of sustained release particles prepared in Example B1 (clothianidin concentration 7.0 mass%) 1 with respect to 100 parts by mass of Kagalite 2 (manufactured by Kagalite Kogyo Co., Ltd., fine particles of pumice, particle size 425 to 1400 ⁇ m) 1 .4 parts by mass were blended and then dried to obtain clothianidin granules.
  • the clothianidin concentration in the granules was about 0.1% by mass.
  • Example B39 In place of the suspension of sustained release particles prepared in Example B1, 1.4 part by mass of the suspension of sustained release particles prepared in Example B27 (clothianidin concentration 7.0 mass%) was used. Were treated in the same manner as in Example B38 to obtain clothianidin granules. The clothianidin concentration in the granules was about 0.1% by mass.
  • Example B7 Example B38 except that 1.2 parts by mass of the sustained-release particle suspension (clothianidin concentration: 8.3% by mass) prepared in Reference Example B3 was used instead of the suspension prepared in Example B1. In the same manner as above, clothianidin granules were obtained. The clothianidin concentration in the granules was about 0.1% by mass. 1. Observation of SEM (Scanning Electron Microscope) Example B1, Example B2, Example B6, Example B30 and Example B35 suspensions (suspension agents) were dropped onto the sample stage, and then After the water was distilled off, the obtained sustained-release particles were observed with a scanning electron microscope Hitachi TM-3000 (manufactured by Hitachi High-Technologies Corporation) by SEM.
  • SEM Scanning Electron Microscope
  • Example B1 Example B2, Example B6, Example B30, and Example B35 are shown in FIGS. B3 to B7, respectively.
  • TEM Transmission Electron Microscope, Transmission Electron Microscope
  • a cross section was obtained by cutting this with an ultramicrotome, stained with osmium tetroxide, and further stained with ruthenium tetroxide as necessary, and this was 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.
  • FIGS. B8 to B11 Image processing diagrams of TEM photographs of Example B2 and Reference Examples B1 to B3 are shown in FIGS. B8 to B11, respectively.
  • FIGS. B8 to B11 the blank indicated by reference numeral 3 is a trace of clothianidin being dissolved and dropped in the process of collecting and recovering the cut ultrathin section in water.
  • the shape of the domain formed from clothianidin is shown in FIG. Represents.
  • the shell 7 is made of polyurea, and specifically, the polyurea concentration with respect to the matrix 2 decreases as it goes inward from the outermost layer (outermost surface). . Further, the shell 7 is located (unevenly distributed) in the surface layer portion of the matrix 2 so as to surround the domain 3.
  • Test A The concentration of each of the suspensions of Examples B1 to B35 is 0.25% for the concentration of the antibiotic compound (for Examples B1 to B34, the concentration of clothianidin, and for Example B35, the concentration of imidacloprid). Diluted with deionized water. 1 mL of the diluted suspension was weighed into a glass bottle, and 4 mL of saturated calcium hydroxide solution was added to prepare a test solution. This test solution was allowed to stand at a constant temperature of 40 ° C.
  • Example B2 to Example B4 the interfacial polymerization is started before the start of the suspension polymerization, so that the phase separation between the clothianidin-containing matrix and the shell can proceed well.
  • Example B5 the interfacial polymerization is started after the start of the suspension polymerization, so that the phase separation between the matrix and the shell cannot proceed well, and Examples B2 to B4 are the same as Example B5. Compared to, it has excellent alkali resistance.
  • Example B6 to Example B8 the interfacial polymerization is started before the start of the suspension polymerization, so that the phase separation between the clothianidin-containing matrix and the shell can proceed well.
  • Example B9 the interfacial polymerization is started after the start of the suspension polymerization, so that the phase separation between the matrix and the shell cannot proceed well, and Examples B6 to B8 are the same as Example B9. Compared to, it has excellent alkali resistance.
  • Example B13 Example B12, Example B11, Example B2, and Example B10
  • the blending ratio of T-1890 to i-BMA and EGDMA increases in this order. Therefore, in Example B13, Example B12, Example B11, Example B2, and Example B10, the thickness of the shell (the concentration of the shell in the sustained-release particles) increases in this order. Therefore, in Example B13, Example B12, Example B11, Example B2, and Example B10, the alkali resistance is improved in this order.
  • Example B18 Example B17, Example B16, Example B15, Example B6, and Example B14
  • the blending ratio of T-1890 to styrene and EGDMA increases in this order. Therefore, in Example B18, Example B17, Example B16, Example B15, Example B6, and Example B14, the thickness of the shell (the concentration of the shell in the sustained-release particles) increases in this order. Therefore, Example B18, Example B17, Example B16, Example B15, Example B6, and Example B14 have improved alkali resistance in this order.
  • Example B28 In Example B28, Example B27, and Example B2, the blending ratio of clothianidin in the sustained release particles decreased in this order, and Example B28, Example B27, and Example B2 decreased in resistance in this order. Alkalinity is improved.
  • Example B30 Example B29 and Example B2
  • the blending ratio of clothianidin in the sustained release particles is reduced in this order, and the alkali resistance is improved.
  • Example B2 and Example B19 to Example B23 Example B2 and Example B19 to Example B21 in which the proportion of i-BMA is relatively high are examples in which the proportion of i-BMA is extremely low.
  • the phase separation between the shell and the matrix containing clothianidin proceeds better. Therefore, Example B2, Example B20, and Example B21 are excellent in alkali resistance compared to Example B22 and Example B23.
  • Example B6 and Example B23 to Example B26 Example B6, Example B24, and Example B25, in which the blending ratio of styrene is relatively high, are different from Examples B23 and B26 in which the blending ratio of styrene is extremely low.
  • Example B6, Example B24, and Example B25 are superior in alkali resistance compared to Example B23 and Example B26.
  • Example B6 contains styrene as the polymerizable vinyl monomer, Example B2 contains i-BMA as the polymerizable vinyl monomer, and the styrene of Example B6 is compared to i-BMA of Example B2. Since the hydrophobicity is high, the phase separation between the shell and the polymer proceeds well. Therefore, Example B6 is excellent in alkali resistance compared to Example B2.
  • Test B The suspension of sustained release particles produced in Example B1, Example B2 and Reference Examples B1 to B3 was filtered through a 100-mesh filter cloth and dried at room temperature for 1 day to obtain a sustained release particle powder ( Dust) was obtained. These powders were diluted 1000 times with deionized water, of which 6.3 mL was weighed into a glass bottle, and 2 mL of saturated calcium hydroxide solution was added to prepare a test solution. This test solution was allowed to stand at a constant temperature of 40 ° C.
  • the suspension containing the sustained release particles of Examples B1 and 2 having a shell has a clothianidin residual rate of 1 and 7 days after the start of the test. In any of the cases, it is found that the amount is higher than the suspension containing the sustained release particles of Reference Example B1 to Reference Example B3 having no shell. 3-2.
  • Granules of sustained release particles 1.0 g of the granules obtained in Example B38, Example B39, Reference Example B6, and Reference Example B7 are weighed, and 3.6 mL of deionized water and 2 mL of saturated aqueous calcium hydroxide solution are used. Test solutions were prepared by addition. This test solution was allowed to stand at a constant temperature of 40 ° C.
  • the granules of Example B38 and Example B39 containing the sustained release particles of Example B1 and Example B2 having a shell have clothianidin residual rate. 1 and 7 days after the start of the test, it is higher than the granules of Reference Example B6 and Reference Example B7 containing the sustained release particles of Reference Example B1 and Reference Example B3 which do not have a shell.
  • Mold prevention test of molded article Silica sand poured to have a moisture content of 8% (optimum moisture content for termite activity) was filled in a plastic container, and then the surface of the quartz sand was filled with Example B36 and Example B37. A strip-shaped molded product was installed.
  • Example B36 and Example B37 a remarkable ant killing effect was recognized.
  • the sustained-release particles obtained by the method for producing sustained-release particles are used in various applications, for example, building materials, for example, electric wire cable materials, and covering materials for the electric wire cables, for example, conduits such as gas, and It is used for the covering material of the conduit, for example, textile products such as clothes and mosquito nets.

Abstract

L'invention concerne un procédé de production de particules à libération prolongée (1) comprenant une étape de préparation de composant en phase huileuse contenant une bouillie hydrophobe préparée par dispersion d'un composé à activité antibiotique, qui est hydrophobe et sensiblement insoluble dans un monomère vinylique polymérisable hydrophobe et dans un monomère vinylique hydrophobe polymérisable en l'absence de solvant ; une étape de dispersion dans l'eau dans laquelle un liquide de dispersion dans l'eau est préparé par dispersion de la bouillie hydrophobe dans l'eau ; et une étape de polymérisation dans laquelle le monomère vinylique polymérisable est soumis à une polymérisation en émulsion, ce qui permet de produire un polymère.
PCT/JP2014/072837 2013-08-30 2014-08-29 Particules à libération prolongée et leur procédé de production, matériau de moulage et article moulé WO2015030213A1 (fr)

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AU2014312780A AU2014312780A1 (en) 2013-08-30 2014-08-29 Extended release particles, method for producing same, molding material and molded article
US14/914,949 US20160235068A1 (en) 2013-08-30 2014-08-29 Controlled release particles, production method thereof, molding material, and molded article
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