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WO2017030041A1 - Particules à développement de fonction et leur procédé de production - Google Patents

Particules à développement de fonction et leur procédé de production Download PDF

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Publication number
WO2017030041A1
WO2017030041A1 PCT/JP2016/073357 JP2016073357W WO2017030041A1 WO 2017030041 A1 WO2017030041 A1 WO 2017030041A1 JP 2016073357 W JP2016073357 W JP 2016073357W WO 2017030041 A1 WO2017030041 A1 WO 2017030041A1
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WIPO (PCT)
Prior art keywords
resin
particles
porous inorganic
function
inorganic particles
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PCT/JP2016/073357
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English (en)
Japanese (ja)
Inventor
大島　純治
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Osaka Gas Chemicals Co Ltd
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Osaka Gas Chemicals Co Ltd
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Priority to JP2016558146A priority Critical patent/JPWO2017030041A1/ja
Publication of WO2017030041A1 publication Critical patent/WO2017030041A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a function-expressing particle and a method for producing the same, for example, bactericides, antibacterial agents, antiseptics, algae-proofing agents, fungicides, herbicides, insecticides, attractants and repellents, as well as flame retardants, curing agents
  • the present invention relates to a function-expressing particle used for an agent and the like, and a production method thereof.
  • Patent Document 1 a porous fine particle in which a supported substance is held by encapsulating the supported substance in porous fine particles and coating the surface thereof with a polymer compound or a curable compound has been proposed (for example, Patent Document 1). reference.).
  • Patent Document 1 an acrylic resin (thermoplastic resin) or an epoxy resin (thermosetting resin) is used as a polymer compound or a curable compound.
  • Patent Document 1 an organic solvent solution of an acrylic resin or an epoxy resin is prepared, filled in the pores of the porous fine particles in which the supported substance exists, and then the organic solvent in the organic solvent solution is removed. As a result, porous fine particles are manufactured. However, when the porous fine particles are manufactured in this way, the organic solvent is removed, and therefore the volume of the acrylic resin or the epoxy resin becomes smaller than the total volume of the holes. Therefore, it becomes difficult to hold the supported substance with respect to the porous fine particles, and there is a problem that the supported substance leaks out of the pores of the porous particle.
  • An object of the present invention is to provide a function-expressing particle that can contain a sufficient amount of resin and that can reliably seal a functional component within the pores of the porous particle by such a resin, and a method for producing the same. There is to do.
  • the present invention [1] containing porous inorganic particles, a functional component taken into the pores of the porous inorganic particles, and a resin sealing the functional component in the pores, the resin being curable
  • a functionally expressed particle characterized by being a cured product obtained by curing a vinyl monomer solution of a resin;
  • the vinyl monomer solution is at least one selected from the group consisting of an unsaturated polyester resin, an epoxy acrylate resin, and a urethane acrylate resin.
  • Expressed particles [9] Any one of the above [1] to [8], wherein the ratio of the total volume of the functional component and the resin to the oil-absorbable volume of the porous inorganic particles is 0.75 or less.
  • Functionally expressed particles according to Item [10] Any one of the above [1] to [9], wherein the ratio of the total volume of the functional component and the resin to the oil-absorbable volume of the porous inorganic particles exceeds 0.50.
  • Functionally expressed particles according to Item [11] A liquid containing a functional component is blended in the porous inorganic particles so that the ratio of the volume of the liquid to the oil-absorbable volume of the porous inorganic particles is 0.75 or less.
  • a vinyl monomer solution of a curable resin in the porous inorganic particles In the pores of the porous inorganic particles (1), a vinyl monomer solution of a curable resin in the porous inorganic particles, and the porous inorganic particles having a total volume of the functional component and the vinyl monomer solution.
  • the step (2) of incorporating the vinyl monomer solution into the pores of the porous inorganic particles by blending so that the ratio of the particles to the oil-absorbable volume is 0.75 or less, and the vinyl monomer solution A method of producing function-expressing particles, comprising a step (3) of sealing the functional component in the hole by curing; [12] The method for producing function-expressing particles according to [11] above, wherein the viscosity of the vinyl monomer solution at 23 ° C.
  • the vinyl monomer solution of the curable resin is a thermosetting resin composition, and the thermosetting resin composition has a normal temperature gelation time measured according to JIS K6901-A method (2008).
  • the vinyl monomer solution of the curable resin is a thermosetting resin composition, The above-mentioned [11] to [13], wherein the thermosetting resin composition has a normal temperature gelation time measured in accordance with JIS K6901-A method (2008) of 1 hour or less. It is a manufacturing method of the function expression particles given in any 1 paragraph.
  • the vinyl monomer solution of the curable resin is blended with the porous inorganic particle, and the vinyl monomer solution is added to the pores of the porous inorganic particle into which the functional component is incorporated. And the vinyl monomer solution is cured. Therefore, as in Patent Document 1, all the vinyl monomer solution in the pores is cured to form a cured product without requiring the step of removing the organic solvent at the time of coating with the polymer compound. A large volume can be secured. Therefore, a sufficient amount of functional components can be reliably sealed in the porous inorganic particles by such a resin.
  • the function-expressing particles of the present invention can exhibit a function by releasing a sufficient amount of functional components under physical conditions such as destruction.
  • One embodiment of the function-expressing particle of the present invention contains porous inorganic particles, a functional component taken into the pores of the porous inorganic particle, and a resin that seals the functional component in the porous inorganic particle. To do.
  • the porous inorganic particles, the functional component, the resin, and the production method, application, and effects of the function-expressing particles will be described in order.
  • porous inorganic particles examples include silicates such as calcium silicate, barium silicate, magnesium silicate, and zeolite, such as calcium phosphate, barium phosphate, magnesium phosphate, and phosphoric acid.
  • silicates such as calcium silicate, barium silicate, magnesium silicate, and zeolite
  • calcium phosphate calcium phosphate
  • barium phosphate magnesium phosphate
  • phosphoric acid examples thereof include phosphates such as zirconium and apatite, for example, silicon oxide (for example, silicon dioxide (silica), silicon monoxide, etc.), oxides such as alumina and magnesium oxide, and a mixture of two or more of these compounds. It is done.
  • an oxide more preferably silicon oxide, and still more preferably silica.
  • the porous inorganic particles have a spherical shape (including a true spherical shape) or an indefinite shape.
  • the porous inorganic particles are usually aggregates (secondary particles and the like) in which primary particles are aggregated with each other.
  • the porous inorganic particles are made of silica (silicon dioxide) and have an indefinite shape
  • the porous inorganic particles are produced, for example, by a wet method, a dry method, or the like, preferably by a wet method.
  • silica is generated by neutralizing water glass (sodium silicate aqueous solution) with a mineral acid such as sulfuric acid.
  • a mineral acid such as sulfuric acid.
  • the porous inorganic particles produced as described above can be prepared by firing.
  • the porous inorganic particles are oxides (specifically, silicon oxide, etc.)
  • the OH groups (specifically, silanol groups, etc.) present on the surface are removed by firing the porous inorganic particles. Is done.
  • the functional component incorporates a compound that reacts with a silanol group (specifically, a compound containing a silanol group or a hydroxyl group) or an interactive compound (specifically an amino group, etc.) into silicon oxide. In some cases, it is preferable to remove the silanol group of silicon oxide by calcination because the functional component is easily released.
  • porous inorganic particles are made of silica (silicon dioxide) and have a spherical shape, for example, in an aqueous phase droplet of a desired size dispersed and stabilized in an inert solvent such as a hydrocarbon, It is produced by producing silica by a wet method.
  • silica silicon dioxide
  • the pores of the porous inorganic particles mean pores inside the primary particles forming the porous inorganic particles and voids between the primary particles.
  • the pore volume of porous inorganic particles (total volume of pores of primary particles) is, for example, 1.0 mL / g or more, preferably 1.5 mL / g or more, and, for example, 3.0 mL / g or less. .
  • the pore volume is measured by a nitrogen gas adsorption method.
  • the pore volume of the porous inorganic particles means the pore volume (mL) per unit mass (g) in the primary particles forming the porous inorganic particles.
  • the specific surface area of the porous inorganic particles is, for example, 150 m 2 / g or more, preferably 300 m 2 / g or more, and, for example, 1000 m 2 / g or less.
  • the specific surface area is measured by a simple BET method.
  • the value obtained by multiplying the pore volume of the porous inorganic particles by 4 and dividing by the specific surface area is usually used as the average pore diameter of the porous inorganic particles.
  • the oil absorption amount of the porous inorganic particles is, for example, 100 mL / 100 g or more, preferably 250 mL / 100 g or more, and, for example, 500 mL / 100 g or less.
  • the oil absorption is measured according to JIS K5101-13-2 (2004).
  • the amount of oil absorption of the porous inorganic particles is the sum of the pore volume inside the primary particles forming the porous inorganic particles, the void volume between the primary particles, and the minimum volume at which the oil wets the surface of the secondary particles.
  • the volume (mL) per 100 g of the fine inorganic particles is shown. Since the oil absorption amount of the porous inorganic particles is the measured value shown above, the pore volume, the specific surface area, and the average pore diameter are not uniquely correlated.
  • the average value of the maximum length of the porous inorganic particles is, for example, 0.5 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, , 50 ⁇ m or less, preferably 30 ⁇ m or less.
  • Functional component is taken into the pores of the porous inorganic particles and sealed (coated) with a resin. Then, the functional component is released from the resin and released from the pores due to physical destruction of the particles during use. Alternatively, the functional component can exhibit sustained release in a harsh environment where it is easily leached during use.
  • Examples of functional components include antibiotic active compounds, flame retardants, curing agents, pigments, fragrances, enzymes, and the like, and preferably antibiotic active compounds, flame retardants, and curing agents.
  • antibiotic active compounds examples include a water-insoluble antibiotic active compound (water-insoluble component) at room temperature and a water-soluble antibiotic active compound (water-soluble component) at room temperature.
  • the water insolubility is a property that does not substantially dissolve in water at room temperature (20 ° C.), and specifically includes a property that does not dissolve in water at all and a property that dissolves in a very small amount (hardly soluble).
  • the solubility of water-insoluble substances in water at room temperature is, for example, 10 g / L or less, and further 5 g / L or less.
  • water-soluble is a property that is substantially soluble in water at room temperature (25 ° C.), and the solubility of the water-soluble substance in water at room temperature is, for example, more than 10 g / L, or more than 20 g / L. It is.
  • Water-insoluble antibiotic active compounds include antibiotic active compounds disclosed in International Publication No. 2011/030824, International Publication No. 2013/100102, and Japanese Patent Application Laid-Open No. 04-009303. And capsaicins disclosed in.
  • water-insoluble antibiotic active compounds have antibacterial, antibacterial, antiseptic, algae, fungicidal, herbicidal, insecticidal, attracting and repellent antibacterial agents, antibacterial agents, antiseptics, and algae control agents. Selected from fungicides, herbicides, insecticides, attractants and repellents.
  • antibacterial, antifungal and antifungal agents include, for example, organic iodine compounds, triazole compounds, carbamoylimidazole compounds, dithiol compounds, isothiazoline compounds, nitroalcohol compounds, paraoxybenzoic acid
  • examples include esters.
  • organic iodine compound examples include 3-iodo-2-propynylbutylcarbamate (IPBC), 1-[[(3-iodo-2-propynyl) oxy] methoxy] -4-methoxybenzene, 3-bromo-2 , 3-diiodo-2-propenylethyl carbonate, and the like.
  • triazole compound examples include 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole (propico Nazole), bis (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethylsilane (also known as flusilazole, 1-[[bis (4-fluorophenyl) methylsilyl] methyl] -1H- 1,2,4-triazole) and the like.
  • carbamoylimidazole compound examples include N-propyl-N- [2- (2,4,6-trichloro-phenoxy) ethyl] imidazole-1-carboxamide (prochloraz).
  • dithiol-based compound examples include 4,5-dichloro-1,2-dithiol-3-one.
  • isothiazoline compound examples include 2-n-octyl-4-isothiazolin-3-one (OIT) and 4,5-dichloro-2-n-octylisothiazolyl-3-one (DCOIT). .
  • nitroalcohol compound examples include 2,2-dibromo-2-nitro-1-ethanol (DBNE).
  • paraoxybenzoic acid ester examples include butyl paraoxybenzoate and propyl paraoxybenzoate.
  • examples of the ant-preventing agent include pyrethroid compounds, neonicotinoid compounds, organochlorine compounds, organophosphorus compounds, carbamate compounds, oxadiazine compounds, and the like.
  • pyrethroid insecticides such as pyrethrin, cineline, and jasmolin obtained from Shirobanamushiyogiku, and arelesrin, bifenthrin, acrinathrin, alpha cypermethrin, tralomethrin, cifluthrin
  • neonicotinoid compounds include (E) -N 1 -[(6-chloro-3-pyridyl) methyl] -N 2 -cyano-N 1 -methylacetamidine (acetamipride).
  • organochlorine compounds examples include Kelsen.
  • organophosphorus compounds examples include oxime, pyridafenthion, fenitrothion, tetrachlorbinphos, diclofenthion, propetanephos, and the like.
  • carbamate compounds examples include fenocarb and propoxur.
  • Examples of the oxadiazine compound include indoxacarb.
  • examples of the herbicide include pyraclonyl, pendimethalin, indanophan and the like.
  • insecticide examples include pyriproxyfen.
  • repellents examples include diet, capsaicins (pungent ingredients), and the like. Preferably, capsaicins are used.
  • capsaicins examples include capsaicin (N-[(4-hydroxy-3-methoxyphenyl) methyl] -8-methyl-6-nonenamide) and capsaicin derivatives.
  • capsaicin derivatives include N-vanillyl nonanamide (noneric acid vanillylamide), decylic acid vanillylamide, nordihydrocapsaicin, dihydrocapsaicin, homodihydrocapsaicin, homocapsaicin and the like.
  • Preferred capsaicins include capsaicin and N-vanillyl nonanamide.
  • water-insoluble antibiotic active compound examples include antiseptic and antifungal agents and repellents.
  • the water-soluble antibiotic active compound is selected from, for example, wood preservatives that impart antiseptic properties to wood, for example, repellents having antibiotic activity such as repelling.
  • Examples of the water-soluble antibiotic compound include sodium borate and denatonium benzoate (a bitter component).
  • Sodium borate includes hydrated salts, specifically, disodium octaborate tetrahydrate and the like.
  • water-soluble antibiotic compounds include 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT), 2-methyl-4-isothiazolin-3-one (H-MIT). ), 2-bromo-2-nitropropane-1,3-diol (bronopol), 2-pyridinethiol-1-oxide sodium (NaPt), hexahydro-1,3,5-tris (2-hydroxyethyl) -1 , 3,5-triazine, methyl 1H-benzimidazol-2-ylcarbamate hydrochloride (carbendazim hydrochloride), and the like.
  • Flame retardant examples include a water-insoluble flame retardant (water-insoluble component) at room temperature and a water-soluble flame retardant (water-soluble component) at room temperature.
  • Water-insoluble flame retardant examples include antimony oxide, aluminum hydroxide, and magnesium hydroxide.
  • Water-soluble flame retardant examples include trimethyl phosphate, guanidine phosphate, and ammonium polyphosphate.
  • the curing agent is a functional component that is released from the function-expressing particles and can undergo a curing reaction (crosslinking reaction) with a resin (second resin described later).
  • the curing agent is also a crosslinking agent (first curing agent) for making the resin (second resin) a crosslinked resin (cured resin) having a three-dimensional network structure. Note that the curing agent and the crosslinking agent are not clearly distinguished.
  • curing agent is a 1st hardening
  • the curing agent has a plurality of first functional groups.
  • a 1st functional group can react with the 2nd functional group which resin (2nd resin) mentioned later has.
  • Examples of the first functional group include an epoxy group, an N-methylol group (N is a nitrogen atom), an N-alkoxymethyl group (N is a nitrogen atom), an isocyanate group, a nitrogen atom-containing group, an aldehyde group, an oxazoline group, and a hydrazide. Group, silanol group, aziridine group, acetoacetoxy group, diacetone group and the like.
  • a plurality of single-type first functional groups are contained in the curing agent, or a plurality of types of first functional groups are contained in the curing agent.
  • a plurality of single-type first functional groups are contained in the curing agent.
  • the curing agent for example, epoxy group-containing compound, N-methylol group-containing compound, N-alkoxymethyl group, isocyanate group-containing compound, nitrogen atom-containing compound, aldehyde group-containing compound, oxazoline group-containing compound, hydrazide
  • examples thereof include a group-containing compound, a silanol group-containing compound, an aziridine group-containing compound, an acetoacetoxy group-containing compound, and a diacetone group-containing compound.
  • Preferred examples of the curing agent include epoxy group-containing compounds, N-methylol group-containing compounds, isocyanate group-containing compounds, and nitrogen atom-containing compounds.
  • the curing agents can be used alone or in combination.
  • the curing agent may be either water-insoluble at room temperature or water-soluble at room temperature.
  • Epoxy group-containing compound examples include an epoxy resin, an epoxy group-containing vinyl monomer (copolymerization) oligomer, an epoxidized unsaturated fatty acid ester, and an epoxidized polybutadiene.
  • an epoxy resin is used.
  • Examples of the epoxy resin include glycidyl ether type epoxy resins (bisphenol A type, bisphenol F type bisphenol type epoxy resins, phenol novolac and cresol novolak type epoxy resins, etc.), alicyclic epoxy resins, glycidyl ester type epoxy resins, glycidyl.
  • Examples include amine type epoxy resins and heterocyclic epoxy resins.
  • Examples of the epoxy group-containing vinyl monomer in the oligomer of the epoxy group-containing vinyl monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
  • Examples of the unsaturated fatty acid ester in the epoxidized unsaturated fatty acid ester include linseed oil, soybean oil, and tung oil. Epoxy group-containing compounds can be used alone or in combination.
  • the epoxy group in the epoxy group-containing compound can react with an amino group, a hydroxyl group, a carboxyl group, an acid anhydride group (described later) and the like contained in the second resin.
  • N-methylol group-containing compounds, N-alkoxymethyl group-containing compounds N-methylol group-containing compounds include, for example, methylolated melamine (melamine initial condensate), methylolated urea (urea initial condensate), urea glyoxal formaldehyde reactant (Glyoxal resin), N-methylolacrylamide (copolymerization) oligomer, and the like.
  • N-alkoxymethyl group-containing compound examples include 3,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine, N-methoxymethylacrylamide (copolymerization) oligomer, N-butoxy Examples thereof include methyl acrylamide (copolymerized oligomers, etc.)
  • the N-methylol group-containing compound and / or the N-alkoxymethyl group-containing compound can be used alone or in combination.
  • the N-methylol group in the N-methylol group-containing compound is represented by> N—CH 2 (OH).
  • the N-alkoxymethyl group is represented by> N—CH 2 —OR (R is an alkyl group).
  • the N-methylol group and the N-alkoxymethyl group can react with a hydroxyl group, a carboxyl group, an amino group (described later) contained in the second resin.
  • Isocyanate group-containing compound examples include diisocyanate.
  • diisocyanates include aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), such as 1,3- or 1,4-xylylene diene.
  • MDI 4,4′-diphenylmethane diisocyanate
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • Aroaliphatic diisocyanates such as isocyanate (XDI), for example, aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), 1,5-pentamethylene diisocyanate (PDI), such as 3-isocyanate methyl-3,5,5-trimethyl Cyclohexyl isocyanate (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (H12MDI), norbornane diisocyanate (NBDI), 1,4-bis (isocyanatomethyl) cyclohexane (1,4 H6XDI) alicyclic diisocyanates such as, for example, aromatic aliphatic diisocyanates such as tetramethylxylylene diisocyanate (TMXDI) and the like.
  • XDI isocyanate
  • HDI hexamethylene diisocyanate
  • PDI 1,5-pentamethylene diisocyanate
  • diisocyanates the above-mentioned alcohol adducts (specifically, trimethylolpropane adducts), biuret modified products, allophanate modified products, multimers (dimers, trimers (isocyanurate modified products)) of each diisocyanate. ) Or polymethylene polyphenyl polyisocyanate (crude MDI) and the like.
  • the isocyanate group-containing compound can be used alone or in combination.
  • the isocyanate group in the isocyanate group-containing compound can react with a hydroxyl group, amino group, thiol group, carboxyl group (described later) and the like contained in the second resin.
  • Nitrogen atom-containing compound A nitrogen atom-containing compound is an active hydrogen group-containing compound having an active hydrogen group containing hydrogen directly bonded to a nitrogen atom.
  • nitrogen atom-containing compound examples include imidazole compounds and polyamine compounds.
  • imidazole compound examples include imidazole, for example, imidazole derivatives. Preferably, an imidazole derivative is used.
  • An imidazole derivative is a compound in which a part of hydrogen atoms in imidazole is substituted with a substituent.
  • Examples of the imidazole derivative include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenylimidazole, Examples include 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole (1B2PZ).
  • polyamine compound examples include chain aliphatic diamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, for example, cyclic aliphatic diamine compounds such as isophoronediamine and diaminodicyclohexylmethane, for example, xylenediamine, And aromatic diamine compounds such as diaminodiphenylmethane (DDM).
  • chain aliphatic diamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine
  • cyclic aliphatic diamine compounds such as isophoronediamine and diaminodicyclohexylmethane, for example, xylenediamine
  • aromatic diamine compounds such as diaminodiphenylmethane (DDM).
  • DDM diaminodiphenylmethane
  • the nitrogen atom-containing compounds can be used alone or in combination.
  • the active hydrogen group in the nitrogen atom-containing compound can react with an epoxy group and an isocyanate group (described later) contained in the second resin.
  • Aldehyde group-containing compound examples include glyoxal and glyoxal resin.
  • the aldehyde group-containing compound can be used alone or in combination.
  • the aldehyde group in the aldehyde group-containing compound can react with a hydroxyl group (described later) contained in the second resin.
  • Oxazoline group-containing compound examples include 2,2 ′-(1,3-phenylene) bis-2-oxazoline.
  • the oxazoline group-containing compounds can be used alone or in combination.
  • the oxazoline group in the oxazoline group-containing compound reacts with a carboxyl group, a thiol group (more specifically, a phenolic thiol group (a thiol group directly bonded to a carbon atom of a benzene ring)), and an acid anhydride group (described later). be able to.
  • Hydrazide Group-Containing Compound examples include carbohydrazides such as adipic acid dihydrazide and 1,3-bis (hydrazidecarboethyl) -5-isopropylhydantoin.
  • the hydrazide group-containing compound can be used alone or in combination.
  • the hydrazide group in the hydrazide group-containing compound can react with a carbonyl group (described later) contained in the second resin.
  • silanol group-containing compound examples include alkoxysilanes and oligomers of alkoxysilanes. Silanol group-containing compounds can be used alone or in combination.
  • the silanol group in the silanol group-containing compound can react (condensation reaction) with a hydroxyl group (described later) contained in the second resin.
  • Aziridine group-containing compound examples include 2- (1-arididinyl) ethyl (meth) acrylate oligomers. Aziridine group-containing compounds can be used alone or in combination.
  • the aziridine group in the aziridine group-containing compound can react with a carboxyl group, a thiol group, or a phenolic hydroxyl group (described later) contained in the second resin.
  • Acetoacetoxy group-containing compound examples include acetoacetoxyethyl (meth) acrylate oligomers.
  • the acetoacetoxy group-containing compound can be used alone or in combination.
  • the acetoacetoxy group can react with an amino group, a hydrazide group (described later) and the like contained in the second resin.
  • Diacetone group-containing compound examples include diacetone (meth) acrylamide oligomers.
  • the diacetone group-containing compound can be used alone or in combination.
  • the diacetone group in the diacetone group-containing compound can react with a carboxyl group, an amino group (described later) and the like contained in the second resin.
  • Resin Resin is a vinyl monomer solution of a low molecular weight polymer (hereinafter referred to as curable resin. Also referred to as first curable resin) containing a plurality of vinyl polymerization reactive double bonds in the molecule. It is a cured product.
  • the vinyl monomer solution is a curable resin composition (first curable resin composition) obtained by dissolving a curable resin with a liquid vinyl monomer at room temperature (25 ° C.), and preferably a curable resin and vinyl. It consists only of monomers and does not contain non-reactive solvents (such as ketone solvents such as methyl ethyl ketone).
  • the curable resin composition is vinyl polymerizable.
  • the curable resin composition can be selected from a room temperature curable thermosetting resin composition, a high temperature curable thermosetting resin composition, or an ultraviolet ray, depending on the selection of a polymerization initiator (described later), a polymerization accelerator (described later), and the like. It becomes an active energy ray-curable resin composition such as an electron beam.
  • curable resin examples include unsaturated polyester, epoxy (meth) acrylate, and urethane (meth) acrylate.
  • unsaturated polyester is used from the viewpoint of obtaining resins with various costs and various performances.
  • Examples of the active energy ray-curable resin include urethane (meth) acrylate.
  • the curable resin is preferably an unsaturated polyester.
  • Unsaturated polyester An unsaturated polyester is obtained by polycondensation (condensation polymerization) of a dibasic acid component containing an unsaturated dibasic acid and a dihydric alcohol (diol) component.
  • unsaturated dibasic acids include maleic acid, fumaric acid, methyl fumaric acid (mesaconic acid), methyl maleic acid (citraconic acid), aconitic acid, itaconic acid (isomers of mesaconic acid and citraconic acid), etc.
  • ⁇ , ⁇ -unsaturated dibasic acid examples include the above-mentioned anhydrides of ⁇ , ⁇ -unsaturated dibasic acid (specifically, maleic anhydride, citraconic anhydride, etc.). These can be used alone or in combination of two or more.
  • an unsaturated dibasic acid Preferably, a fumaric acid and maleic anhydride are mentioned, More preferably, maleic anhydride is mentioned.
  • the content ratio of the unsaturated dibasic acid in the dibasic acid component is, for example, 20% or more, preferably 40% or more, and, for example, 80% or less, preferably 60% or less, on a molar basis. .
  • the dibasic acid component can also contain a saturated dibasic acid in addition to the unsaturated dibasic acid described above.
  • saturated dibasic acid include phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 3,6-endodichloromethylenetetrachlorophthalic anhydride (Het Acid), 3,6-endomethylenetetrahydrophthalic anhydride (nadic anhydride), adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like.
  • the saturated dibasic acid examples include phthalic anhydride and adipic acid, and more preferred is phthalic anhydride.
  • the saturated dibasic acid has 6 or more carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. It is effective to select a saturated fatty acid dicarboxylic acid of 10 or less.
  • the content ratio of the saturated dibasic acid in the dibasic acid component is, for example, 20% or more, preferably 40% or more, and, for example, 80% or less, preferably 60% or less, on a molar basis. Further, the content ratio of the saturated dibasic acid to 100 mol parts of the unsaturated dibasic acid is, for example, 50 mol parts or more, preferably 75 mol parts or more, and for example, 150 mol parts or less, preferably 125 mol parts or less.
  • dihydric alcohol component examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyethylene glycol such as diethylene glycol, triethylene glycol, and tetraethylene glycol, such as dipropylene glycol, Polypropylene glycol such as tripropylene glycol, eg neopentyl glycol, eg 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A), eg bisphenol A propylene oxide adduct, bisphenol A ethylene oxide addition Examples include the body.
  • the dihydric alcohol component is preferably diethylene glycol or triethylene glycol from the viewpoint of making the cured product flexible.
  • the dihydric alcohol component can be used alone or in combination of two or more.
  • Preferred examples of the dihydric alcohol component include a combined use of propylene glycol and diethylene glycol, and a combined use of triethylene glycol and ethylene glycol.
  • the cured product becomes soft. Therefore, an unsaturated polyester obtained with such a composition is defined as a soft unsaturated polyester.
  • Soft unsaturated polyester generally uses phthalic acid as a raw material as a saturated dibasic acid. When phthalic anhydride or orthophthalic acid is used as the saturated dibasic acid, a cured product that is brittle and easily broken can be obtained.
  • a cured product resistant to acids, alkanes and the like can be obtained.
  • phthalic anhydride or orthophthalic acid is preferably used as the saturated dibasic acid.
  • flexible soft unsaturated polyesters generally use adipic acid as a raw material as a saturated dibasic acid.
  • the dibasic acid component and the dihydric alcohol component described above are, for example, such that the molar ratio of the dihydric alcohol component to the dibasic acid component is in a ratio of 1.00 to 1.10. And then polycondensed by heating.
  • the reaction temperature is, for example, 180 ° C. or higher, for example, 220 ° C. or lower.
  • the reaction temperature is, for example, 3 hours or more, for example, 20 hours or less.
  • polymerization inhibitor examples include hydroquinone compounds such as hydroquinone and methylhydroquinone, benzoquinone compounds such as benzoquinone and methyl-p-benzoquinone, and catechol compounds such as t-butylcatechol, such as 2,6-di- Examples thereof include phenol compounds such as t-butyl-4-methylphenol and 4-methoxyphenol (hydroquinone methyl ether), such as phenothiazine and copper naphthenate. These can be used alone or in combination of two or more. Preferably, hydroquinone is used.
  • the addition ratio of the polymerization inhibitor is, for example, 1 ppm or more, preferably 10 ppm or more, based on the mass of the mixture of the dibasic acid component and the dihydric alcohol component, and, for example, 1000 ppm or more, preferably 100 ppm or less.
  • the unsaturated polyester can also be obtained, for example, by ring-opening polymerization.
  • a polyhydric alcohol is used as an initiator, and a metal soap such as zirconium or zinc is used in combination with a polymerization catalyst if necessary.
  • Manufacture of unsaturated polyester by ring-opening polymerization uses maleic anhydride as an essential component as a dibasic acid component, and acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride are used, and propylene oxide as a dihydric alcohol component.
  • Ring-opening polymerization using alkylene oxide such as ethylene oxide, butylene oxide, styrene oxide, epichlorohydrin and the like as a monomer.
  • the polymer obtained by ring-opening polymerization can be produced by increasing the degree of polymerization by polycondensation.
  • the acid value of the unsaturated polyester is, for example, 5 [mg KOH / g] or more, preferably 10 [mg KOH / g] or more, and for example, 80 [mg KOH / g] or less, preferably 40 [mg KOH / g]. g] is as follows.
  • the acid value of the unsaturated polyester is measured according to JIS K6901-A method (2008).
  • Epoxy (meth) acrylate is also called vinyl ester.
  • Epoxy (meth) acrylate is obtained, for example, by the following method. That is, by reacting a bisphenol type epoxy resin with an unsaturated carboxylic acid such as (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid) in the presence of a catalyst such as a tertiary amine, an epoxy ring is formed.
  • Method (1) of generating an ester bond by ring-opening with a carboxyl group for example, a carboxyl group end of an unsaturated oligoester and an epoxy group of an acrylate ester containing an epoxy group such as glycidyl (meth) acrylate
  • a carboxyl group for example, a carboxyl group end of an unsaturated oligoester and an epoxy group of an acrylate ester containing an epoxy group such as glycidyl (meth) acrylate
  • an epoxy (meth) acrylate is obtained by a method (2) in which an ester bond is introduced by reacting in the presence of a catalyst such as a tertiary amine to open an epoxy ring with a carboxyl group.
  • Urethane (meth) acrylate is a diisocyanate such as isophorone diisocyanate and a hydroxyl group of a hydroxy group-containing (meth) acrylic ester such as 2-hydroxyethyl methacrylate, for example, a catalyst such as dibutyltin dilaurate. It is an oligomer containing a urethane bond and an ester bond obtained by reacting under the following conditions.
  • Vinyl monomer As the vinyl monomer, a monomer which is liquid at room temperature and has a property of performing addition polymerization (vinyl polymerization) by radical initiation is selected. Further, the vinyl monomer dissolves the curable resin to lower the viscosity and plays a role as a crosslinkable monomer that vinyl-polymerizes with the unsaturated double bond of the curable resin.
  • vinyl monomers examples include monofunctional vinyl monomers, and specific examples include styrene, methylstyrene ( ⁇ -methylstyrene, ⁇ -methylstyrene) (vinyltoluene), tert-butylstyrene, Styrenic monomers such as chlorostyrene (o-chlorostyrene, m-chlorostyrene, p-chlorostyrene) such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) And (meth) acrylic acid ester monomers such as butyl acrylate and 2-hydroxyethyl (meth) acrylate.
  • a styrene monomer is used.
  • Vinyl monomers can be used alone or in combination of two or more.
  • the mixing ratio of the vinyl monomer is, for example, 30 parts by mass or more, preferably 70 parts by mass or more, and, for example, 150 parts by mass or less, preferably 130 parts by mass or less with respect to 100 parts by mass of the curable resin. It is.
  • the blending ratio of the vinyl monomer is, for example, 35% by mass or more, preferably 50% by mass or more, and more preferably 51% by mass or more with respect to the total amount of curable resin and vinyl monomer (amount of resin). For example, it is 55 mass% or less, Preferably, it is 53 mass% or less.
  • the mixing ratio of the vinyl monomer is equal to or more than the lower limit described above, the viscosity (described later) of the curable resin composition can be reduced, and the curable resin composition is quickly taken into the pores of the porous inorganic particles ( Adsorbed and supported).
  • the blending ratio of the vinyl monomer is equal to or less than the above upper limit, a resin (cured product) having a high crosslinking density can be obtained.
  • curable resin composition 3-5-1 Preparation of curable resin composition 3-5-1. Dissolution of curable resin in vinyl monomer A vinyl monomer solution of curable resin is prepared by blending the above-described curable resin and vinyl monomer in the above-described ratio. Specifically, in the production of a curable resin, it is prepared by cooling after completion of the reaction and pouring a curable resin having sufficient fluidity into a separately prepared vinyl monomer under stirring. (Hot Dilution). In the production of the curable resin, it may be prepared by cooling to room temperature after completion of the reaction, injecting the vinyl monomer into the high viscosity curable resin, and dissolving it (cold dilution).
  • the vinyl monomer solution of curable resin is unsaturated polyester resin, epoxy acrylate resin, urethane acrylate resin when curable resin is each of unsaturated polyester, epoxy (meth) acrylate, and urethane (meth) acrylate.
  • unsaturated polyester resin epoxy acrylate resin
  • urethane acrylate resin when curable resin is each of unsaturated polyester
  • epoxy (meth) acrylate epoxy (meth) acrylate
  • urethane (meth) acrylate urethane (meth) acrylate.
  • the unsaturated polyester resin can be prepared by the above-described method, or a commercially available product can be used.
  • an unsaturated polyester resin for example, in the Polyhope series of Japan Composite, the Sandoma series of DIC Materials, the Rigolac series of Showa Denko, etc., the physical property values displayed on the product test table, and Commercially available product numbers that can be adjusted to the predetermined physical property values described below from composition analysis values analyzed by NMR or the like can be used.
  • the epoxy acrylate resin the Neopol series of Nippon Iupika, the vinyl ester series of DIC Materials, etc. are used, and as the urethane acrylate, the Iupika series of Japan Iupika, etc. are used.
  • curable resin composition is adjusted so as to exhibit normal temperature gelation time and viscosity suitable for the use of the present invention.
  • the curable resin composition will be described by taking an unsaturated polyester resin, which is a room temperature curable thermosetting resin composition, as an example.
  • the adsorption rate of the unsaturated polyester resin to the porous inorganic particles is sufficiently high.
  • the viscosity of the unsaturated polyester resin at 23 ° C. is adjusted to, for example, 100 mPa ⁇ s or less, preferably 70 mPa ⁇ s or less.
  • the viscosity of the vinyl monomer solution is measured with a BM viscometer. If the viscosity of the unsaturated polyester resin is less than or equal to the above upper limit, the vinyl monomer solution can be taken up in a short time without decreasing the rate of taking the unsaturated polyester resin into the pores of the porous inorganic particles. It is possible to suppress the vinyl monomer solution from being sufficiently taken into the pores and remaining on the surface of the porous inorganic particles.
  • Viscosity is adjusted by post-addition of vinyl monomer.
  • the total vinyl monomer amount is, for example, 55% by mass or less, preferably 53% by mass or less, based on the total amount of the unsaturated polyester resin.
  • normal temperature gelation time in normal temperature curing is adjusted.
  • the normal temperature gelation time is measured according to JIS K6901-A method (2008).
  • the normal temperature gelation time is, for example, 10 minutes or more, preferably 20 minutes or more, and is adjusted to be, for example, 2 hours or less, preferably 1 hour or less.
  • the unsaturated polyester resin is surely incorporated into the pores of the porous inorganic particles before the unsaturated polyester resin is cured. be able to. That is, when the normal temperature gelation time of the unsaturated polyester resin is less than the lower limit described above, the unsaturated polyester resin starts to be cured before the unsaturated polyester resin is taken into the pores of the porous inorganic particles. End up. Therefore, the unsaturated polyester resin may not be reliably taken into the pores of the porous inorganic particles.
  • the functional component taken into the pores of the porous inorganic particles is a vinyl monomer contained in the vinyl monomer solution. It can be prevented that it melts into the surface and subsequently moves to the surface of the porous inorganic particles.
  • the methyl ketone solution of the epoxy resin is heated for a time longer than the above upper limit, so that the supported substance dissolves in methyl ethyl ketone during that time. And move to the surface of the silica fine particles.
  • unsaturated polyester resin can be hardened rapidly and with high crosslink density.
  • Preparation of the room temperature curing type unsaturated polyester resin is carried out by blending the unsaturated polyester resin with a polymerization accelerator, and if necessary, a polymerization acceleration assistant and a polymerization retarder (second polymerization inhibitor).
  • a polymerization accelerator include oxidizing metal soaps such as cobalt octylate and cobalt naphthenate.
  • the polymerization promoting aid include aromatic amines such as dimethylaniline and carbonyl compounds such as acetylacetone.
  • the polymerization retarder (second polymerization inhibitor) include those exemplified for the first polymerization inhibitor, preferably hydroquinone methyl ether and hydroquinone.
  • the room temperature gelation time is adjusted as follows.
  • a predetermined amount of a polymerization accelerator and, if necessary, a predetermined amount of a polymerization acceleration aid are blended into a predetermined amount of the unsaturated polyester resin, and then a predetermined amount of polymerization initiator. (Methyl ethyl ketone peroxide, etc.) is blended and the room temperature gelation time is measured.
  • several amounts of different polymerization retarders (second polymerization inhibitors) are blended with the above blended resin, and the normal temperature gelation time is measured.
  • the polymerization retarder (second polymerization inhibitor) include those exemplified for the first polymerization inhibitor.
  • the amount of the polymerization retarder (second polymerization inhibitor) is, for example, 5 ppm or more and 1000 ppm or less with respect to the vinyl monomer as the active ingredient amount on a mass basis.
  • the relationship between the amount of the polymerization retarder (second polymerization inhibitor) and the normal temperature gelation time is represented by a graph, and the amount of the polymerization retarder (second polymerization inhibitor) corresponding to the desired normal temperature gelation time is obtained. It is done.
  • the polymerization accelerator is a formulation in which 0.5% by mass of 6% cobalt naphthenate or 8% cobalt octylate is blended with respect to the unsaturated polyester resin and no polymerization accelerator is blended.
  • Use standard recipe is a method in which 1.0% by mass of 55% methyl ethyl ketone peroxide is added to the polymerization initiator and the normal temperature gelation time is measured.
  • the ratio (Vl / Voa) of the volume (Vl) of the liquid containing the functional component to the porous inorganic particles to the oil-absorbable volume (Voa) of the porous inorganic particles is 0.
  • the vinyl monomer solution was made porous by blending so that the ratio ((Vf + Vr) / Voa) of the total volume (Vf + Vr) of the solution to the oil-absorbable volume (Voa) of the porous inorganic particles was 0.75 or less.
  • the functional component is liquid at room temperature, prepare the functional component as a liquid as it is.
  • the functional component has a viscosity at 23 ° C. of 100 mPa ⁇ s or less, the functional component is prepared as a liquid as it is.
  • the method for measuring the viscosity is the same as the method for measuring the viscosity of the vinyl monomer solution described above.
  • the functional component at 23 ° C. exceeds 100 mPa ⁇ s
  • the functional component is diluted with a solvent described below, and the viscosity at 23 ° C. is, for example, 100 mPa ⁇ s or less.
  • a solution of functional components of 70 mPa ⁇ s or less is prepared.
  • the functional component is semi-solid or solid at room temperature, prepare a solution of the functional component.
  • a solution of a functional component having a viscosity at 23 ° C. of 100 mPa ⁇ s or less, more preferably 70 mPa ⁇ s or less is prepared.
  • the functional component is semi-solid or solid at room temperature, the functional component is dissolved in a solvent to prepare a functional component solution.
  • the solvent examples include an organic solvent and water. Specific examples of the solvent include organic solvents as long as the functional component is a water-insoluble antibiotic active compound, a water-insoluble flame retardant, a water-insoluble curing agent, and the like. If it is water-soluble components, such as an antibiotic active compound, a water-soluble flame retardant, and a water-soluble hardener, water will be mentioned.
  • the organic solvent is selected from solvents that can dissolve water-insoluble components.
  • examples of the organic solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as dichloroethane and trichloroethane.
  • Esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol, and isopropanol, such as 1,4-dioxane, tetrahydrofuran, and the like And ethers.
  • the organic solvent can be used alone or in combination of two or more.
  • ketones and alcohols are used.
  • the mixing ratio of the solvent and the functional component is adjusted so that the viscosity of the solution at 23 ° C. is, for example, 100 mPa ⁇ s or less, preferably 70 mPa ⁇ s or less.
  • the blending ratio of the functional component is, for example, 30% by mass or more, preferably 50% by mass or more, and, for example, 80% by mass or less with respect to the total amount of the solvent and the functional component.
  • the mixing ratio of the solvent and the functional component is adjusted.
  • a liquid containing a functional component is blended with the porous inorganic particles.
  • the porous particles are weighed in a closed container equipped with a stirrer, and a liquid containing a functional component is dropped while stirring.
  • the ratio of the total volume of the functional component volume (Vf) and the volume of the solvent Vs that is, the volume of the liquid containing the functional component (Vl) to the oil-absorbable volume (Voa) of the porous inorganic particles (Vl /
  • the liquid containing a functional component is mix
  • the density of the liquid containing the functional component at this time is assumed to be 1.0 g / mL.
  • the oil-absorbable volume Voa (mL) of the porous inorganic particles is an oil absorption amount per 1 g of the porous inorganic particles converted from the oil absorption amount Vo (mL / 100 g) of the porous inorganic particles as shown in the following formula. It is a volume obtained by multiplying (mL / g) by the mass M (g) of the porous inorganic particles.
  • Voa (mL) Vo (mL / 100 g) / 100 ⁇ M (g)
  • the oil absorption amount Vo (mL / 100 g) of the porous inorganic particles is determined by the pore volume (V 1 ) inside the primary particles forming the porous inorganic particles, the void volume (V 2 ) between adjacent primary particles, and The volume (mL) per 100 g of porous inorganic particles of the sum (V 1 + V 2 + V 3 ) of the minimum volume (V 3 ) that the oil wets the surface of the secondary particles is shown.
  • the pore volume (V 1 ) inside the primary particles and the total volume (V 1 + V 2 ) of the void volume (V 2 ) between the primary particles can be absorbed as shown in the following formula. Over 75% of volume Voa.
  • the liquid containing the functional component is made porous so that the ratio (Vl / Voa) of the volume (Vl) of the liquid to the oil-absorbable volume Voa of the porous inorganic particles is 0.75 or less. It mix
  • the liquid containing the functional component may be blended with the porous inorganic particles at normal pressure, or if the pressure is reduced and the pores of the porous inorganic particles are in a vacuum state, The adsorption rate of the liquid containing the component to the porous inorganic particles can be accelerated.
  • the stirring speed of the porous inorganic particles, the stirring mode, and the dropping time of the liquid containing the functional component are appropriately adjusted.
  • the solvent is distilled off under atmospheric pressure and / or reduced pressure at room temperature and / or heating conditions.
  • a desired amount of the functional component can be taken into the porous particles by performing the step (1) a plurality of times. Specifically, in the first time, the liquid containing the functional component is blended with the porous inorganic particles, and then the solvent is removed. Then, in the second time, the liquid containing the functional component is Further blending is performed on the porous inorganic particles incorporating the functional component blended at the first time, and then the solvent is distilled off. This operation is repeated for the third and subsequent times.
  • the volume Vf 1 of the functional component taken into the porous inorganic particles in the first time and the total volume Vf 1 + Vl 2 of the volume Vl 2 of the liquid blended in the second time are obtained.
  • the second liquid is added to the porous inorganic particles so that the ratio of the porous inorganic particles to the oil-absorbable volume Voa is 0.75 or less.
  • the third and subsequent times are the same as described above.
  • the n-th liquid is blended with the porous inorganic particles so that the ratio to is 0.75 or less.
  • Step (2) Thereafter, a vinyl monomer solution of a curable resin is blended with the porous inorganic particles having the functional component taken into the pores, and the vinyl monomer solution of the curable resin is taken into the pores of the porous inorganic particles.
  • a vinyl monomer solution of a curable resin is dropped onto the porous inorganic particles while stirring the porous inorganic particles obtained in the step (1).
  • the stirring speed of the porous inorganic particles, the stirring mode, and the dropping time of the vinyl monomer solution are appropriately adjusted.
  • a polymerization initiator is blended in the vinyl monomer solution of the curable resin before dropping onto the porous inorganic particles.
  • the polymerization initiator is a radical polymerization initiator that acts as an initiator in radical polymerization (vinyl polymerization) in step (3) described below.
  • examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
  • thermal polymerization initiator examples include acetylacetone peroxide, methyl ethyl ketone peroxide, diethyl ketone peroxide, methyl propyl ketone peroxide, methyl isobutyl ketone peroxide, methyl acetoacetate peroxide, ethyl acetoacetate peroxide.
  • Cyclohexanone peroxide methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, cumene peroxide, benzoyl peroxide, t-butylisopropylperoxycarbonate, 1,1-dibutylperoxy-3,3,5 -Trimethylcyclohexanone, t-butylperoxy-2-ethylhexanoate, amylperoxy-p-2-ethylhexanoe DOO, 2-ethylhexyl peroxy-2-ethylhexanoate, t- butyl peroxybenzoate, peroxy compounds such as hexyl peroxybenzoate.
  • t- preferably, methyl ethyl ketone peroxide.
  • a photoinitiator a benzoin derivative is mentioned, for example. These can be used alone or in combination.
  • the blending ratio of the polymerization initiator is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more with respect to 100 parts by mass of the vinyl monomer solution of the curable resin. It is 3 parts by mass or less, preferably 3 parts by mass or less.
  • the standard formulation is a formulation in which 1% of 55% methyl ethyl peroxide is added to the vinyl monomer solution.
  • the vinyl monomer solution of the curable resin is taken into the pores of the porous inorganic particles.
  • a vinyl monomer solution of a curable resin in which a polymerization initiator is blended, is stirred while stirring a sealed container equipped with a stirrer in which the porous inorganic particles obtained in the step (1) are charged. Dripping.
  • the vinyl monomer solution of the curable resin may be dropped onto the porous inorganic particles at normal pressure, or the curable resin may be removed by reducing the pressure and keeping the pores of the porous inorganic particles in a vacuum state. The adsorption rate of the vinyl monomer solution on the porous inorganic particles can be accelerated.
  • the vinyl monomer solution of the curable resin taken into the pores of the porous inorganic particles is cured.
  • the thermal polymerization initiator blended in the vinyl monomer solution of the curable resin is room temperature curable, it will be cured after 24 hours or more at room temperature (25 ° C.).
  • the film can be completely cured by leaving it at room temperature (25 ° C.), for example, after 5 hours or more, and by leaving it at 40 ° C. to 60 ° C. for 5 hours or more.
  • a high-temperature curable thermal polymerization initiator is added to the vinyl monomer solution of the curable resin, the resin is cured at a desired curing temperature and curing time.
  • a room temperature curable thermal polymerization initiator is used, and more preferably, polymerization is performed on an unsaturated polyester resin in which 6% cobalt naphthenate or 8% cobalt octylate is blended in the polymerization accelerator.
  • the initiator is blended with a room temperature curable thermal polymerization initiator 55% methyl ethyl ketone peroxide.
  • a vinyl monomer solution of a curable resin containing a photopolymerization initiator such as a benzoin derivative can be cured by, for example, irradiation with ultraviolet rays or electron beams.
  • a photopolymerization initiator such as a benzoin derivative
  • UV curing can be suitably performed.
  • the above-described curing proceeds by vinyl copolymerization (radical copolymerization) of the vinyl group of the vinyl monomer and the unsaturated double bond of the curable resin.
  • the functional component is sealed with the cured resin.
  • the ratio (Vl / Voa) of the volume (Vl) of the liquid containing the functional component to the oil absorbing capacity (Voa) of the porous inorganic particles is 0.40 or more, for example. Preferably, it is 0.50 or more, and preferably 0.75 or less.
  • step (2) the ratio of the volume of the functional component and the total volume of the resin (Vf + Vr) to the oil-absorbable volume (Voa) of the porous inorganic particles ((Vf + Vr) / Voa) is 0.75 or less. That is, it mix
  • the density of the functional component at this time and the vinyl monomer solution of the curable resin is assumed to be 1.0 and g / mL.
  • (Vf + Vr) / Voa is, for example, 0.45 or more, preferably more than 0.45, more preferably 0.50 or more, still more preferably more than 0.50, and more preferably, 0.60 or more.
  • the functional component and the resin can be included in a sufficient amount in the porous inorganic particles.
  • the ratio (Vr / Voa) of the volume (Vr) of the resin to the oil-absorbable volume (Voa) of the porous inorganic particles is, for example, 0.15 or more, preferably 0.20 or more, more preferably 0.30. For example, it is 0.60 or less.
  • Patent Document 1 does not disclose the concept of oil absorption, but it is estimated that Vr / Voa is less than the lower limit described above in order to remove the organic solvent in the organic solvent solution.
  • the ratio of the mass of the functional component adsorbed in the step (1) to the mass of the curable resin vinyl monomer solution (that is, the mass of the resin) (the mass of the functional component / the mass of the vinyl monomer solution, that is, the functional component).
  • Mass / resin mass is, for example, 2.25 or less, preferably 2.00 or less, more preferably 1.70 or less, and for example, 0.10 or more, preferably 0.50. That's it.
  • the mass ratio of the functional component is not more than the above upper limit, the functional component is surely sealed in the pores of the porous inorganic particles by a sufficient amount of resin. Therefore, it can suppress that a functional component leaks out of the hole of a porous inorganic particle.
  • the ratio of the total mass of the functional component and the vinyl monomer solution (resin) of the curable resin to the mass of the porous inorganic particles is, for example, 1.30 or more, preferably 1.50 or more, more preferably 1.60 or more, further preferably more than 1.60, and particularly preferably 1.70 or more. Furthermore, it is 1.80 or more, further 1.90 or more, further 2.00 or more, for example, 2.50 or less.
  • the function-expressing particles can contain a sufficient amount of the functional component and the resin depending on the purpose.
  • Function-expressing particles can be applied to various industrial products, such as indoor and outdoor paints, resins (thermosetting resins), rubber, fibers, putty, adhesives, joint agents, and sealing agents. , Building materials, caulking agents, wood treatment agents, soil treatment agents, white water, pigments, printing plate treatment liquids, cooling water, solvents (specifically paint solvents, etc.), inks, cutting oils, cosmetics, It can be added to and mixed with binders for nonwoven fabrics, spinning oils, leather treatment materials and the like.
  • the content of the functional component for these industrial products is, for example, 10 mg / kg to 100 g / kg (product mass).
  • the function-expressing particles can be kneaded with a resin (thermoplastic resin), a thermoplastic elastomer, rubber, or the like to form a molded body as it is or once as a molding material.
  • a resin thermoplastic resin
  • thermoplastic elastomer thermoplastic elastomer
  • rubber or the like to form a molded body as it is or once as a molding material.
  • Such shaped bodies have antibiotic activity when the functional ingredient is an antibiotic compound.
  • the functional component is released from the function-expressing particles, so that the molded product exhibits antibiotic activity (for example, repellent properties).
  • a molded object expresses antibiotic activity (for example, antiseptic
  • the functional component is a flame retardant, the functional component is exposed when the resin in the function-expressing particles burns, whereby the molded product exhibits flame retardancy.
  • the function-expressing particles are blended with the second resin to prepare a second curable resin composition.
  • the function-expressing particles function as a latent curing agent, and the second curable resin composition is prepared as a one-component curable resin composition.
  • the second curable resin composition is cured to produce a cured resin (crosslinked resin).
  • thermoplastic resins examples include thermoplastic resins, thermosetting resins (main materials thereof), hard resins such as biodegradable resins, and soft resins such as rubber and elastomer.
  • the second resin has a plurality of second functional groups that undergo a curing reaction (crosslinking reaction) with the first functional group contained in the curing agent.
  • Examples of the second functional group include an amino group, a hydroxyl group, a carbonyl group (including a carboxyl group and an acid anhydride group), a thiol group (including a phenolic thiol group), an epoxy group, an isocyanate group, a silanol group, and a hydrazide group. Etc. These can be used alone or in combination.
  • Examples of the second resin include carboxyl group-modified synthetic rubber (for example, carboxyl group-modified SBR rubber), carboxyl group-modified acrylic resin, polyvinyl alcohol, rayon, epoxy resin, polyisocyanate prepolymer, polyester, polyurethane, acrylic polyol, and the like. Can be mentioned.
  • carboxyl group-modified synthetic rubber for example, carboxyl group-modified SBR rubber
  • carboxyl group-modified acrylic resin for example, polyvinyl alcohol, rayon, epoxy resin, polyisocyanate prepolymer, polyester, polyurethane, acrylic polyol, and the like. Can be mentioned.
  • the property of the second resin is not particularly limited.
  • a polymer dispersion such as latex or non-aqueous dispersion (NAD), for example, a resin solution (polymer solution) dissolved in a solvent or water, for example, a powder or a compound.
  • molding materials such as pellets and blocks, such as resin fibers (polymer fibers).
  • carboxyl group-modified synthetic rubber latex such as carboxyl group-modified SBR rubber latex
  • carboxyl group-modified acrylic latex such as carboxyl group-modified acrylic latex, polyvinyl alcohol aqueous solution, rayon fiber, epoxy resin liquid resin, carboxyl group-modified compound , Polyisocyanate prepolymer solution, polyester powder, polyurethane block and the like.
  • the blending ratio of the curing agent with respect to 100 parts by mass of the second resin is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and for example, 80 parts by mass or less, preferably It mix
  • the second curable resin composition can be reliably cured.
  • the functionally expressed particles have an equivalent ratio of the first functional group to the second functional group (first functional group / second functional group) of, for example, 0.7 or more, preferably 0.9 or more. For example, it is blended with the second resin so as to be 1.3 or less, preferably 1.1 or less.
  • a curing catalyst that accelerates the reaction of the functional component can be blended in the second curable resin composition in an appropriate ratio, for example, in the following combinations.
  • Epoxy group-containing compounds 3 such as 1,4-diazabicyclo [2,2,2] octane (triethylenediamine) (DABCO), 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine Secondary amine compound N-methylol group-containing compound or N-alkoxymethyl group-containing compound: various amine salts Isocyanate group-containing compound: carboxylic acid metal salt such as dibutyltin dilaurate
  • the second curable resin composition described above is specifically Used as various water-based paints, adhesives for fibers and wood, caulking materials, molding / casting materials, fiber treatment agents, etc.
  • the second curable resin composition (one-component curable resin composition)
  • the second curable resin composition is heated and pressurized as necessary. That is, the curing agent in the function-expressing particle is released by heating or heating and pressurization as a trigger, whereby the curing agent (first functional group thereof) and the second resin (second functional group thereof) are released.
  • the second curable resin composition (one-component curable resin composition) is cured.
  • the second curable resin composition is prepared as a one-component curable resin composition.
  • a two-component curable resin composition separately having function-expressing particles and a second resin is prepared.
  • the mixed liquid after mixing the function-expressing particles and the second resin is cured by the trigger described above.
  • the porous inorganic particles are mixed with the vinyl monomer solution of the curable resin, and the vinyl monomer solution is added to the pores of the porous inorganic particles in which the functional component is incorporated. Then, the vinyl monomer solution is cured. Therefore, as in Patent Document 1, all the vinyl monomer solution in the hole is cured to form a cured product without requiring a step of removing the organic solvent, so that a large resin volume (Vr) is ensured in the hole. can do. Therefore, a sufficient amount of functional components in the porous inorganic particles can be reliably sealed or sustained-released by such a resin.
  • the function-expressing particles obtained by the above-described production method can release a sufficient amount of an antibiotic compound under physical conditions such as destruction, and can exhibit antibiotic activity.
  • the functional component in an environment such as in a solvent, can exhibit sustained release.
  • the functional component is a curing agent and the function-expressing particles and the second resin are blended to prepare the second curable resin composition
  • the function-expressing particles contain a sufficient amount of the curing agent.
  • the curing agent is not released during the storage period (for example, at normal temperature and pressure). Therefore, the curing agent can be used as a latent curing agent.
  • the one-component curable resin composition containing the function-expressing particles and the second resin does not cure until it is used, and has a long pot life even when preheating by heating. It can be cured rapidly by heating (for example, heating at 100 ° C. or higher) and, if necessary, pressing.
  • a soft unsaturated polyester resin is preferably used as the resin for sealing the curing agent.
  • the curing agent is an epoxy group-containing compound, an N-methylol group-containing compound or N -Alkoxymethyl group-containing compound, isocyanate group-containing compound, nitrogen atom-containing compound, aldehyde group-containing compound, oxazoline group-containing compound, hydrazide group-containing compound, silanol group-containing compound, aziridine group-containing compound, acetoacetoxy group-containing compound and diacetone
  • the curing agent is a carboxyl group contained in the unsaturated polyester resin, and / or By reacting with the hydroxyl group, Resin film can be formed. Therefore, the blending amount of the first resin can be relatively reduced.
  • the functional component is a water-insoluble component
  • a production method in which suspension polymerization or miniemulsion polymerization is performed in water as in the production methods disclosed in International Publication No. 2011/030824, International Publication No. 2013/100102, and the like.
  • the functional component when the functional component is a water-insoluble component, the functional component can be taken into the pores of the porous inorganic particles in the same manner as the above-mentioned proposal.
  • the functional component is a water-soluble component (water-soluble antibiotic active compound, water-soluble flame retardant)
  • the functional component is eluted in water in the same manner as the above-mentioned proposal. Ingredients cannot be dispersed or included in the vinyl polymer.
  • the functional component is a water-soluble component
  • the functional component is taken into the pores of the porous inorganic particles, and then the vinyl monomer solution of the curable resin is porous inorganic. Since the vinyl monomer solution is hardened after being taken into the pores of the particles, the functional component can be taken into the porous inorganic particles and sealed with the resin.
  • the ratio (Vr / Voa) of the volume (Vr) of the resin to the oil-absorbable volume (Voa) of the porous inorganic particles is equal to or more than the lower limit described above, the porous inorganic particles take in a sufficient amount of resin. Thereby, the functional component can be reliably sealed in the pores of the porous particles.
  • Vr / Voa becomes less than a specific lower limit.
  • the ratio (Vf + Vr) / Voa) of the total volume (Vf + Vr) of the functional component and resin to the oil-absorbable volume (Voa) of the porous inorganic particles is equal to or less than the above-described upper limit.
  • the functional component and the resin are made porous. It can be included in a sufficient amount with respect to the fine inorganic particles.
  • the supported substance and the polymer compound or curable compound are not included in a sufficient amount with respect to the porous fine particles.
  • step (2) if the ratio (Vf + Vr) / Voa of the total volume (Vf + Vr) of the functional component and resin to the oil-absorbable volume (Voa) of the porous inorganic particles exceeds the lower limit, the functional component and resin Can be included in a sufficient amount with respect to the porous inorganic particles.
  • the function-expressing particles have a sufficient amount of functions depending on the purpose.
  • Components and resins can be included.
  • the functional component is surely sealed in the pores of the porous inorganic particles by a sufficient amount of the resin. Stopped. Therefore, it can suppress that a functional component leaks out of the hole of a porous inorganic particle.
  • the adsorption rate (uptake rate) of the vinyl monomer solution into the pores of the porous inorganic particles is not lowered, and the vinyl monomer solution is reduced.
  • the vinyl monomer solution can be sufficiently taken into the pores to be prevented from remaining on the surface of the porous inorganic particles.
  • step (1) when the ratio (Vl / Voa) of the volume Vl of the liquid containing the functional component to the oil-absorbable volume Voa of the porous inorganic particles exceeds 0.75, a part of the functional component May be located on the surface of the porous inorganic particles and may not be taken into the inorganic porous particles.
  • step (1) the ratio (Vl / Voa) of the volume Vl of the liquid containing the functional component to the oil-absorbable volume Voa of the porous inorganic particles is 0.75 or less.
  • the functional component can be positioned inside the porous inorganic particles and reliably included in the inorganic porous particles.
  • the vinyl monomer solution of the curable resin is a thermosetting resin composition
  • the thermosetting resin composition has a normal temperature gelation time measured according to JIS K6901-A method (2008), the lower limit described above. If it is above, in a process (2), before a thermosetting resin composition hardens
  • thermosetting resin composition if the room temperature gelation time of the thermosetting resin composition is less than the above upper limit, the thermosetting resin can be thermoset in a short time. Therefore, there is no above-mentioned malfunction, that is, elution with respect to the vinyl monomer of a functional component can be prevented.
  • thermosetting resin composition can be hardened rapidly and with a high crosslinking density.
  • blending ratio content ratio
  • physical property values and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and the corresponding blending ratio (content ratio) ), Physical property values, parameters, etc. may be replaced with the upper limit values (numerical values defined as “less than” or “less than”) or lower limit values (numbers defined as “greater than” or “exceeded”). it can.
  • IPBC Trade name “Fangitrol 400”, 3-iodo-2-propynylbutylcarbamate, antiseptic / fungal agent, water-insoluble component, solubility in water: 0.15 g / L (20 ° C.), International Specialty Products Tinboa PCO: Nippon Borate's trade name, disodium octaborate tetrahydrate, wood preservative, water-soluble component, solubility in water: 250 g / L (20 ° C.), Nippon Borate Co., Ltd.
  • Denatonium benzoate bitterness Ingredient, repellent, water-soluble component, solubility in methanol: 50 g / L (20 ° C.), slightly soluble in water, manufactured by Wako Pure Chemical Industries, Ltd.
  • Synthetic capsaicin N-vanillyl nonanamide, pungent component, repellent, water Insoluble in epoxy resin manufactured by Wako Pure Chemical Industries, Ltd .: Trade name “jER806”, bisphenol F type epoxy resin, epoxy equivalent 160-170 , Viscosity 1500-2500 mPa ⁇ s (25 ° C.), water-insoluble component, manufactured by Mitsubishi Chemical Corporation Epoxy resin: Trade name “jER828”, bisphenol A type epoxy resin, epoxy equivalent 184-194, viscosity 12,000-15,000 mPa ⁇ s (25 ° C.), water-insoluble component, manufactured by Mitsubishi Chemical Corporation methylolated melamine: trade name “Beccamin M-3 (60)”, 54-60% non-volatile solution, DIC Corporation T-1890: trade name “
  • DDM 4,4′-diaminodiphenylmethane, aromatic diamine compound , Nitrogen atom-containing compound, water-insoluble component, manufactured by Tokyo Chemical Industry Co., Ltd.
  • Silicia 310P Fuji Silicia's trade name, porous inorganic particles, gel type silica particles, pore volume 1.60 mL / g, specific surface area 300 m 2 / g Oil absorption amount 330 mL / 100 g, average particle size 2.7 ⁇ m, manufactured by Fuji Silysia Co.
  • Permec N trade name of NOF Corporation, polymerization initiator (second curing agent), methyl ethyl ketone peroxide 55% dimethyl phthalate solution, NOF Corporation
  • Manufactured carboxyl group-modified SBR latex trade name “Nalstar SR-116”, concentrated solids Degree 50.5%, made by Nippon A & L
  • This resin is allowed to stand in a constant temperature water bath to 25 ° C., 1.0 mass% of a curing agent (second curing agent) Permec N is added and stirred, and the normal temperature gelation time is measured.
  • a two-component curable resin is prepared in the same manner as described above, and three arbitrary points of HQ 10% from 0.1% by mass to 0.5% by mass are selected and stirred.
  • the normal temperature gelation time is measured, the normal temperature gelation time is taken on the vertical axis, and the added amount of HQ 10% is taken on the horizontal axis, and a graph is prepared.
  • the physical properties of unsaturated polyester resin A were as follows.
  • Preparation Example 2 195 g of styrene monomer was added to 500 g of unsaturated polyester resin “Polyhop RHF1077M” (manufactured by Japan Composite). Subsequently, unsaturated polyester resin B was prepared by mix
  • the properties of unsaturated polyester resin B were as follows.
  • the physical properties of the soft unsaturated polyester resin C were as follows.
  • Preparation Example 4 190 g of styrene monomer was added to 500 g of orthophthalic acid-based soft unsaturated polyester resin “Polyhope N-423PW” (manufactured by Japan Composite).
  • soft unsaturated polyester resin D was prepared by blending 0.7 g of HQ 10% and adjusting the normal temperature gelation time to 25 minutes.
  • the properties of the soft unsaturated polyester resin D were as follows.
  • Example 1 Viscosity 59mPa ⁇ s (BM viscometer, 60rpm, 23 ° C) Room temperature gelation time 25 minutes (JIS K6901-A method (2008)) (Preparation of functionally expressed particles)
  • Example 1 A 500 mL flat bottom separable flask was charged with 9 g of Silicia 310P (silica particles, oil-absorbable volume Voa: 29.7 mL), and equipped with three inclined stirring blades having a blade diameter of 90% of the flask inner diameter. The top of the separable flask equipped with a 50 mL dropping funnel was joined to the flat bottom separable flask.
  • a vacuum pump, a three-way cock, a manometer, a trap (a trap using dry ice and methanol) and a flask top adapter were connected with a pressure-resistant tube, and the flask was evacuated.
  • the inside of the Kolben was closed with a three-way cock, and stirring was started at 600 rpm.
  • IPBC 60% acetone solution (viscosity (23 ° C.): 53 mPa ⁇ s) (IPBC 9 g, IPBC volume Vf: 9 mL, total liquid volume Vl: 15 mL) was added dropwise over 3 minutes. Subsequently, the valve of the dropping funnel was opened and the pressure was returned to normal pressure. Then, the bottom of the round bottom separable flask was removed, and vacuum drying was performed at room temperature for 5 hours to distill away acetone. Again, the top of the separable flask was joined to the flat bottom separable flask.
  • Functional component / porous inorganic particle / resin [mass basis], resin / porous inorganic particle [mass basis], functional component / function-expressing particle [mass basis], (functional component + resin) / porous inorganic particle [mass basis] ], Functional component / resin [mass standard], Vl / Voa [volume standard], Vf / Voa [volume standard], (Vf + Vr) / Voa [volume standard], Vr / Voa [volume standard] are shown in Table 1. To do. Similarly for the following Examples 2 and later, the above ratios are shown in Tables 1 to 4.
  • Example 2 In Example 1, instead of 15 g of IPBC 60% acetone solution, 15 g of Timbore PCO 20% aqueous solution (viscosity (23 ° C.): 23 mPa ⁇ s) (Tiboa PCO volume Vf: 3 mL, water volume Vs: 12 mL, aqueous solution volume) (Vl: 15 mL) was taken into 9 g of silica particles (adsorbed) and vacuum-dried at 80 ° C. for 5 hours to distill off water.
  • 15 g of IPBC 60% acetone solution 15 g of Timbore PCO 20% aqueous solution (viscosity (23 ° C.): 23 mPa ⁇ s) (Tiboa PCO volume Vf: 3 mL, water volume Vs: 12 mL, aqueous solution volume) (Vl: 15 mL) was taken into 9 g of silica particles (adsorbed) and vacuum-dried
  • Vl / Voa is 0.50, 0.60, and 0.71, respectively.
  • Vf / Voa was 0.10, 0.20, and 0.30, respectively.
  • Example 2 60 mg of Permec N was added to 6 g of the unsaturated polyester resin A, and a mixed liquid (volume Vr: 6 mL) was prepared by stirring and uniforming. Subsequently, the mixed solution was dropped onto the silica particles over 1 minute while stirring the silica particles at 600 rpm.
  • Example 3 In Example 1, instead of 15 g of IPBC 60% acetone solution, 15 g of denatonium benzoate 30% ethanol solution (viscosity (23 ° C.): 20 mPa ⁇ s or less) 15 g (4.5 g of denatonium benzoate, volume of denatonium benzoate Vf: 4 5 mL, total volume of liquid Vl: 15 mL) was taken into 9 g of silica particles (adsorbed), and 9 g of unsaturated polyester resin A and 90 mg of Permec N were used instead of unsaturated polyester resin B 10.
  • the function expressing particles were kneaded with polyethylene at 3%.
  • An anti-mold molding material could be produced without any problem in the working environment during kneading.
  • Example 5 Preparation of functionally expressed particles
  • a 500 mL round bottom separable flask was charged with 9 g of Silicia 310P (silica particles, oil-absorbable volume Voa: 29.7 mL), equipped with a stirrer with a half-moon shaped stirring blade matched to the curvature of the round bottom, and a 50 mL dropping funnel
  • the top of the separable flask was joined to a round bottom separable flask.
  • Parmec N was added to 7.5 g of the soft unsaturated polyester resin C, and a mixed solution (volume Vr: 7.5 mL) was prepared by stirring and uniforming. Subsequently, the mixed solution was dropped onto the silica particles over 3 minutes while stirring the silica particles at 600 rpm.
  • Example 5 was prepared such that a latex obtained by diluting a carboxyl group-modified SBR latex (Nalstar SR-116) with deionized water to a solid concentration of 20% had a jER806 of 5 parts by mass with respect to 100 parts by mass of the solid content. A latex to which the function-expressing particles were added was prepared. Next, 2.5 parts by mass of a 20% aqueous solution of 1,4-diazabicyclo [2.2.2] octane (DABCO) as a curing catalyst was added to the latex and stirred to obtain a uniform nonwoven fabric impregnating latex. This was left still at room temperature for 1 week.
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • the nonwoven fabric-impregnated latex was allowed to stand at room temperature for 2 weeks.
  • Example 6 (Preparation of functionally expressed particles)
  • 15 g of an 80% ethyl acetate solution of epoxy resin (jER806) (12 g of jER806, volume Vf of jER806: 12 mL, total volume of liquid Vl: 15 mL) was 13 g (jER806 10.4 g, volume of jER806 Vf: 10).
  • 70 mg of Permec N was added to 7.5 g of soft unsaturated polyester resin C, and the mixed solution (volume Vr: 7.5 mL) that was made uniform by stirring was soft.
  • Example 6 was prepared such that the latex obtained by diluting a carboxyl group-modified SBR latex (Nalstar SR-116) with deionized water to a solid concentration of 20% had a jER806 of 5 parts by mass with respect to 100 parts by mass of the solid content. A latex to which the function-expressing particles were added was prepared. Next, 2.5 parts by mass of a 20% aqueous solution of 1,4-diazabicyclo [2.2.2] octane (DABCO) as a curing catalyst was added to the latex and stirred to obtain a uniform nonwoven fabric impregnating latex. This was left still at room temperature for 1 week.
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • the nonwoven fabric-impregnated latex was allowed to stand at room temperature for 2 weeks.
  • Control 1 Separately, 2 parts by weight of an anionic emulsifier and 5 parts by weight of a nonionic emulsifier were added to 100 parts by weight of jER806, and deionized water was gradually added with stirring to prepare an epoxy resin emulsion containing 44% of jER806.
  • Control 1 was prepared by adding 11 parts by mass (5 parts by mass as jER806) of this emulsion instead of the function-expressing particles. This was left still at room temperature for 1 week.
  • Control 1 was allowed to stand at room temperature for 2 weeks.
  • the wet latex was squeezed with mangles while being sandwiched between wire meshes so that the amount of impregnation latex was 220 g / m 2 , pre-dried at 110 ° C. for 10 minutes, and cured at 140 ° C. for 5 minutes.
  • the resin-impregnated nonwoven fabric impregnated with the latex added with the function-expressing fine particles of Example 6 did not lose any shape, but the function-expressing fine particles of Example 5 were added.
  • the resin-impregnated nonwoven fabric impregnated with latex was slightly out of shape.
  • Example 7 (Preparation of functionally expressed particles)
  • 15 g of 80% acetone solution of epoxy resin jER806 15 g of becamine M-3 (60) (viscosity (23 ° C.): 38 mPa ⁇ s), which is a 60% aqueous solution of methylolated melamine, (methylolated melamine) 9 g, volume of methylolated melamine Vf 9 mL, total volume Vl of liquid: 15 mL) was taken into 9 g of silica particles (adsorbed), the temperature in vacuum drying was changed from 50 ° C. to room temperature, and 3.75 g of water was distilled off.
  • liquidity at the time of use is given as a hardening
  • Example 5 (Preparation of latex for nonwoven impregnation) In the latex for impregnation of Example 5, the function-expressing particles of Example 7 were added so that the methylolated melamine was 5 parts by mass with respect to 100 parts by mass of the solid content of the carboxyl group-modified SBR latex. Next, 0.5 parts by mass of catalyst ACX (manufactured by DIC) was added as a catalyst and stirred to obtain a uniform latex for impregnating nonwoven fabric. This was left still at room temperature for 1 week.
  • catalyst ACX manufactured by DIC
  • the nonwoven fabric-impregnated latex was allowed to stand at room temperature for 2 weeks.
  • Example 8 In the same manner as in Example 7 except that 17.3 g of becamine M-3 (60), 10.4 g of soft unsaturated polyester resin C, and 104 mg of Permec N were changed, functionally expressed particles were obtained. It was.
  • the expressed particle was 32.4 g.
  • the nonwoven fabric-impregnated latex was allowed to stand at room temperature for 2 weeks.
  • the resin-impregnated nonwoven fabric impregnated with the latex added with the function-expressing fine particles of Example 8 did not lose any shape, but the function-expressing fine particles of Example 7 were added.
  • the resin-impregnated nonwoven fabric impregnated with latex was slightly out of shape.
  • Example 9 (Preparation of functionally expressed particles)
  • T-1890 which is an isocyanate group-containing compound (isocyanate curing agent)
  • T-1890 9.9 g, T-1890 volume Vf 9.9 mL, liquid total volume Vl: 15 mL was taken in (adsorbed to) 9 g of silica particles, and the same operation as in Example 5 was performed.
  • Control 3 a resin solution obtained by adding 5 parts by mass of T-1890 to 100 parts by mass of acrylic polyol and mixing them was used as Control 3.
  • Example 5 The results were as follows. -Resin composition to which Example 9 was added 8 days-Resin composition to which Example 10 was added 11 days-Resin liquid of control 3 immediately after preparation Example 11 (Preparation of functionally expressed particles)
  • Example 5 In Example 5, in place of 15 g of 80% acetone solution of epoxy resin jER806, 90% ethyl acetate solution of Millionate MR-200, an isocyanate group-containing compound (isocyanate curing agent) (viscosity (23 ° C.): 43 mPa ⁇ s) Except that 15 g (Millionate MR-200 13.5 g, Millionate MR-200 volume Vf 13.5 mL, total volume Vl of liquid: 15 mL) was incorporated into 9 g of silica particles (adsorbed), exactly the same as Example 5 To obtain 30 g of function-expressing particles encapsulating (incorporating) 45 mass% of Millionate MR-200 (Millionate MR-200 / silic
  • Control 4 a resin solution obtained by adding 5 parts by mass of Millionate MR-200 to 100 parts by mass of acrylic polyol and mixing them was used as Control 4.
  • Example 5 (Measurement of pot life of Examples 11 and 12 and Control 3) The pot life at 50 ° C. of each of the one-component polyurethane resin compositions of Examples 11 and 12 and the resin solution of Control 4 was measured. The results were as follows. -Resin composition to which Example 11 was added 5 days Resin composition to which Example 12 was added 7 days-Resin liquid of control 4 immediately after preparation Example 13 (Preparation of functionally expressed particles) In Example 5, instead of 15 g of 80% acetone solution of epoxy resin jER806, 80% ethyl acetate solution of Takenate D-170N, which is an isocyanate group-containing compound (isocyanate curing agent) (viscosity (23 ° C.): 91 mPa ⁇ s) 15 g, (Takenate D-170N 12 g, Takenate D-170N volume Vf 12 mL, total volume Vl of liquid: 15 mL) were incorporated in silica particles 9 g
  • Control 5 was a resin solution obtained by adding 5 parts by mass of Takenate D-170N to 100 parts by mass of acrylic polyol and mixing them.
  • Example 5 (Measurement of pot life of Examples 13 and 14 and Control 5) The pot life at 50 ° C. of each of the one-component polyurethane resin compositions of Examples 13 and 14 and the resin solution of Control 5 was measured. The results were as follows. -Resin composition to which Example 13 was added 8 days Resin composition to which Example 14 was added 11 days-Resin liquid of control 5 immediately after preparation Example 15 (Preparation of functionally expressed particles) In Example 5, instead of 15 g of 80% acetone solution of epoxy resin jER806, 15 g of 70% acetone solution (viscosity (23 ° C.): 8 mPa ⁇ s) of 1-benzyl-2-phenylimidazole (1B2PZ), (1B2PZ 10 0.5 g, 1B2PZ volume Vf 10.5 mL, total volume Vl of liquid: 15 mL) was taken into 9 g of silica particles (adsorbed), and soft unsaturated polyester resin C 6 g
  • 1-part epoxy resin composition was prepared by adding 13.5 parts by mass of function-expressing particles (5 parts by mass as 1B2PZ) to 100 parts by mass of epoxy resin (jER828) as the second resin, and uniformly mixing at room temperature. .
  • control 6 a resin solution obtained by adding 5 parts by mass of 1B2PZ to 100 parts by mass of epoxy resin (jER828) and mixing them was used as control 6.
  • Example 15 (Measurement of pot life of Example 15 and Control 6) The pot life at 50 ° C. of each of the one-component epoxy resin composition and the resin solution of Control 6 was measured. The results were as follows. -One-pack type epoxy resin composition of Example 15 6 weeks-Resin solution of Control 6 3 days Example 16 (Preparation of functionally expressed particles) In Example 5, instead of 15 g of 80% acetone solution of epoxy resin jER806, 15 g of 60% acetone solution of 4,4′-diaminodiphenylmethane (DDM) (viscosity (23 ° C.): 7 mPa ⁇ s), 9 g of DDM, The DDM volume Vf (9 mL, total liquid volume Vl: 15 mL) was taken up (adsorbed) into 9 g of silica particles, and soft unsaturated polyester resin C 6 g was added with 60 mg of Permec N.
  • DDM 4,4′-diaminodiphenyl
  • Control 7 a resin solution obtained by adding 14 parts by mass of DDM to 100 parts by mass of epoxy resin (jER828) was used as Control 7.
  • Comparative Example 2 Dissolve 6.0 g of bisphenol type epoxy resin jER828 (manufactured by Mitsubishi Chemical Corporation) and 3.0 g of amine-based curing agent YN3080 (manufactured by Mitsubishi Chemical Corporation) in 13.5 g of MEK, have a viscosity of 100 mPa ⁇ s or less, and a pot life at 23 ° C. A resin solution for 5 hours was prepared.
  • the function-expressing particles are used, for example, as a bactericidal agent, an antibacterial agent, an antiseptic, an algae-proofing agent, an antifungal agent, a herbicide, an insecticide, an attractant and a repellent, as well as a flame retardant and a curing agent.

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Abstract

La présente invention concerne des particules à développement de fonction comprenant des particules minérales poreuses, un ingrédient fonctionnel enfermé dans les pores des particules minérales poreuses, et une résine avec laquelle l'ingrédient fonctionnel a été bloqué à l'intérieur des particules minérales poreuses. La résine est un objet durci obtenu par durcissement d'une solution de monomère vinylique d'une résine durcissable.
PCT/JP2016/073357 2015-08-14 2016-08-08 Particules à développement de fonction et leur procédé de production Ceased WO2017030041A1 (fr)

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WO2020203587A1 (fr) * 2019-03-29 2020-10-08 株式会社クラレ Particules d'agrégat composite, et matériau absorbant, corps moulé ainsi qu'épurateur d'eau mettant en œuvre celles-ci
JP2021042113A (ja) * 2019-09-13 2021-03-18 大阪ガスケミカル株式会社 疎水性無機粒子および粒子含有樹脂組成物
CN112853807A (zh) * 2021-02-23 2021-05-28 广东施彩新材料科技有限公司 一种改性丙烯酸树脂缓释抗菌剂及其制备方法和应用

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