JP6804384B2 - Function-expressing particles and their manufacturing method - Google Patents

Description

The present invention relates to functional particles and methods for producing them, such as fungicides, antibacterial agents, preservatives, algae repellents, fungicides, herbicides, insecticides, attractants and repellents, as well as flame retardants and hardeners. The present invention relates to functional expression particles used for agents and the method for producing the same.

Conventionally, fine particles in which functional substances such as pigments, fragrances, pesticides, pharmaceuticals, enzymes, and physiologically active substances are encapsulated or adsorbed in porous fine particles have been used for various purposes.

For example, there has been proposed a porous fine particle in which a supported substance is encapsulated in porous fine particles and the surface thereof is coated with a polymer compound or a curable compound to retain the supported substance (for example, Patent Document 1). reference.). In Patent Document 1, an acrylic resin (thermoplastic resin) or an epoxy resin (thermosetting resin) is used as the polymer compound or the curable compound.

Japanese Unexamined Patent Publication No. 2009-12996

However, in 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 substance to be supported is present, and then the organic solvent in the organic solvent solution is removed. As a result, porous fine particles are produced. However, when the porous fine particles are produced in this way, the volume of the acrylic resin or epoxy resin becomes smaller than the total volume of the pores because the organic solvent is removed. 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 particles.

An object of the present invention is to provide functional expression particles capable of containing a sufficient amount of resin and reliably sealing functional components in the pores of the porous particles by such resin, and a method for producing the same. To do.

The present invention
[1] The resin contains porous inorganic particles, a functional component incorporated into the pores of the porous inorganic particles, and a resin that seals the functional component in the pores, and the resin is curable. Function-developing particles, which are cured products obtained by curing a vinyl monomer solution of a resin.
[2] The functional expression according to the above [1], wherein 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. particle,
[3] The functional expression particles according to the above [1] or [2], wherein the vinyl monomer solution is an unsaturated polyester resin.
[4] The functional expression particle according to any one of the above [1] to [3], wherein the functional component is a water-insoluble component.
[5] The functional expression particle according to any one of [1] to [3] above, wherein the functional component is a water-soluble component.
[6] The item according to any one of [1] to [5] above, wherein the ratio of the total mass of the functional component and the resin to the mass of the porous inorganic particles is 1.60 or more. Described functional particles,
[7] The functional expression particle according to any one of [1] to [6] above, wherein the ratio of the mass of the functional component to the mass of the resin is 2.25 or less.
[8] The function according to any one of the above [1] to [7], wherein the ratio of the volume of the resin to the oil-absorbable volume of the porous inorganic particles is 0.30 or more. Expression 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. The functional expression particles described in the section,
[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. The functional expression particles described in the section,
[11] The functional component is blended with 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. In the step (1) of incorporating the porous inorganic particles into the pores of the porous inorganic particles, a vinyl monomer solution of a curable resin is added to the porous inorganic particles, and the total volume of the functional component and the vinyl monomer solution is the porous inorganic. The step (2) of blending the particles so that the ratio of the particles to the oil-absorbable volume is 0.75 or less and incorporating the vinyl monomer solution into the pores of the porous inorganic particles, and the vinyl monomer solution. A method for producing functional-expressing particles, which comprises a step (3) of sealing the functional component in the pores by curing.
[12] The method for producing functional particles according to the above [11], wherein the viscosity of the vinyl monomer solution at 23 ° C. is 100 mPa · s or less.
[13] The vinyl monomer solution of the curable resin is a thermosetting resin composition, and the thermosetting resin composition has a normal temperature gelling time measured in accordance with JIS K6901-A method (2008). The method for producing a functional-expressing particle according to the above [11] or [12], wherein the method is 10 minutes or longer.
[14] The vinyl monomer solution of the curable resin is a thermosetting resin composition.
The thermosetting resin composition according to the above [11] to [13], wherein the normal temperature gelling time measured according to the JIS K6901-A method (2008) is 1 hour or less. The method for producing functional expression particles according to any one of the above.

According to the method for producing functional expression particles of the present invention, a vinyl monomer solution of a curable resin is mixed with the porous inorganic particles, and the vinyl monomer solution is mixed in the pores of the porous inorganic particles in which the functional components are incorporated. The vinyl monomer solution is cured. Therefore, unlike Patent Document 1, all the vinyl monomer solutions in the pores are cured to form a cured product without requiring a step of removing the organic solvent when coating with the polymer compound, so that the resin in the pores is formed. A large volume can be secured. Therefore, such a resin can reliably seal a sufficient amount of functional components in the porous inorganic particles.

As a result, the function-expressing particles of the present invention can express their functions by releasing a sufficient amount of functional components under physical conditions such as destruction.

One embodiment of the function-expressing particles of the present invention contains porous inorganic particles, a functional component incorporated into the pores of the porous inorganic particles, and a resin that seals the functional component in the porous inorganic particles. To do. Hereinafter, methods, uses, and effects of producing porous inorganic particles, functional components, resins, and functional particles will be described in order.

1. 1. Porous Inorganic Particles Examples of the inorganic substance forming the porous inorganic particles include silicates such as calcium silicate, barium silicate, magnesium silicate and zeolite, such as calcium phosphate, barium phosphate, magnesium phosphate and phosphoric acid. Phosphates such as zirconium and apatite, such as silicon oxide (eg, silicon dioxide (silica), silicon monoxide, etc.), alumina, oxides such as magnesium oxide, and mixtures of two or more compounds thereof. Be done. Oxides are preferred, silicon oxide is more preferred, and silica is more preferred.

Porous inorganic particles have a spherical shape (including a true spherical shape) or an indefinite shape. Further, the porous inorganic particles are usually aggregates (secondary particles or the like) in which primary particles are aggregated with each other.

When the porous inorganic particles are made of silica (silicon dioxide) and have an indefinite shape, the porous inorganic particles are produced by, for example, a wet method, a dry method, or the like, and are preferably produced by a wet method. In the wet method, silica is produced by neutralizing water glass (aqueous solution of sodium silicate) with a mineral acid such as sulfuric acid. At this time, by advancing the neutralization reaction in the high temperature and alkaline pH range, the growth of the primary silica particles proceeds rapidly, and the precipitation method silica that precipitates the primary particles in a floc shape and the neutralization reaction are carried out in the acidic pH range. There is a gel method silica in which the growth of primary particles is suppressed by advancing, and the reaction solution is made into a mass gel by a three-dimensional network structure. The gel method silica is preferable because the primary particles are smaller and the pore volume is larger than that of the sedimentation method silica.

Further, the porous inorganic particles produced as described above can be prepared by firing. When the porous inorganic particles are oxides (specifically, silicon oxide, etc.), the OH groups (specifically, silanol groups, etc.) existing on the surface are removed by firing the porous inorganic particles. Will be done. When the functional component incorporates a compound that reacts with a silanol group (specifically, a compound containing a silanol group or a hydroxyl group) or a compound having an interaction (specifically, an amino group, etc.) into silicon oxide. In some cases, it is preferable to remove the silanol group of silicon oxide by firing because the functional component is easily released.

When the porous inorganic particles are composed of silica (silicon dioxide) and have a spherical shape, they are dispersed and stabilized in an inert solvent such as a hydrocarbon in an aqueous phase droplet of a desired size. It is produced by producing silica by a wet method.

Further, the pores of the porous inorganic particles mean the pores inside the primary particles forming the porous inorganic particles and the voids between the primary particles.

The pore volume of the porous inorganic particles (total volume of the pores of the 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 the nitrogen gas adsorption method. The pore volume of the porous inorganic particles means the pore volume (mL) per unit mass (g) inside 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 the 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 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 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 quality inorganic particles is shown. Since the oil absorption of the porous inorganic particles is the measured value shown above, it does not uniquely correlate with the pore volume, the specific surface area, and the average pore diameter.

The average value of the maximum lengths of the porous inorganic particles (the average particle diameter in the case of having a spherical shape) is, for example, 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more, and for example. , 50 μm or less, preferably 30 μm or less.

2. 2. Functional component The functional component is incorporated into the pores of the porous inorganic particles and sealed (coated) with a resin. Then, due to physical destruction of the particles during use, the functional component is released from the resin and released from the pores. Alternatively, the functional component can exhibit sustained release in a harsh environment such as in a solvent where it is easily leached during use.

Examples of the functional ingredient include antibiotic active compounds, flame retardants, curing agents, pigments, fragrances, enzymes and the like, and preferred examples include antibiotic active compounds, flame retardants and curing agents.

2-1. Antibiotics-active compounds Examples of the antibiotic-active compounds include antibiotic-active compounds that are water-insoluble at room temperature (water-insoluble components) and antibiotic-active compounds that are water-soluble at room temperature (water-soluble components).
In addition, water insoluble is a property that is substantially insoluble in water at room temperature (20 ° C.), and specifically, includes a property that is completely insoluble in water and a property that is extremely soluble (slightly soluble). Specifically, the solubility of a water-insoluble substance in water at room temperature is, for example, 10 g / L or less, and further 5 g / L or less.

On the other hand, water-soluble is a property that is substantially soluble in water at room temperature (25 ° C.), and the solubility of a water-soluble substance in water at room temperature exceeds, for example, 10 g / L, and further 20 g / L or more. Is.

2-1-1. Water-insoluble antibiotic-active compounds Water-insoluble antibiotic-active compounds include antibiotic-active compounds disclosed in International Publication No. 2011/030824, International Publication No. 2013/100102, and the like, Japanese Patent Application Laid-Open No. 04-093030. Examples include capsaicins disclosed in.

In addition, water-insoluble antibiotic active compounds have antibiotic activity such as bactericidal, antibacterial, antiseptic, antiseptic, antifungal, herbicide, insecticide, attraction and repellent, bactericidal, antibacterial, antiseptic, antiseptic , Antifungal agents, herbicides, pesticides, attractants and repellents, etc.

Examples of bactericidal antiseptic and algae antiseptic agents (including antiseptic and antifungal agents) include organic iodine compounds, triazole compounds, carbamoylimidazole compounds, dithiol compounds, isothiazoline compounds, nitroalcohol compounds, and paraoxybenzoic acid. Examples include ester.

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

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

Examples of the carbamoylimidazole-based compound include N-propyl-N- [2- (2,4,5-trichloro-phenoxy) ethyl] imidazole-1-carboxamide (prochloraz).

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

Examples of the isothiazolin-based compound include 2-n-octyl-4-isothiazolin-3-one (OIT) and 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT). ..

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

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

Examples of the anti-termite agent (anticide) include pyrethroid compounds, neonicotinoid compounds, organochlorine compounds, organophosphorus compounds, carbamate compounds, and oxadiadin compounds.

Examples of the pyrethroid compound include pyrethroid insecticides such as pyrethrin, cinerin, and jasmorin obtained from Shirobanamushiyokegiku, and allethrin, bifenthrin, acrinathrin, alphacypermethrin, tralomethrin, cypermethrin, ciphenothrin, and prarethrin derived from these. , Etofenprox (2- (4-ethoxyphenyl) -2-methylpropyl = 3-phenoxybenzyl = ether), cypermethrin, fenvalerate and other pyrethroid insecticides.

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

Examples of the organochlorine compound include Kelsen and the like.

Examples of the organophosphorus compound include phoxim, pyridafenthion, fenitrothion, tetrachlorobinphos, diclofenthion, propetanephos and the like.

Examples of the carbamate compound include phenocarb, propoxul and the like.

Examples of the oxadiazine compound include indoxacarb and the like.

Further, examples of the herbicide include pyracronyl, pendimethalin, indanophan and the like.

Examples of the insecticide include pyriproxyfen.

Examples of the repellent include DEET and capsaicins (pungent ingredients). Preferred are capsaicins.

Examples of capsaicins include capsaicin (N-[(4-hydroxy-3-methoxyphenyl) methyl] -8-methyl-6-nonenamide) and capsaicin derivatives. Examples of the capsaicin derivative include N-vanillyl nonanamide (nonylic acid vanillyl amide), decylic acid vanillyl amide, nordihydrocapsaicin, dihydrocapsaicin, homodihydrocapsaicin, homocapsaicin and the like. Preferred examples of capsaicins include capsaicin and N-vanillyl nonaneamide.

Preferred examples of the water-insoluble antibiotic active compound include antiseptic and antifungal agents and repellents.

2-1-2. Water-soluble antibiotic-active compound The water-soluble antibiotic-active compound is selected from, for example, a wood preservative that imparts antiseptic properties to wood, for example, a repellent having antibiotic activity such as repellent. Examples of the water-soluble antibiotic active compound include sodium borate, denatonium benzoate (bitterness component) and the like.

Sodium borate contains a hydrated salt, specifically, disodium octaborate tetrahydrate and the like.

Examples of the water-soluble antibiotic active compound include 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT) and 2-methyl-4-isothiazolin-3-one (H-MIT). ), 2-Bromo-2-nitropropane-1,3-diol (bronopol), 2-pyridinethiol-1-sodium oxide (NaPt), hexahydro-1,3,5-tris (2-hydroxyethyl) -1 , 3,5-Triazine, methyl 1H-benzimidazol-2-ylcarbamate hydrochloride (carbendazim hydrochloride) and the like.

2-2. Flame Retardants Examples of flame retardants include flame retardants that are water-insoluble at room temperature (water-insoluble components) and flame retardants that are water-soluble at room temperature (water-soluble components).

2-2-1. Water-insoluble flame retardant Examples of the water-insoluble flame retardant include antimony oxide, aluminum hydroxide, magnesium hydroxide and the like.

2-2-2. Water-soluble flame retardant Examples of the water-soluble flame retardant include trimethyl phosphate, guanidine phosphate, ammonium polyphosphate and the like.

2-3. Curing agent A curing agent is a functional component that can be released from functional particles and undergo a curing reaction (crosslinking reaction) with a resin (second resin described later). The curing agent is also a cross-linking agent (first curing agent) for converting the resin (second resin) into a cross-linked resin (curing resin) having a three-dimensional network structure. The curing agent and the cross-linking agent are not clearly distinguished.

As a functional component, the curing agent is a first curing agent and is distinguished from a second curing agent which is a component blended in an unsaturated polyester resin described later.

The curing agent has a plurality of first functional groups. The first functional group can react with the second functional group of the resin (second resin) described later.

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. Examples thereof include a group, a silanol group, an aziridine group, an acetoacetoxy group, and a diacetone group. A plurality of single types of first functional groups are contained in the curing agent, or a plurality of types of first functional groups are contained in the curing agent. Preferably, a plurality of first functional groups of a single type are contained in the curing agent.

Specifically, as the curing agent, for example, an epoxy group-containing compound, an N-methylol group-containing compound, an N-alkoxymethyl group, an isocyanate group-containing compound, a nitrogen atom-containing compound, an aldehyde group-containing compound, an oxazoline group-containing compound, and hydrazide. Examples thereof include group-containing compounds, silanol group-containing compounds, aziridine group-containing compounds, acetoacetoxy group-containing compounds, and diacetone group-containing compounds. Preferred examples of the curing agent include an epoxy group-containing compound, an N-methylol group-containing compound, an isocyanate group-containing compound, and a nitrogen atom-containing compound. The curing agent can be used alone or in combination.

The curing agent may be either water-insoluble at room temperature or water-soluble at room temperature.

2-3-1. Epoxy group-containing compounds Examples of epoxy group-containing compounds include epoxy resins, epoxy group-containing vinyl monomer (copolymerization) oligomers, epoxidized unsaturated fatty acid esters, and epoxidized polybutadienes. An epoxy resin is preferable.

Examples of the epoxy resin include glycidyl ether type epoxy resin (bisphenol A type, bisphenol F type bisphenol type epoxy resin, phenol novolac and cresol novolac type epoxy resin, etc.), alicyclic epoxy resin, glycidyl ester type epoxy resin, and glycidyl. Examples thereof include amine type epoxy resin and heterocyclic epoxy resin. 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. The epoxy group-containing compound 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.

2-3-2. N-methylol group-containing compound, N-alkoxymethyl group-containing compound Examples of the N-methylol group-containing compound include methylolated melamine (melamine initial condensate), methylolated urea (urea initial condensate), and urea glioxal formaldehyde reactant. (Glioxal resin), N-methylolacrylamide (copolymerization) oligomer and the like can be mentioned. Examples of the N-alkoxymethyl group-containing compound include 3,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine, N-methoxymethylacrylamide (copolymerization) oligomer, and N-butoxy. Methylacrylamide (copolymerized oligomers and the like. N-methylol group-containing compounds and / or N-alkoxymethyl group-containing compounds 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) and the like contained in the second resin.

2-3-3. Isocyanate group-containing compound Examples of the isocyanate group-containing compound include diisocyanate. As the diisocyanate, for example, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), for example, 1,3- or 1,4-xylylene diisocyanate. Aromatic aliphatic diisocyanates such as isocyanate (XDI), eg, aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), 1,5-pentamethylene diisocyanate (PDI), eg 3-isocyanate methyl-3,5,5-trimethyl Alicyclic diisocyanates such as cyclohexylisocyanate (IPDI), 4,4'-methylenebis (cyclohexylisocyanate) (H12MDI), norbornandiisocyanate (NBDI), 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H6XDI) For example, aromatic aliphatic diisocyanates such as tetramethylxylylene diisocyanate (TMXDI) can be mentioned. Further, as the diisocyanate, the alcohol adduct of each of the above diisocyanates (specifically, the trimethylolpropane adduct), the biuret modified product, the allophanate modified product, and the multimer (dimer, trimerate (isocyanurate modified product)). ) 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, an amino group, a thiol group, a carboxyl group (described later) and the like contained in the second resin.

2-3-4. Nitrogen Atom-Containing Compound A nitrogen atom-containing compound is an active hydrogen group-containing compound having an active hydrogen group containing hydrogen that is directly bonded to a nitrogen atom.

Examples of the nitrogen atom-containing compound include an imidazole compound and a polyamine compound.

Examples of the imidazole compound include imidazole, for example, an imidazole derivative. Preferably, an imidazole derivative is mentioned.

An imidazole derivative is a compound in which a part of a hydrogen atom in imidazole is substituted with a substituent. Examples of the imidazole derivative include 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1-2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl imidazole, and the like. Examples thereof include 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole (1B2PZ).

Examples of the polyamine compound include chain aliphatic diamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and cyclic aliphatic diamine compounds such as isophoronediamine and diaminodicyclohexylmethane, for example, xylene diamine. Examples thereof include aromatic diamine compounds such as diaminodiphenylmethane (DDM).

The nitrogen atom-containing compound can be used alone or in combination.
The active hydrogen group in the nitrogen atom-containing compound can react with the epoxy group and the isocyanate group (described later) contained in the second resin.

2-3-5. Aldehyde group-containing compound Examples of the aldehyde group-containing compound include glyoxal and glyoxal-based resins. 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 or the like.

2-3-6. Oxazoline group-containing compound Examples of the oxazoline group-containing compound include 2,2'-(1,3-phenylene) bis-2-oxazoline. The oxazoline group-containing compound 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.

2-3-7. Hydrazide Group-Containing Compounds Examples of the hydrazide group-containing compound include dihydrazide adipate and carbohydrazides such as 1,3-bis (hydrazidecarboethyl) -5-isopropylhydrantin. 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) or the like contained in the second resin.

2-3-8. Silanol group-containing compound Examples of the silanol group-containing compound include an alkoxysilane and an oligomer of alkoxysilane. The silanol group-containing compound can be used alone or in combination.

The silanol group in the silanol group-containing compound can react (condensation reaction) with the hydroxyl group (described later) contained in the second resin.

2-3-9. Aziridine Group-Containing Compound Examples of the aziridine group-containing compound include 2- (1-arididinyl) ethyl (meth) acrylate oligomer. The aziridine group-containing compound can be used alone or in combination.

The aziridine group in the aziridine group-containing compound can react with the carboxyl group, the thiol group, and the phenolic hydroxyl group (described later) contained in the second resin.

2-3-10. Acetoxy Group-Containing Compounds Examples of the acetoxy group-containing compound include acetoxyethyl (meth) acrylate oligomers. The acetoxy group-containing compound can be used alone or in combination.

The acetoxy group can react with an amino group, a hydrazide group (described later) and the like contained in the second resin.

2-3-11. Diacetone group-containing compound Examples of the diacetone group-containing compound include diacetone (meth) acrylamide oligomer and the like. 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.

3. 3. Resin The resin (first resin) is a vinyl monomer solution of a low molecular weight polymer (hereinafter referred to as a curable resin, which is also a first curable resin) containing a plurality of vinyl polymerization-reactive double bonds in the molecule. It is a cured product that has been cured.

The vinyl monomer solution is a curable resin composition (first curable resin composition) in which a curable resin is dissolved in a liquid vinyl monomer at room temperature (25 ° C.), preferably a curable resin and vinyl. It consists only of a monomer and does not contain a non-reactive solvent (such as a ketone solvent such as methyl ethyl ketone).

The curable resin composition is vinyl polymerizable. The curable resin composition may be a room temperature curable thermosetting resin composition, a high temperature curable thermosetting resin composition, or ultraviolet rays, depending on the selection of a polymerization initiator (described later), a polymerization accelerator (described later), or the like. , An active energy ray-curable resin composition such as an electron beam.

Examples of the curable resin include unsaturated polyester, epoxy (meth) acrylate, and urethane (meth) acrylate. Preferably, unsaturated polyesters are mentioned from the viewpoint of cost and obtaining resins having various performances.

Examples of the active energy ray-curable resin include urethane (meth) acrylate.

As the curable resin, unsaturated polyester is preferable.

3-1. Unsaturated polyester Unsaturated polyester is obtained by polycondensation (condensation polymerization) of a dibasic acid component containing an unsaturated dibasic acid and a dihydric alcohol (diol) component.

Specific examples of the unsaturated dibasic acid include maleic acid, fumaric acid, methyl fumaric acid (mesaconic acid), methyl maleic acid (citraconic acid), aconitic acid, and itaconic acid (isomers of mesaconic acid and citraconic acid). Α, β-unsaturated dibasic acid and the like. Further, examples of the unsaturated dibasic acid include the above-mentioned anhydrides of α, β-unsaturated dibasic acid (specifically, maleic anhydride, citraconic anhydride, etc.). These can be used alone or in combination of two or more. Further, as the unsaturated dibasic acid, fumaric acid and maleic anhydride are preferably mentioned, and maleic anhydride is more preferable.

The content ratio of 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 may include saturated dibasic acid in addition to the unsaturated dibasic acid described above. Specific examples of the saturated dibasic acid include phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, and 3,6-endodichloromethylene tetrachlorophthalic anhydride (Hett). Acids), 3,6-endomethylenetetrahydrophthalic anhydride (phthalic anhydride), adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. As the saturated dibasic acid, phthalic anhydride and adipic acid are preferable, and phthalic anhydride is more preferable. From the viewpoint of lowering the viscosity of the unsaturated polyester resin or making the cured product flexible, the saturated dibasic acid has 6 or more carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. It is effective to select a saturated fatty acid dicarboxylic acid of 10 or less.

The content ratio of 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. The content ratio of saturated dibasic acid to 100 mol parts of 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. It is 125 mol parts or less.

Examples of the dihydric alcohol component include polyethylene glycols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, for example, dipropylene glycol. Polypropylene glycols such as tripropylene glycol, such as neopentyl glycol, such as 2,2-bis (4-hydroxycyclohexyl) propane (hydrided bisphenol A), such as bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct. The body etc. can be mentioned. As the divalent alcohol component, diethylene glycol and triethylene glycol are preferable from the viewpoint of softening the cured product.

The dihydric alcohol component can be used alone or in combination of two or more. The divalent alcohol component preferably includes a combination of propylene glycol and diethylene glycol, and a combination of triethylene glycol and ethylene glycol.

In addition, unsaturated polyester having an unsaturated dibasic acid content of 40 mol% or less in the dibasic acid component and a total content of polyethylene glycol and polypropylene glycol in the dihydric alcohol component of 60 mol% or more. The cured product of is soft. Therefore, the unsaturated polyester obtained with such a composition is defined as a soft unsaturated polyester. The 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 brittle and easily broken cured product can be obtained. On the other hand, when isophthalic acid and / or terephthalic acid is used as the saturated dibasic acid, a cured product resistant to acids, alcals and the like can be obtained. When the functional component is released by pressurization and / or heating, phthalic anhydride and orthophthalic acid are preferably used as the saturated dibasic acid. Further, the flexible soft unsaturated polyester generally uses adipic acid as a raw material as a saturated dibasic acid.

In the unsaturated polyester, the above-mentioned dibasic acid component and the above-mentioned dihydric alcohol component are arranged so that, for example, the molar ratio of the dihydric alcohol component to the dibasic acid component is 1.00 or more and 1.10 or less. And then polycondensed them 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.

Further, in the above-mentioned polycondensation of the dibasic acid component and the dihydric alcohol component, in order to prohibit the addition polymerization (vinyl polymerization) of the unsaturated dibasic acid, the polymerization is prohibited in the mixture of the dibasic acid component and the dihydric alcohol component. An agent (first polymerization inhibitor) is added.

Examples of the polymerization inhibitor include hydroquinone compounds such as hydroquinone and methylhydroquinone, benzoquinone compounds such as benzoquinone and methyl-p-benzoquinone, and catechol compounds such as t-butylcatechol, for example, 2,6-di-. Phenolic compounds such as t-butyl-4-methylphenol and 4-methoxyphenol (hydroquinone methyl ether), such as phenothiazine and copper naphthenate, can be mentioned. These can be used alone or in combination of two or more. Hydroquinone is preferred.

The addition ratio of the polymerization inhibitor is, for example, 1 ppm or more, preferably 10 ppm or more, and for example, 1000 ppm or more, preferably 1000 ppm or more, based on a mass, with respect to the mixture of the dibasic acid component and the dihydric alcohol component. It is 100 ppm or less.

The unsaturated polyester can also be obtained by, for example, ring-opening polymerization. Specifically, a polyhydric alcohol is used as an initiator, and if necessary, a metal soap such as zirconium or zinc is used in combination with a polymerization catalyst. In the production of unsaturated polyester by ring-opening polymerization, maleic anhydride is an essential component as a dibasic acid component, acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride are used, and propylene oxide is used as a divalent alcohol component. Ring-opening polymerization using alkylene oxides such as ethylene oxide, butylene oxide, styrene oxide, and epichlorohydrin as monomers. Further, 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 [mgKOH / g] or more, preferably 10 [mgKOH / g] or more, and for example, 80 [mgKOH / g] or less, preferably 40 [mgKOH / g] or more. g] or less. The acid value of unsaturated polyester is measured according to JIS K6901-A method (2008).

3-2. Epoxy (meth) acrylate Epoxy (meth) acrylate is also referred to as vinyl ester. The epoxy (meth) acrylate can be obtained, for example, by the following method. That is, a bisphenol type epoxy resin and an unsaturated carboxylic acid such as (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid) are reacted in the presence of a catalyst such as a tertiary amine to form an epoxy ring. A method of forming an ester bond by opening a ring with a carboxyl group (1), for example, a carboxyl group terminal of an unsaturated oligo ester and an epoxy group of an epoxy group-containing acrylic acid ester such as glucidyl (meth) acrylicate. For example, an epoxy (meth) acrylate can be obtained by a method (2) in which an epoxy ring is opened with a carboxyl group and an ester bond is introduced by reacting in the presence of a catalyst such as a tertiary amine.

3-3. Urethane (meth) acrylate Urethane (meth) acrylate contains a diisocyanate such as isophorone diisocyanate and a hydroxyl group of a hydroxy group-containing (meth) acrylic acid ester such as 2-hydroxyethyl methacrylate in the presence of a catalyst such as dibutyltin dilaurate. It is an oligomer obtained by reacting below and containing a urethane bond and an ester bond.

3-4. Vinyl Monomer As the vinyl monomer, a monomer that 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 reduce the viscosity, and also plays a role as a crosslinkable monomer that copolymerizes with the unsaturated double bond of the curable resin. Examples of such a vinyl monomer include a monofunctional vinyl monomer. Specifically, for example, styrene, methylstyrene (α-methylstyrene, β-methylstyrene) (vinyltoluene), tert-butylstyrene, and the like. Styrene-based monomers such as chlorostyrene (o-chlorostyrene, m-chlorostyrene, p-chlorostyrene), for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Examples thereof include (meth) acrylate-based monomers such as butyl acrylate and 2-hydroxyethyl (meth) acrylate. Styrene-based monomers are preferable.

The vinyl monomer 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, based on 100 parts by mass of the curable resin. Is. The blending ratio of the vinyl monomer is, for example, 35% by mass or more, preferably 50% by mass or more, more preferably 51% by mass or more, based on the total amount of the curable resin and the vinyl monomer (the amount of the resin). Yes, and for example, 55% by mass or less, preferably 53% by mass or less.

When the compounding ratio of the vinyl monomer is equal to or higher than the above lower limit, the viscosity of the curable resin composition (described later) can be reduced, and the curable resin composition is rapidly incorporated into the pores of the porous inorganic particles ( Can be adsorbed and supported). On the other hand, if the compounding ratio of the vinyl monomer is not more than the above upper limit, a resin (cured product) having a high crosslink density can be obtained.

3-5. Preparation of curable resin composition 3-5-1. Dissolution of the curable resin in vinyl monomer The vinyl monomer solution of the curable resin is prepared by blending the above-mentioned curable resin and vinyl monomer in the above-mentioned ratios. Specifically, in the production of a curable resin, it is prepared by cooling after the reaction is completed and injecting the curable resin in a state of sufficient fluidity into a separately prepared vinyl monomer with stirring. (Hot dilution). Further, in the production of a curable resin, it may be prepared by a method of cooling to room temperature after completion of the reaction and injecting a vinyl monomer into the high-viscosity curable resin to dissolve it (cold dilution).

When the curable resin is an unsaturated polyester, an epoxy (meth) acrylate, or a urethane (meth) acrylate, the vinyl monomer solution of the curable resin is an unsaturated polyester resin, an epoxy acrylate resin, or a urethane acrylate resin. Each of them.

Further, the unsaturated polyester resin can be prepared by the above-mentioned method, or a commercially available product can also be used. Specifically, as unsaturated polyester resins, 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 shown in the product test table, and From the composition analysis value analyzed by NMR or the like, a commercially available product number that can be adjusted to a predetermined physical property value described below can be used. Similarly, as the epoxy acrylate resin, the Neopole series of Japan U-Pica Company, the vinyl ester series of DIC Material Corporation, and the like are used, and as the urethane acrylate, the Yupica series of Japan U-Pica Company and the like are used.

3-5-2. Adjustment of Physical Properties of Curable Resin Composition The obtained curable resin composition is adjusted so as to exhibit a normal temperature gelling 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.

First, the adsorption rate (rate of being taken into the pores) of the unsaturated polyester resin to the porous inorganic particles needs to be sufficiently high. For that purpose, 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 by a BM type viscometer. When the viscosity of the unsaturated polyester resin is not more than the above upper limit, the vinyl monomer solution can be taken in in a short time without reducing the rate of taking in the unsaturated polyester resin into the porous inorganic particle pores, and further. , The vinyl monomer solution can be sufficiently taken into the pores to prevent it from remaining on the surface of the porous inorganic particles.

Viscosity adjustment is carried out by post-addition of vinyl monomer. As described above, the total amount of vinyl monomer is, for example, 55% by mass or less, preferably 53% by mass or less, based on the total amount of the unsaturated polyester resin.

Next, the normal temperature gelling time in normal temperature curing is adjusted. The normal temperature gelling time is measured according to JIS K6901-A method (2008). The normal temperature gelling time is adjusted to be, for example, 10 minutes or more, preferably 20 minutes or more, and for example, 2 hours or less, preferably 1 hour or less.

If the room temperature gelling time of the unsaturated polyester resin is equal to or longer than the above lower limit, the unsaturated polyester resin is surely incorporated into the pores of the porous inorganic particles before being cured in the step (2) described below. be able to. That is, when the room temperature gelling time of the unsaturated polyester resin does not meet the above lower limit, the unsaturated polyester resin starts to cure before the unsaturated polyester resin is taken into the pores of the porous inorganic particles. It ends up. Therefore, the unsaturated polyester resin may not be reliably taken into the pores of the porous inorganic particles.

On the other hand, if the room temperature gelling time of the unsaturated polyester resin is equal to or less than the above upper limit, the functional component incorporated into the pores of the porous inorganic particles in the step (2) is contained in the vinyl monomer solution. It can be prevented from leaching into and subsequently migrating to the surface of the porous inorganic particles. On the other hand, in the method described in Examples 3, 4, 7, etc. of Patent Document 1, the methyl ketone solution of the epoxy resin is heated for a time equal to or longer than the above upper limit, so that the supported substance dissolves in the methyl ethyl ketone during that time. , Moves to the surface of silica fine particles.

Then, if the room temperature gelling time of the unsaturated polyester resin is equal to or less than the above upper limit, the unsaturated polyester resin can be cured quickly and with a high crosslink density in the step (3) described below. ..

The room temperature curing type unsaturated polyester resin is prepared by adding a polymerization accelerator, if necessary, a polymerization accelerator and a polymerization retarder (second polymerization inhibitor) to the unsaturated polyester resin. Examples of the polymerization accelerator include oxidizing metal soaps such as cobalt octylate and cobalt naphthenate. Examples of the polymerization promoting aid include aromatic amines such as dimethylaniline and carbonyl compounds such as acetylacetone. Examples of the polymerization retarder (second polymerization inhibitor) include those exemplified by the first polymerization inhibitor, preferably hydroquinone methyl ether and hydroquinone.

The normal temperature gelling time is adjusted as follows. In accordance with JIS K6901-A method (2008), a predetermined amount of a polymerization accelerator and, if necessary, a predetermined amount of a polymerization accelerator aid are added to a predetermined amount of the unsaturated polyester resin, and then a predetermined amount of the polymerization initiator is added. Add (methyl ethyl ketone peroxide, etc.) and measure the gelation time at room temperature. At the same time, several different amounts of different polymerization retarders (second polymerization inhibitors) are added to the above-mentioned compounded resin, and the gelation time at room temperature is measured. Examples of the polymerization retarder (second polymerization inhibitor) include those exemplified by 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 based on the mass of the vinyl monomer as the amount of the active ingredient. 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. Be done. After that, a predetermined amount of the polymerization accelerator, if necessary, a polymerization accelerator, and the amount of the polymerization retarder (second polymerization inhibitor) obtained above are blended with the unsaturated polyester resin. An unsaturated polyester resin having an adjusted gelation time and viscosity at room temperature is prepared.

In this one embodiment, the polymerization accelerator contains 0.5% by mass of 6% cobalt naphthenate or 8% cobalt octylate with respect to the unsaturated polyester resin, and does not contain a polymerization accelerator. Standard prescription. The standard measurement method is a method in which 1.0% by mass of 55% methyl ethyl ketone peroxide is added to the polymerization initiator and the gelation time at room temperature is measured.

4. Method for Producing Function-Expressing Particles Next, a method for producing function-expressing particles will be described.

In the method for producing functional particles, a liquid containing a functional component is added to the porous inorganic particles, and the ratio (Vl / Voa) of the volume of the liquid (Vl) to the oil-absorbable volume (Voa) of the porous inorganic particles is 0. In the step (1) of blending the functional components so as to be .75 or less and incorporating the functional components into the pores of the porous inorganic particles, a vinyl monomer solution of a curable resin is added to the porous inorganic particles, and the functional components and the vinyl monomer The vinyl monomer solution is 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 is 0.75 or less. It includes a step (2) of incorporating the inorganic particles into the pores and a step (3) of sealing the functional component in the pores by curing the vinyl monomer solution.

Hereinafter, each step will be described in sequence.

4-1. Process (1)
First, in this step (1), a liquid containing a functional component is prepared.

When the functional ingredient is liquid at room temperature, the functional ingredient is prepared as a liquid as it is. Preferably, when the viscosity of the functional component at 23 ° C. is 100 mPa · s or less, the functional component is prepared as it is as a liquid. The method for measuring the viscosity is the same as the method for measuring the viscosity of the vinyl monomer solution described above.

On the other hand, if the viscosity of the functional component at 23 ° C. exceeds 100 mPa · s, the functional component is diluted with the solvent described below, and the viscosity at 23 ° C. is, for example, 100 mPa · s or less, preferably. Prepare a solution of functional ingredients of 70 mPa · s or less.

If the functional ingredient is semi-solid or solid at room temperature, prepare a solution of the functional ingredient. A solution of functional components having a viscosity at 23 ° C. of 100 mPa · s or less, more preferably 70 mPa · s or less is prepared.

Specifically, if the functional component is semi-solid or solid at room temperature, the functional component is dissolved in a solvent to prepare a solution of the functional component.

Examples of the solvent include organic solvents and water. Specific examples of the solvent include organic solvents as long as the functional component is a water-insoluble component such as a water-insoluble antibiotic active compound, a water-insoluble flame retardant, or a water-insoluble curing agent, and the functional component is water-soluble. Examples of water-soluble components such as antibiotic-active compounds, water-soluble flame retardants, and water-soluble curing agents include water.

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. , Ethyl acetate, butyl acetate, etc., eg, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, eg, alcohols such as methanol, ethanol, propanol, isopropanol, eg 1,4-dioxane, tetrahydrofuran, etc. Examples of ethers. The organic solvent can be used alone or in combination of two or more. Preferred examples include ketones and alcohols.

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. Specifically, 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, based on the total amount of the solvent and the functional component. Adjust the mixing ratio of the solvent and functional ingredients.

Subsequently, a liquid containing the functional component is blended with the porous inorganic particles. Specifically, for example, the porous particles are weighed in a closed container equipped with a stirrer, and the liquid containing the functional component is dropped while stirring. At this time, the volume of the functional component (Vf) and the total volume of the volume Vs of the solvent, that is, the ratio of the volume of the liquid containing the functional component (Vl) to the oil-absorbable volume (Voa) of the porous inorganic particles (Vl /). A liquid containing a functional component is blended so that Voa) is 0.75 or less. 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 the amount of oil absorbed per 1 g of the porous inorganic particles converted from the oil-absorbing amount Vo (mL / 100 g) of the porous inorganic particles, as shown in the following formula. It is the volume obtained by multiplying (mL / g) by the mass M (g) of the porous inorganic particles.

Voa (mL) = Vo (mL / 100g) / 100 × M (g)
The oil absorption amount Vo (mL / 100 g) of the porous inorganic particles is the pore volume (V ₁ ) inside the primary particles forming the porous inorganic particles, the void volume between adjacent primary particles (V ₂ ), and the void volume (V ₂ ). The volume (mL) per 100 g of the porous inorganic particles, which is the total (V ₁ + V ₂ + V ₃ ) of the minimum volume (V ₃ ) for wetting the surface of the secondary particles with oil, is shown. On the other hand, when the liquid containing the functional component is dropped up to the above total (V ₁ + V ₂ + V ₃ ), all of the functional component cannot be supported in the porous inorganic particles. In that case, 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 absorb oil as shown in the following formula. More than 75% of the volume Voa.

0.75 <(V ₁ + V ₂ ) / Voa <1.0
Therefore, in the present invention, 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. Blended with inorganic particles.

At this time, a liquid containing the functional component may be blended with the porous inorganic particles at normal pressure, or when the pressure is reduced and the inside of the pores of the porous inorganic particles is kept in a vacuum state, the function is performed. 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.

Then, if the solution contains a solvent (ie, if the solution is a solution), the solvent is distilled off at room temperature and / or heating conditions at atmospheric pressure and / or reduced pressure.

As a result, the functional component is incorporated into the pores of the porous inorganic particles.

Further, in the above, when only a liquid containing less than 30% by mass of the functional component can be obtained, 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 was blended with the porous inorganic particles, then the solvent was removed, and then in the second time, the liquid containing the functional component was added. The functional component compounded in the first step is further compounded with respect to the incorporated porous inorganic particles, and then the solvent is distilled off. From the third time onward, this operation is repeated.

At this time, in the second time, the total volume Vf ₁ + Vl ₂ of the volume Vf _{1 of the} functional component incorporated into the porous inorganic particles in the first time and the volume Vl _{2 of} the liquid to be mixed in the second time is porous. The second liquid is blended with the porous inorganic particles so that the ratio of the quality inorganic particles to the oil-absorbable volume Voa is 0.75 or less. The same applies to the third and subsequent times.

That is, in the nth time, the total volume of the functional components incorporated into the porous inorganic particles by the _n- 1th time is Vf ₁ + Vf ₂ ... + Vf _n-1 (= ΣVf _n-1 ), and the nth time. The total volume of the liquid to be blended with Vl _n (= Vf _n + Vs) and the total volume Vf ₁ + Vf ₂ ... + Vf _n-1 + Vl _n (= ΣVf _n-1 + Vl), the oil-absorbable volume Voa of the porous inorganic particles The nth liquid is blended with the porous inorganic particles so that the ratio to 0.75 or less is 0.75 or less.

4-2. Process (2)
Then, the vinyl monomer solution of the curable resin is mixed with the porous inorganic particles in which the functional components are incorporated into the pores, and the vinyl monomer solution of the curable resin is incorporated into the pores of the porous inorganic particles.

Specifically, the vinyl monomer solution of the 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 added to the vinyl monomer solution of the curable resin before being dropped onto the porous inorganic particles. The polymerization initiator is a radical polymerization initiator that acts as an initiator in the radical polymerization (vinyl polymerization) of the step (3) described below. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. Specifically, examples of the thermal polymerization initiator include acetylacetone peroxide, methyl ethyl ketone peroxide, diethyl ketone peroxide, methyl propyl ketone peroxide, methyl isobutyl ketone peroxide, methyl acetoacetate peroxide, and ethyl acetoacetate peroxide. , Cyclohexanone peroxide, Methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, Cumempoxide, Benoxyl peroxide, t-Butylisopropylperoxycarbonate, 1,1-dibutylperoxy-3,3,5 -Trimethylcyclohexanone, t-butylperoxy-2-ethylhexanoate, amylperoxy-p-2-ethylhexanoate, 2-ethylhexylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t -Peroxy compounds such as hexyl peroxybenzoate can be mentioned, preferably methyl ethyl ketone peroxide. Further, examples of the photopolymerization initiator include benzoin derivatives. These can be used alone or in combination. The blending ratio of the polymerization initiator is, for example, 0.1 part by mass or more, preferably 0.3 part by mass or more, and, for example, 5 parts by mass with respect to 100 parts by mass of the vinyl monomer solution of the curable resin. It is by mass or less, preferably 3% by mass or less.

In the present invention, when the vinyl monomer solution of the curable resin is an unsaturated polyester resin, the standard formulation is a formulation in which 1% of 55% methylethyl chloride is mixed with the vinyl monomer solution.

Then, the vinyl monomer solution of the curable resin is incorporated into the pores of the porous inorganic particles. Specifically, for example, a vinyl monomer solution of a curable resin containing a polymerization initiator is mixed while stirring a closed container equipped with a stirrer in which the porous inorganic particles obtained in step (1) are charged. Drop. At this time, a vinyl monomer solution of the curable resin may be dropped onto the porous inorganic particles at normal pressure, or if the pressure is reduced and the pores of the porous inorganic particles are kept in a vacuum state, the curable resin The adsorption rate of the vinyl monomer solution to the porous inorganic particles can be accelerated.

4-3. Process (3)
Subsequently, in the step (3), the vinyl monomer solution of the curable resin taken into the pores of the porous inorganic particles is cured. When the thermosetting initiator blended in the vinyl monomer solution of the curable resin is curable at room temperature, it cures after 24 hours or more at room temperature (25 ° C.). In order to shorten the curing time, it can be completely cured by leaving it at room temperature (25 ° C.) for 5 hours or more, and then at 40 ° C. to 60 ° C. for 5 hours or more. When a high-temperature curable thermosetting initiator is mixed with a vinyl monomer solution of a curable resin, it is cured at a desired curing temperature and curing time. In the present invention, a room temperature curable thermal polymerization initiator is preferably used, and more preferably, it is polymerized on an unsaturated polyester resin containing 6% cobalt naphthenate or 8% cobalt octylate as a polymerization accelerator. As the initiator, a room temperature curable thermal polymerization initiator 55% methyl ethyl ketone peroxide is blended.

On the other hand, 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. In particular, when the porous inorganic particles are made of silica, the silica has a high ultraviolet transmittance, so that it can be suitably cured by ultraviolet rays.

The above-mentioned curing proceeds by vinyl copolymerization (radical copolymerization) of the vinyl group of the vinyl monomer and the unsaturated double bond of the curable resin. Then, in the porous inorganic particles, the functional component is sealed by the cured resin.

4-4. Blending ratio of each raw material In the 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, for example, 0.40 or more. It is preferably 0.50 or more, and preferably 0.75 or less.

In the step (2), the ratio ((Vf + Vr) / Voa) 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 is set to 0.75 or less. That is, it is blended so as to satisfy the following formula. The densities of the functional components and the vinyl monomer solution of the curable resin at this time are assumed to be 1.0 and g / mL.

(Vf + Vr) / Voa ≤ 0.75
here,
When (Vf + Vr) / Voa exceeds 0.75, the vinyl monomer solution is not completely taken into the pores of the porous inorganic particles, and the excess vinyl monomer solution adheres to the surface of the porous inorganic particles, and therefore the porous inorganic particles. Particles can aggregate to form a lumpy cured product. In other words, when (Vf + Vr) / Voa is 0.75 or less, it prevents the adjacent porous inorganic particles from adhering or adhering to each other, and the plurality of porous inorganic particles have excellent fluidity (smoothness). It is possible to secure the feeling that it was done.

Further, (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. It is 0.60 or more.

If (Vf + Vr) / Voa exceeds the above lower limit, the functional component and the resin can be included in a sufficient amount with respect to 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. The above, and for example, 0.60 or less.

When Vr / Voa is equal to or higher than the above lower limit, the porous inorganic particles can take in a sufficient amount of resin, whereby the functional component can be reliably sealed in the pores of the porous particles. On the other hand, although the concept of oil absorption is not disclosed in Patent Document 1, it is presumed that Vr / Voa is less than the above lower limit in order to remove the organic solvent in the organic solvent solution.

Further, the ratio of the mass of the functional component adsorbed in the step (1) to the mass of the vinyl monomer solution of the curable resin (that is, the mass of the resin) (mass of the functional component / mass of the vinyl monomer solution, that is, the functional component). (Mass of resin / mass of resin) 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 is all.

When the mass ratio of the functional component is not more than the above-mentioned upper limit, the functional component is surely sealed in the pores of the porous inorganic particles with a sufficient amount of resin. Therefore, it is possible to prevent the functional component from leaking out of the pores of the porous inorganic particles.

Further, 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 (the total mass of the functional component and the vinyl monomer solution (resin) of the curable resin / 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, still more preferably 1.60 or more, and particularly preferably 1.70 or more. Further, it is 1.80 or more, further 1.90 or more, further 2.00 or more, and for example, 2.50 or less.

If the ratio of the total mass of the functional component and the vinyl monomer solution (resin) exceeds the above-mentioned lower limit, the functional expression particles can contain a sufficient amount of the functional component and the resin, depending on the purpose.

5. Applications of Function-Expressing Particles Function-expressing particles can be applied to various industrial products, for example, indoor and outdoor paints, resins (thermosetting resins), rubbers, fibers, putties, adhesives, joint agents, sealing agents. , Building materials, coking agents, wood treatment agents, soil treatment agents, white water in the papermaking process, pigments, treatment liquids for printing plates, cooling water, solvents (specifically, paint solvents, etc.), inks, cutting oils, cosmetics, It can be added and mixed with a solvent for a non-woven fabric, a spinning oil, a leather treatment material, and the like. The content of the functional component in these industrial products is, for example, 10 mg / kg to 100 g / kg (product mass).

Further, the function-developing particles can be kneaded with a resin (thermoplastic resin), a thermoplastic elastomer, rubber, or the like to form a molded product as it is or once as a molding material. Such an article has antibiotic activity when the functional ingredient is an antibiotic active compound. Specifically, when the molded product is bitten by a vermin, the functional component is released from the functional expression particles, so that the molded product exhibits antibiotic activity (for example, rodent repellent property). Alternatively, the molded product exhibits antibiotic activity (for example, antiseptic property, antifungal property, etc.) by the sustained release of the functional component from the functional expression particles in water or a solvent. When the functional component is a flame retardant, the functional component is exposed when the resin in the functional expression particles burns, whereby the molded product exhibits flame retardancy.

Further, when the functional component is a curing agent, the functional expression particles are blended with the second resin to prepare a second curable resin composition. At this time, the function-expressing particles act as a latent curing agent, and the second curable resin composition is prepared as a one-component curable resin composition.

Then, the second curable resin composition is cured to produce a cured resin (crosslinked resin).

Examples of the second resin include thermoplastic resins, thermosetting resins (main materials), hard resins such as biodegradable resins, and soft resins such as rubber and elastomers.

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.

The second functional group is, for example, 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. And so on. These can be used alone or in combination of two or more.

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.

The properties of the second resin are not particularly limited, and for example, a polymer dispersion such as latex or a non-aqueous dispersion (NAD), for example, a resin solution (polymer solution) dissolved in a solvent or water, for example, a powder or a compound. , Pellets, blocks and other molding materials, such as resin fibers (polymer fibers). Specifically, as the second resin, carboxyl group-modified synthetic rubber latex (for example, carboxyl group-modified SBR rubber latex, etc.), 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 body and the like.

For the function-expressing particles, the mixing ratio of the curing agent to 100 parts by mass of the second resin is, for example, 0.1 part by mass or more, preferably 1 part by mass or more, and for example, 80 parts by mass or less, preferably. It is blended in the second resin so as to be 50 parts by mass or less. When the compounding ratio of the curing agent to 100 parts by mass of the second resin is within the above range, the second curable resin composition can be reliably cured. Further, the function-expressing particles have an equivalent ratio (first functional group / second functional group) of the first functional group to the second functional group, for example, 0.7 or more, preferably 0.9 or more, and also. For example, it is blended with the second resin so as to be 1.3 or less, preferably 1.1 or less.

Further, together with the function-expressing particles, for example, a curing catalyst that promotes the reaction of the functional component can be blended into the second curable resin composition in an appropriate ratio in the following combinations, for example.

Epoxy group-containing compounds: 1,4-diazabicyclo [2,2,2] octane (triethylenediamine) (DABCO), 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine and the like 3 Class amine compounds N-methylol group-containing compounds or N-alkoxymethyl group-containing compounds: various amine salts
Isocyanate group-containing compound: Carboxylic acid metal salt such as dibutyltin dilaurate The above-mentioned second curable resin composition specifically includes various water-based paints, adhesives for fibers and wood, caulking materials, molding / casting materials, and the like. It is used as a fiber treatment agent.

Then, in order to cure the second curable resin composition (one-component curable resin composition), for example, the second curable resin composition is heated and, if necessary, pressurized. That is, heating or heating and pressurization triggers the release of the curing agent in the function-developing particles, whereby the curing agent (first functional group) and the second resin (second functional group) are released. As a reaction, 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. For example, a two-component curable resin composition having the function-expressing particles and the second resin separately is prepared. In that case, the mixed solution after mixing the function-expressing particles and the second resin is cured by the trigger described above.

6. Action effect According to the above-mentioned method for producing function-expressing particles, a vinyl monomer solution of a curable resin is mixed with the porous inorganic particles, and the vinyl monomer solution is mixed with the pores of the porous inorganic particles in which the functional components are incorporated. It is taken into the inside, and then the vinyl monomer solution is cured. Therefore, unlike Patent Document 1, all the vinyl monomer solutions in the pores are cured to form a cured product without requiring a step of removing the organic solvent, so that a large volume (Vr) of the resin in the pores is secured. can do. Therefore, such a resin can surely seal a sufficient amount of functional components in the porous inorganic particles or make them sustained-release.

As a result, the function-expressing particles obtained by the above-mentioned production method can release a sufficient amount of the antibiotic-active compound under physical conditions such as destruction to express the antibiotic activity. Alternatively, the functional component can exhibit sustained release in an environment such as in a solvent.

Further, when the functional component is a curing agent and the function-expressing particles and the second resin are mixed to prepare a second curable resin composition, the function-expressing particles contain a sufficient amount of the curing agent. However, 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. Specifically, the one-component curable resin composition containing the function-developing particles and the second resin does not cure until it is used, and has a long pot life even when preheated by heating. When heated (for example, heating at 100 ° C. or higher) and, if necessary, pressurized, it can be rapidly cured.

At this time, if it is desired to increase the release rate of the curing agent, a soft unsaturated polyester resin is preferably used as the resin for sealing the curing agent.

When the first functional group is a carboxyl group and / or a group capable of reacting with a hydroxyl group, specifically, the curing agent is an epoxy group-containing compound, an N-methylol group-containing compound or N. -Aalkoxymethyl 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 If it is at least one selected from the group consisting of group-containing compounds and the resin is an unsaturated polyester resin, the curing agent is a carboxyl group contained in the unsaturated polyester resin and / or By reacting with the hydroxyl group, a firm resin film can be formed. Therefore, the blending amount of the first resin can be relatively small.

Moreover, unlike the method described in Patent Document 1, since the vinyl monomer solution does not contain a solvent, it is not necessary to take health measures caused by the solvent.

However, when the functional component is a water-insoluble component, a production method for suspension polymerization or miniemulsion polymerization in water, as in the production method disclosed in International Publication No. 2011/030824 and International Publication No. 2013/100102. Has proposed a method of dispersing or containing a functional component in vinyl polymer particles.

Then, when the functional component is a water-insoluble component as in the above-described embodiment, the functional component can be incorporated into the pores of the porous inorganic particles as in the above-mentioned proposal.

On the other hand, when the functional component is a water-soluble component (water-soluble antibiotic active compound, water-soluble flame retardant), the functional component is eluted into water and functions in the same manner as the above proposal. The component cannot be dispersed or contained in the vinyl polymer.

On the other hand, in the above-described embodiment, even when the functional component is a water-soluble component, the functional component is incorporated into the pores of the porous inorganic particles, and then a vinyl monomer solution of the curable resin is added to the porous inorganic. Since it is incorporated into the pores of the particles and then the vinyl monomer solution is cured, the functional component can be incorporated into the porous inorganic particles and sealed with the resin.

Further, if 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 higher than the above lower limit, the porous inorganic particles take in a sufficient amount of resin. This allows the functional component to be reliably sealed within the pores of the porous particles. On the other hand, in Patent Document 1, it is estimated that Vr / Voa is less than a specific lower limit in order to remove the organic solvent in the organic solvent solution.

Further, in the above-described embodiment, if the ratio ((Vf + Vr) / Voa) of the total volume (Vf + Vr) of the functional component and the resin to the oil-absorbable volume (Voa) of the porous inorganic particles is equal to or less than the above-mentioned upper limit. , It is possible to prevent the adjacent porous inorganic particles from adhering or adhering to each other, and to ensure excellent fluidity of the plurality of porous inorganic particles.

On the other hand, if the ratio ((Vf + Vr) / Voa) of the total volume (Vf + Vr) of the functional component and the resin to the oil-absorbable volume (Voa) of the porous inorganic particles exceeds the above lower limit, the functional component and the resin are porous. It can be encapsulated in a sufficient amount with respect to the quality-inorganic particles. On the other hand, in Patent Document 1, the supported substance and the polymer compound or the curable compound are not included in a sufficient amount with respect to the porous fine particles.

Further, in the step (2), if the ratio (Vf + Vr) / Voa of the total volume (Vf + Vr) of the functional component and the resin to the oil-absorbable volume (Voa) of the porous inorganic particles exceeds the above lower limit, the functional component and the resin Can be encapsulated in a sufficient amount with respect to the porous inorganic particles.

Further, in the above-described embodiment, if the ratio of the total mass of the functional component and the resin to the mass of the porous inorganic particles is equal to or higher than the above-mentioned lower limit, the functional expression particles have a sufficient amount of function depending on the purpose. It can contain ingredients and resins.

Further, in the above-described embodiment, if the ratio of the functional component to the mass of the resin is equal to or less than the above-mentioned upper limit, the resin with a sufficient amount of the functional component ensures that the porous inorganic particles are sealed in the pores. It will be stopped. Therefore, it is possible to prevent the functional component from leaking out of the pores of the porous inorganic particles.

Further, in the above method, if the viscosity of the vinyl monomer solution is equal to or less than the above upper limit, the vinyl monomer solution does not decrease in the adsorption rate (uptake rate) of the vinyl monomer solution into the pores of the porous inorganic particles. Can be taken in in a short time, and further, the vinyl monomer solution can be sufficiently taken into the pores to prevent the solution from remaining on the surface of the porous inorganic particles.

Further, in the 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. Is located on the surface of the porous inorganic particles and may not be incorporated into the inorganic porous particles.

However, in the above method, in the 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 can be reliably encapsulated in the inorganic porous particles.

The vinyl monomer solution of the curable resin is a thermosetting resin composition, and the thermosetting resin composition has a lower limit of the normal temperature gelling time measured in accordance with JIS K6901-A method (2008). As described above, in the step (2), the thermosetting resin can be surely incorporated into the pores of the porous inorganic particles before the thermosetting resin composition is cured. On the other hand, if the above-mentioned normal temperature gelling time is equal to or less than the above-mentioned upper limit, the functional component incorporated into the pores of the porous inorganic particles dissolves in the vinyl monomer contained in the vinyl monomer solution in the step (2). , Subsequently, it can be prevented from moving to the surface of the porous inorganic particles.

On the other hand, in the method described in Examples 3, 4, 7, etc. of Patent Document 1, the methyl ketone solution of the epoxy resin is heated for a time equal to or longer than the above upper limit, so that the supported substance dissolves in the methyl ethyl ketone during that time. , There is a problem that it moves to the surface of silica fine particles.

However, if the normal temperature gelling time of the thermosetting resin composition is not more than the above upper limit, the thermosetting resin can be thermally cured in a short time. Therefore, the above-mentioned problems do not occur, that is, elution of the functional component with respect to the vinyl monomer can be prevented.

When the normal temperature gelling time of the thermosetting resin composition is not more than the above upper limit, the thermosetting resin composition can be cured quickly and with a high crosslink density in the step (3).

Specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios (content ratio) corresponding to those described in the above-mentioned "Form for carrying out the invention". ), Physical property values, parameters, etc., can be replaced with the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess"). it can.

First, details of raw materials and the like will be described.

IPBC: Trade name "Fangitrol 400", 3-iodo-2-propynylbutylcarbamate, antiseptic and antifungal agent, water-insoluble component, solubility in water: 0.15 g / L (20 ° C), International Specialty Products Co., Ltd. Timboa PCO: Brand name of Nippon Borate, disodium octaborate tetrahydrate, wood preservative, water-soluble component, solubility in water: 250 g / L (20 ° C), Nippon Borate denatonium benzoate: bitter taste Ingredients, repellents, water-soluble ingredients, solubility in methanol: 50 g / L (20 ° C), slightly soluble in water, manufactured by Wako Junyaku Co., Ltd. Synthetic capsaicin: N-vanylylnonanamide, spicy ingredients, repellents, water Insoluble in, Wako Junyaku Co., Ltd. Epoxy resin: Trade name "jER806", Bisphenol F type epoxy resin, Epoxy equivalent 160-170, Viscosity 1500-2500 mPa · s (25 ° C), Water-insoluble component, Epoxy resin manufactured by Mitsubishi Chemical Co., Ltd. : Product name "jER828", bisphenol A type epoxy resin, epoxy equivalent 184 to 194, viscosity 12,000 to 15,000 mPa · s (25 ° C), water-insoluble component, methylolated melamine manufactured by Mitsubishi Chemical Co., Ltd .: Product name "Beccamin" M-3 (60) ”, 54-60% non-volatile content aqueous solution, T-1890 manufactured by DIC: trade name“ VESTANAT T 1890/100 ”, isocyanurate modified product of IPDI, water-insoluble component, milionate manufactured by Epoxy Industries MR-200: Product name, Crude MDI, Isocyanate content 30.5 to 32.0% by mass, Water-insoluble component, Takenate D-170N manufactured by Toso Co., Ltd .: Product name, Isocyanurate modified product of HDI, Water-insoluble component, Mitsui Chemicals 1B2PZ: 1-benzyl-2-phenylimidazole, imidazole compound, nitrogen atom-containing compound, water-insoluble component, Shikoku Kasei DDM: 4,4'-diaminodiphenylmethane, aromatic diamine compound, nitrogen atom-containing compound, water Insoluble component, Silicia 310P manufactured by Tokyo Kasei Kogyo Co., Ltd .: Product name of Fuji Silicia Co., Ltd., Porous inorganic particles, Gel type silica particles, Pore volume 1.60 mL / g, Specific surface area 300 m ² / g, Oil absorption 330 mL / 100 g, Average particle size 2.7 μm, Fuji Silicia Permec N: Nichiyu Co., Ltd. trade name, polymerization initiator (second curing agent), methyl ethyl ketone peroxide 55% dimethyl phthalate solution, Nichiyu Co., Ltd. carboxyl group-modified SBR latex: Product name "Narsta -SR-116 ", solid content concentration 50.5%, manufactured by Nippon A & L Inc.

(Preparation of unsaturated polyester resin)
Preparation Example 1
490 g (5.0 mol) of maleic anhydride and 741 g (5. mol) of phthalic anhydride in a 5 L4 cervical corben equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a series of partial and total condensers. 0 mol), 418 g (5.5 mol) of propylene glycol, 531 g (5.0 mol) of diethylene glycol, 0.14 g of hydroquinone (first polymerization inhibitor), and nitrogen gas was blown at a rate of 0.1 L / min. It is. Then, when the mixture was heated to 180 ° C. by the ring-opening heat of the mantle heater and the acid anhydride under stirring, the polycondensation reaction started and the condensed water began to distill out. Further, the mixture was heated to 200 ° C. in 20 minutes and subjected to a polycondensation reaction at 200 to 210 ° C. for 6 hours while blowing nitrogen gas at a ratio of 0.5 L / min to have an acid value of 23.0 [mgKOH]. / G] 2090 g of unsaturated polyester was obtained.

Then, 2220 g of styrene was added to the unsaturated polyester, and the unsaturated polyester was dissolved (viscosity adjusted) to prepare an unsaturated polyester resin.

Subsequently, a small amount of hydroquinone (second polymerization inhibitor) 10% styrene solution (HQ10%) was added, and the normal temperature gelation time was measured according to JIS K6901-A method (2008) to obtain a normal temperature gel. The conversion time was adjusted to 25 minutes. Specifically, 50 g of a viscosity-adjusted unsaturated polyester resin is weighed in a 100 mL polycup, and 6% of a curing accelerator and 0.5% by mass of cobalt naphthenate are added and stirred to create a two-component curable resin (containing a curing agent). Then, the resin is prepared to be cured). The resin is allowed to stand in a constant temperature water bath at 25 ° C., 1.0% by mass of a curing agent (second curing agent) Permec N is added and stirred, and the gelation time at room temperature is measured. A two-component curable resin is prepared in the same manner as described above, and HQ 10% is added and stirred at any three points from 0.1% by mass to 0.5% by mass. The normal temperature gelling time is measured, and the vertical axis represents the normal temperature gelling time and the horizontal axis represents the amount of HQ 10% added to create a graph. Within the working time of step (2), determine the amount of HQ 10% compounded so that gelation does not occur, adjust the viscosity used for adsorption and support, and determine the resin containing 6% cobalt naphthenate 0.5 mass%. Add 10% of HQ in the blended amount and stir. The guideline for the normal temperature gelling time to be adjusted is t _g , assuming that the working time in step (2) is t.
t _g = t + 20
In this example, the working time of step (2) was set to 5 minutes, and the normal temperature gelling time was set to 25 minutes.

As a result, the unsaturated polyester resin A was prepared.

The physical properties of the unsaturated polyester resin A were as follows.

Percentage of curable resin 48.2% by mass
Viscosity 52 mPa · s (BM type viscometer, 60 rpm, 23 ° C)
Room temperature gelation time 25 minutes (JIS K6901-A method (2008))

Preparation Example 2
195 g of styrene monomer was added to 500 g of unsaturated polyester resin "Polyhope RHF1077M" (manufactured by Japan Composite Co., Ltd.). Next, an unsaturated polyester resin B was prepared by blending 0.7 g of HQ 10% and adjusting the normal temperature gelling time to 25 minutes.

The properties of the unsaturated polyester resin B were as follows.

Viscosity 68 mPa · s (BM type viscometer, 60 rpm, 23 ° C)
Room temperature gelation time 25 minutes (JIS K6901-A method (2008))

Preparation Example 3
In the same manner as in Preparation Example 1, 235 g (2.4 mol) of maleic anhydride, 710 g (4.8 mol) of phthalic anhydride, 117 g (0.8 mol) of adipic acid, and 960 g (6.4 mol) of triethylene glycol. , 112 g (1.8 mol) of ethylene glycol and 0.1 g of hydroquinone (first polymerization inhibitor) were charged to obtain 2060 g of unsaturated polyester having an acid value of 24.0 [mgKOH / g].

Then, 2200 g of styrene in which 0.3 g of hydroquinone (second polymerization inhibitor) was dissolved was added to the unsaturated polyester, and the unsaturated polyester was dissolved (viscosity adjusted) to prepare a soft unsaturated polyester resin.

Subsequently, in the same manner as in Preparation Example 1, a small amount of hydroquinone (second polymerization inhibitor) 10% styrene solution (HQ10%) was blended, and the normal temperature gelation time was set according to JIS K6901-A method (2008). The gelation time at room temperature was adjusted to 25 minutes.

As a result, a soft unsaturated polyester resin C was prepared.

The physical properties of the soft unsaturated polyester resin C were as follows.

Percentage of curable resin 48.2% by mass
Viscosity 43 mPa · s (BM type viscometer, 60 rpm, 23 ° C)
Room temperature gelation time 25 minutes (JIS K6901-A method (2008))

Preparation Example 4
190 g of styrene monomer was added to 500 g of the orthophthalic acid-based soft unsaturated polyester resin "Polyhope N-423PW" (manufactured by Japan Composite Co., Ltd.). Next, a soft unsaturated polyester resin D was prepared by blending 0.7 g of HQ 10% and adjusting the normal temperature gelling time to 25 minutes.

The properties of the soft unsaturated polyester resin D were as follows.

Viscosity 59 mPa · s (BM type viscometer, 60 rpm, 23 ° C)
Room temperature gelation time 25 minutes (JIS K6901-A method (2008))

(Preparation of function-expressing particles)
Example 1
A stirrer with a decompression seal equipped with 9 g of Syricia 310P (silica particles, oil-absorbable volume Voa: 29.7 mL) in a 500 mL flat-bottomed separable flask and equipped with three inclined stirring blades having a blade diameter of 90% of the inner diameter of the flask. , The top of the separable flask with a 50 mL drop funnel was joined to the flat bottom separable flask.

A vacuum pump, a three-way cock, a manometer, and a trap (a trap using dry ice and methanol) were connected to the upper adapter of the flask with a pressure-resistant tube, and the flask was evacuated. The inside of Kolben was set to a vacuum closed system by a three-way cock, and stirring was started at 600 rpm.

Then, 15 g (IPBC 9 g, IPBC volume Vf: 9 mL, total volume Vl: 15 mL) of IPBC 60% acetone solution (viscosity (23 ° C.): 53 mPa · s) was added dropwise over 3 minutes. Subsequently, the valve of the dropping funnel was opened, the pressure was returned to normal pressure, the lower part of the round bottom separable flask was removed, and the mixture was vacuum dried at room temperature for 5 hours to distill off acetone. Again, the top of the separable flask was joined to the flat bottom separable flask.

Next, 90 mg of Permec N was added to 9 g of unsaturated polyester resin A, and the mixture was stirred to make a uniform mixed solution (volume Vr: 9 mL). Subsequently, the mixed solution was added dropwise to the silica particles at normal pressure over 3 minutes while stirring the silica particles incorporating the IPBC at 600 rpm.

Subsequently, stirring was continued for about 30 minutes until the unsaturated polyester resin A began to gel, and the unsaturated polyester resin A was allowed to stand for 18 hours at room temperature to completely cure the unsaturated polyester resin A. As a result, 27 g of function-expressing particles containing (incorporating) IPBC in 33% (IPBC / silica particles / resin (cured product) = 1/1/1 (mass ratio)) were obtained.

Functional component / porous inorganic particles / resin [mass standard], resin / porous inorganic particles [mass standard], functional component / functional expression particles [mass standard], (functional component + resin) / porous inorganic particles [mass standard] ], 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, the above ratios are shown in Tables 1 to 4 for the following Examples 2 and subsequent examples.

When 5 g of the function-expressing particles were dispersed in 95 g of sorbesso (paint solvent) and allowed to stand at room temperature for 30 days, the IPBC concentration in the sorbesso after filtering the function-expressing particles was measured by HPLC, and the eluted IPBC was incorporated. However, it was 1.2% of IPBC.

Example 2
In Example 1, instead of 15 g of the IPBC 60% acetone solution, 15 g of a 20% aqueous solution of Timboa PCO (viscosity (23 ° C.): 23 mPa · s) (volume Vf of Timboa PCO: 3 mL, volume Vs of water: 12 mL, volume of aqueous solution). Vl: 15 mL) was incorporated into 9 g of silica particles (adsorbed), and the mixture was vacuum dried at 80 ° C. for 5 hours to distill off water. Then, by repeating the same operation twice, 45 g of a 20% timboa PCO aqueous solution (9 g of timboa PCO, volume Vf: 9 mL) was incorporated (adsorbed) into 9 g of silica particles, and 9 g of timboa PCO was supported (incorporated). All of the above adsorption steps were carried out in a vacuum closed system.

In the first, second, and third times of uptake (adsorption) of the 20% aqueous solution of Tinpore PCO into silica particles, Vl / Voa was 0.50, 0.60, and 0.71, respectively, and Vf / Voa were 0.10, 0.20, and 0.30, respectively.

Then, in the same manner as in Example 1, 60 mg of Permec N was added to 6 g of unsaturated polyester resin A, and the mixture was stirred to make a uniform mixture (volume Vr: 6 mL). Subsequently, the mixed solution was added dropwise to the silica particles over 1 minute while stirring the silica particles at 600 rpm.

Subsequently, stirring was continued for about 30 minutes until the unsaturated polyester resin A began to gel, and the unsaturated polyester resin B was allowed to stand for 18 hours at room temperature to completely cure the unsaturated polyester resin B. As a result, 24 g of function-expressing particles containing (incorporating) timboa PCO in an amount of 37.5% by mass (timboa PCO / silica particles / resin (cured product) = 3/3/2 (mass ratio)) was obtained.

When 5 g of the function-expressing particles were dispersed in 95 g of deionized water and allowed to stand at room temperature for 30 days, the concentration of disodium octaborate tetrahydrate in the deionized water after filtering the function-expressing particles was measured by mass. The eluted disodium octaborate tetrahydrate was 5.8% of the inclusion amount.

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) (4.5 g of denatonium benzoate, volume Vf of denatonium benzoate: 4) .5 mL, total volume of liquid Vl: 15 mL) was incorporated (adsorbed) into 9 g of silica particles, and 9 g of unsaturated polyester resin A and 90 mg of Permec N were replaced with unsaturated polyester resin B 10. Except for the fact that 5 g and 105 mg of Permec N (total volume Vr: 10.5 mL) were used, the same procedure was carried out to add 18.8% denatonium benzoate (denatonium benzoate / silica particles / resin (cured product). ) = 3/6/7) 24 g of functional expression particles to be included (incorporated) were obtained.

The function-developing particles were kneaded with 3% of polyethylene. We were able to produce a rodent-proof molding material without any problems in the working environment during kneading.

Example 4
In Example 1, instead of 15 g of IPBC 60% acetone solution, 15 g of synthetic capsaicin 20% ethanol solution (viscosity (23 ° C.): 20 mPa · s or less) (synthetic capsaicin 3 g, synthetic capsaicin Vf: 3 mL, total volume Vl of the solution). : 15 mL) was incorporated (adsorbed) into 9 g of silica particles, and instead of 9 g of unsaturated polyester resin A and 90 mg of capmec N, 12 g of unsaturated polyester resin B and 120 mg of permec N (total volume). 24 g of function-expressing particles containing (incorporated) 12.5% (synthetic capsaicin / silica particles / cured resin = 1/3/4) of synthetic capsaicin by the same operation except that Vr: 12 mL) was used. Got

The function-developing particles were kneaded with polyethylene at 2%. We were able to produce a rodent-proof molding material without any problems in the working environment during kneading.

Example 5
(Preparation of function-expressing particles)
A 500 mL round bottom separable flask is charged with 9 g of Syricia 310P (silica particles, oil-absorbable volume Voa: 29.7 mL), equipped with a stirrer with a crescent-shaped stirring blade that matches the curvature of the round bottom, and a 50 mL dropping funnel. The upper part of the separable flask was joined to the round bottom separable flask.

Next, while stirring at 600 rpm at normal pressure, 15 g of an 80% ethyl acetate solution (viscosity (23 ° C.): 45 mPa · s) of epoxy resin (jER806) (12 g of jER806, volume of jER806 Vf: 12 mL, total volume of the solution) Vl: 15 mL) was added dropwise over 3 minutes. Subsequently, the lower part of the round bottom separable flask was removed and vacuum dried at 50 ° C. for 5 hours to distill off ethyl acetate. Again, the top of the separable flask was joined to the round bottom separable flask.

Next, 70 mg of Permec N was added to 7.5 g of the soft unsaturated polyester resin C, and the mixture was stirred to make a uniform mixed solution (volume Vr: 7.5 mL). Subsequently, the mixed solution was added dropwise to the silica particles over 3 minutes while stirring the silica particles at 600 rpm.

Subsequently, stirring was continued for about 30 minutes until gelation of the soft unsaturated polyester resin C started, and the mixture was allowed to stand at room temperature for 18 hours to completely cure the soft unsaturated polyester resin C. As a result, 28.5 g of function-expressing particles containing (incorporating) jER806 in 42% (jER806 / silica particles / resin (cured product) = 8/6/5 (mass ratio)) were obtained.

(Preparation of latex for non-woven fabric impregnation)
First, Example 5 in which jER806 is 5 parts by mass with respect to 100 parts by mass of the solid content of the latex obtained by diluting the carboxyl group-modified SBR latex (Nalster SR-116) with deionized water so as to have a solid concentration of 20%. A latex to which the functional expression particles of the above was added was prepared. Next, as a curing catalyst, 2.5 parts by mass of a 20% aqueous solution of 1,4-diazabicyclo [2.2.2] octane (DABCO) was added to the latex and stirred to obtain a uniform latex for impregnating a non-woven fabric. This was allowed to stand at room temperature for 1 week.

Separately, the latex for impregnating the non-woven fabric was allowed to stand at room temperature for 2 weeks.

Example 6
(Preparation of function-expressing particles)
In Example 5, 15 g (12 g of jER806, volume Vf of jER806, total volume of liquid Vl: 15 mL) of an 80% ethyl acetate solution of epoxy resin (jER806) was 13 g (10.4 g of jER806, volume Vf: 10 of jER806). Change to .4 mL, total volume of liquid Vl: 13 mL), add 70 mg of Permec N to 7.5 g of soft unsaturated polyester resin C, and stir to make the mixed solution uniform (volume Vr: 7.5 mL) soft. The same operation was carried out except that 104 mg of Permec N was added to 10.4 g of unsaturated polyester resin C and the mixture was changed to a uniform mixed solution (volume Vr: 10.4 mL) by stirring to make jER806 35% (volume Vr: 10.4 mL). jER806 / silica particles / resin (cured product) = 7/6/7 (mass ratio)) 29.8 g of function-expressing particles contained (incorporated) were obtained.

(Preparation of latex for non-woven fabric impregnation)
First, Example 6 is a latex obtained by diluting a carboxyl group-modified SBR latex (Nalster SR-116) with deionized water so as to have a solid concentration of 20% so that jER806 is 5 parts by mass with respect to 100 parts by mass of solid content. A latex to which the functional expression particles of the above was added was prepared. Next, as a curing catalyst, 2.5 parts by mass of a 20% aqueous solution of 1,4-diazabicyclo [2.2.2] octane (DABCO) was added to the latex and stirred to obtain a uniform latex for impregnating a non-woven fabric. This was allowed to stand at room temperature for 1 week.

Separately, the latex for impregnating the non-woven fabric was allowed to stand at room temperature for 2 weeks.

(Preparation of control 1)
Separately, 2 parts by mass of an anionic emulsifier and 5 parts by mass of a nonionic emulsifier were added to 100 parts by mass of jER806, and deionized water was gradually added under stirring to prepare an epoxy resin emulsion containing 44% of jER806. In the above-mentioned latex for impregnating a non-woven fabric, 11 parts by mass (5 parts by mass as jER806) of this emulsion was added instead of the function-expressing particles, and this was designated as Control 1. This was allowed to stand at room temperature for 1 week.

Separately, Control 1 was allowed to stand at room temperature for 2 weeks.

(Preparation of resin-impregnated non-woven fabric)
A 150 g / m ² non-woven fabric (web) made by Tetron (registered trademark) is cut into a size of 15 cm x 20 cm, and the non-woven fabric is sandwiched between two 10-mesh wire meshes of the same size and clipped, and a 20 cm x 30 cm stainless steel bat. I put it in. Next, each of the latex for impregnating the non-woven fabric and the control 1 was stirred and made uniform, and then poured into a stainless steel vat to impregnate the non-woven fabric. Then, it was squeezed with a mangle while being sandwiched between wire meshes so that the amount of impregnated latex was 220 g / m ^{2 in} a wet state, pre-dried at 110 ° C. for 10 minutes, and cured at 140 ° C. for 5 minutes.

(Dry cleaning resistance of the resin-impregnated non-woven fabric of Examples 5 and 6 and Control 1)
The dry cleaning resistance of the resin-impregnated nonwoven fabrics of Examples 5 and 6 and Control 1 was evaluated. Specifically, each non-woven fabric was cut into 3 cm squares and immersed in perchlorethylene at 40 ° C. with stirring.

As a result, none of the resin-impregnated non-woven fabrics impregnated with the latex containing the functionally-expressing fine particles of Examples 5 and 6 left to stand at room temperature for one week did not lose their shape at all. On the other hand, in the resin-impregnated nonwoven fabric impregnated with latex to which the epoxy resin emulsion added, which is Control 1, the nonwoven fabric did not retain its original shape and the fibers were separated.

Further, in the latex left at room temperature for 2 weeks, the resin-impregnated non-woven fabric impregnated with the latex to which the functional expression fine particles of Example 6 was added did not lose its shape at all, but the functional expression fine particles of Example 5 were added. The resin-impregnated non-woven fabric impregnated with latex was slightly out of shape.

Example 7
(Preparation of function-expressing particles)
In Example 5, instead of 15 g of the 80% acetone solution of the epoxy resin jER806, 15 g of Beccamin 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 incorporated (adsorbed) into 9 g of silica particles, the temperature in vacuum drying was changed from 50 ° C. to room temperature, and 3.75 g of water was distilled off. Except for the above, the same operation as in Example 5 was carried out to add 32% by mass of methylolated melamine (methylated melamine / water / silica particles / resin (cured product) = 6 / 1.5 / 6/5 (mass ratio)). ) 27.7 g of the function-expressing particles contained (incorporated) were obtained. In addition, water corresponding to 25% of melamine is left to give fluidity at the time of use as a curing agent.

(Preparation of latex for non-woven fabric impregnation)
In the impregnating latex of Example 5, the functional expression 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, as a catalyst, 0.5 parts by mass of Catalyst ACX (manufactured by DIC Corporation) was added and stirred to obtain a uniform latex for impregnating a non-woven fabric. This was allowed to stand at room temperature for 1 week.

Separately, the latex for impregnating the non-woven fabric was allowed to stand at room temperature for 2 weeks.

Example 8
The same procedure as in Example 7 was carried out in the same manner as in Example 7 except that Beccamin M-3 (60) was changed to 17.3 g, soft unsaturated polyester resin C was changed to 10.4 g, and Permec N was changed to 104 mg to obtain functional expression particles. It was.

This function-expressing particle has a function of containing (incorporating) 32% by mass of methylolated melamine (methylolated melamine / water / silica particles / resin (cured product) = 7 / 1.7 / 6/7 (mass ratio)). The amount of expressed particles was 32.4 g.

(Preparation of latex for non-woven fabric impregnation)
In the impregnating latex of Example 5, the functional expression particles of Example 8 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, as a catalyst, 0.5 parts by mass of Catalyst ACX (manufactured by DIC Corporation) was added and stirred to obtain a uniform latex for impregnating a non-woven fabric. This was allowed to stand at room temperature for 1 week.

Separately, the latex for impregnating the non-woven fabric was allowed to stand at room temperature for 2 weeks.

(Preparation of control 2)
In the non-woven fabric impregnating latex of Example 7, the non-woven fabric impregnating latex in which 8.3 parts by mass (5 parts by mass as methylolated melamine) of Beccamin M-3 (60) was added instead of the function-expressing particles was used as Control 2. This was allowed to stand at room temperature for 1 week.

(Preparation of resin-impregnated non-woven fabric of Examples 7 and 8 and Control 2 and dry cleaning property)
The resin-impregnated non-woven fabrics of Examples 7 and 8 were prepared in the same manner as in Example 5, and the dry cleaning resistance was evaluated. As a result, the resin-impregnated non-woven fabric impregnated with the latex to which the functional expression fine particles of Examples 7 and 8 were added, which had been allowed to stand at room temperature for 1 week, did not lose its shape at all. However, in the resin-impregnated non-woven fabric impregnated with latex to which an aqueous solution of methylolated melamine, which is control 2, was added, the non-woven fabric did not retain its original shape and the fibers were separated.

Further, in the latex left at room temperature for 2 weeks, the resin-impregnated nonwoven fabric impregnated with the latex to which the functional expression fine particles of Example 8 was added did not lose its shape at all, but the functional expression fine particles of Example 7 were added. The resin-impregnated non-woven fabric impregnated with latex was slightly out of shape.

Example 9
(Preparation of function-expressing particles)
In Example 5, instead of 15 g of an 80% acetone solution of the epoxy resin jER806, 15 g of a 66% ethyl acetate solution (viscosity (23 ° C.): 83 mPa · s) of T-1890, which is an isocyanate group-containing compound (isocyanate curing agent). , (T-1890 9.9 g, T-1890 volume Vf 9.9 mL, total liquid volume Vl: 15 mL) was incorporated (adsorbed) into 9 g of silica particles, and the same operation as in Example 5 was performed. This was carried out to obtain 26.4 g of function-expressing particles containing (incorporating) T-1890 in an amount of 38% by mass (T-1890 / silica particles / resin (cured product) = 6.6 / 6/5 (mass ratio)). ..
(Preparation of 1-component polyurethane resin composition)
A one-component polyurethane resin composition was prepared by adding the function-expressing particles of Example 9 to 100 parts by mass of acrylic polyol as the second resin and uniformly mixing them at room temperature so as to have 5 parts by mass of T-1890. did.

Example 10
In Example 9, the same operation was carried out except that the 66% ethyl acetate solution of T-1890 was changed to 15.8 g, the soft unsaturated polyester resin C was changed to 10.4 g, and the Permec N was changed to 104 mg, and T-1890 was changed to 35 mass by mass. % (T-1890 / silica particles / resin (cured product) = 7/6/7 (mass ratio)) 29.8 g of function-expressing particles contained (incorporated) were obtained.
(Preparation of 1-component polyurethane resin composition)
A one-component polyurethane resin composition was prepared by adding the function-expressing particles of Example 10 to 100 parts by mass of acrylic polyol as the second resin and uniformly mixing them at room temperature so as to have 5 parts by mass of T-1890. did.

(Preparation of control 3)
Separately, a resin solution prepared 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.

(Measurement of pot life of Examples 9, 10 and Control 3)
The pot life of the one-component polyurethane resin composition of Examples 9 and 10 and the resin solution of Control 3 at 50 ° C. was measured. The pot life at 50 ° C. is based on "Method 1 How to obtain the pot life (pot life) of adhesive-other component adhesive" of JIS K6870: 2008, "Method 1 How to obtain by apparent viscosity change". The time when the apparent viscosity measured by the Brookfield type rotational viscometer (B type, spindle number 3, rotation speed 30 rpm) exceeded 3 Pa · s was calculated. The following pot life at 50 ° C. is the same as above.

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 ・ Immediately after the preparation of the resin solution of Control 3

Example 11
(Preparation of function-expressing particles)
In Example 5, instead of 15 g of an 80% acetone solution of the epoxy resin jER806, a 90% ethyl acetate solution of mylionate MR-200, which is an isocyanate group-containing compound (isocyanate curing agent) (viscosity (23 ° C.): 43 mPa · s). Exactly the same as in Example 5 except that 15 g (13.5 g of Millionate MR-200, volume Vf of Millionate MR-200, total volume of liquid Vl: 15 mL) was incorporated (adsorbed) into 9 g of silica particles. (Millionate MR-200 / silica particles / resin (cured product) = 9/6/5 (mass ratio)) containing (incorporated) 30 g of functional expression particles containing 45% by mass of Millionate MR-200. It was.
(Preparation of 1-component polyurethane resin composition)
A one-component polyurethane resin composition was prepared by adding the functional expression particles of Example 11 to 100 parts by mass of acrylic polyol as the second resin and uniformly mixing them at room temperature so as to have 5 parts by mass of mylionate MR-200. Prepared.

Example 12
In Example 11, the operation was carried out in the same manner except that the 90% ethyl acetate solution of Millionate MR-200 was changed to 11.6 g, the soft unsaturated polyester resin C was changed to 10.4 g, and Permec N was changed to 104 mg, and the Millionate MR-200 was prepared. 29.8 g of function-expressing particles contained (incorporated) were obtained in an amount of 35% by mass (millionate MR-200 / silica particles / resin (cured product) = 7/6/7 (mass ratio)).
(Preparation of 1-component polyurethane resin composition)
A one-component polyurethane resin composition was prepared by adding the functional expression particles of Example 12 to 100 parts by mass of acrylic polyol as the second resin and uniformly mixing them at room temperature so as to have 5 parts by mass of mylionate MR-200. Prepared.

(Preparation of control 4)
Separately, the resin solution obtained by adding and mixing 5 parts by mass of Millionate MR-200 to 100 parts by mass of acrylic polyol was used as Control 4.

(Measurement of pot life of Examples 11 and 12 and Control 3)
The pot life of the one-component polyurethane resin composition of Examples 11 and 12 and the resin solution of Control 4 at 50 ° C. 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-Immediately after the preparation of the resin solution of Control 4

Example 13 (Preparation of functional expression particles)
In Example 5, instead of 15 g of an 80% acetone solution of the epoxy resin jER806, an 80% ethyl acetate solution of Takenate D-170N, which is an isocyanate group-containing compound (isocyanate curing agent) (viscosity (23 ° C.): 91 mPa · s). The same operation as in Example 5 was performed except that 15 g (12 g of Takenate D-170N, volume Vf of Takenate D-170N, total volume of liquid Vl: 15 mL) was incorporated (adsorbed) into 9 g of silica particles. , 42% by mass of Takenate D-170N (Takenate D-170N / Silica particles / Resin (cured product) = 8/6/5 (mass ratio)) was contained (incorporated) in 28.5 g of function-expressing particles.

(Preparation of 1-component polyurethane resin composition)
A one-component polyurethane resin composition was prepared by adding the functional expression particles of Example 13 to 100 parts by mass of acrylic polyol as the second resin and uniformly mixing them at room temperature so as to have 5 parts by mass of Takenate D-170N. Prepared.

Example 14
In Example 13, 13 g of an 80% ethyl acetate solution of Takenate D-170N, 10.4 g of soft unsaturated polyester resin C, and 104 mg of Permec N were operated in the same manner, and 35% by mass of Takenate D-170N was added. (Takenate D-170N / silica particles / resin (cured product) = 7/6/7 (mass ratio)) 29.8 g of function-expressing particles to be encapsulated (incorporated) were obtained.

(Preparation of 1-component polyurethane resin composition)
A one-component polyurethane resin composition was prepared by adding the functional expression particles of Example 14 to 100 parts by mass of acrylic polyol as the second resin and uniformly mixing them at room temperature so as to have 5 parts by mass of Takenate D-170N. Prepared.

(Preparation of control 5)
Separately, the resin solution obtained by adding and mixing 5 parts by mass of Takenate D-170N to 100 parts by mass of acrylic polyol was used as Control 5.

(Measurement of pot life in Examples 13 and 14 and Control 5)
The pot life of the one-component polyurethane resin composition of Examples 13 and 14 and the resin solution of Control 5 at 50 ° C. 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 ・ Immediately after the preparation of the resin solution of Control 5

Example 15
(Preparation of function-expressing particles)
In Example 5, instead of 15 g of the 80% polyester solution of the epoxy resin jER806, 15 g of a 70% acetone solution (viscosity (23 ° C.): 8 mPa · s) of 1-benzyl-2-phenylimidazole (1B2PZ), (1B2PZ 10). .5 g, 1B2PZ volume Vf 10.5 mL, total solution volume Vl: 15 mL) was incorporated (adsorbed) into 9 g of silica particles, and 6 g of soft unsaturated polyester resin C with 60 mg of Permec N added. Instead, the same operation as in Example 5 was carried out except that 9 g of soft unsaturated polyester resin D to which 90 mg of Permec N was added was used, and 1B2PZ was added to 37% by mass (1B2PZ / silica particles / resin (cured product). ) = 7/6/6 (mass ratio)) 28.5 g of the function-expressing particles contained (incorporated) were obtained.

(Preparation of 1-component epoxy resin composition)
13.5 parts by mass of functional expression particles (5 parts by mass as 1B2PZ) were added to 100 parts by mass of an epoxy resin (jER828) as a second resin to prepare a one-component epoxy resin composition uniformly mixed at room temperature. ..

(Preparation of control 6)
Separately, the resin liquid obtained by adding 5 parts by mass of 1B2PZ to 100 parts by mass of the epoxy resin (jER828) and mixing them in the same manner was used as control 6.

(Measurement of pot life of Example 15 and Control 6)
The pot life of the one-component epoxy resin composition and the resin solution of Control 6 at 50 ° C. was measured. The results were as follows.
-One-component epoxy resin composition of Example 15 6 weeks-Resin solution of control 6 3 days

Example 16
(Preparation of function-expressing particles)
In Example 5, instead of 15 g of an 80% acetone solution of the epoxy resin jER806, 15 g of a 60% acetone solution of 4,4′-diaminodiphenylmethane (DDM) (viscosity (23 ° C.): 7 mPa · s), (DDM 9 g, DDM volume Vf 9 mL, total solution volume Vl: 15 mL) was incorporated (adsorbed) into 9 g of silica particles, and instead of 6 g of soft unsaturated polyester resin C with 60 mg of Permec N added, it was not soft. Except for the fact that 9 g of saturated polyester resin D to which 90 mg of Permec N was added was used, the same operation as in Example 5 was carried out, and the DDM was 33% by mass (DDM / silica particles / resin (cured product) = 1/1. / 1 (mass ratio)) 27 g of function-expressing particles contained (incorporated) were obtained.

(Preparation of 1-component epoxy resin composition)
To 100 parts by mass of the epoxy resin (jER828) as the second resin, 42 parts by mass of the function-expressing particles (14 parts by mass as DDM) were added to prepare a one-component epoxy resin composition uniformly mixed at room temperature.

(Preparation of control 7)
Separately, a resin solution prepared by adding and mixing 14 parts by mass of DDM to 100 parts by mass of epoxy resin (jER828) was used as control 7.

(Measurement of pot life of Example 16 and Control 7)
The pot life of the one-component epoxy resin composition and the resin solution of Control 7 at 50 ° C. was measured. The results were as follows.
・ One-component epoxy resin composition 10 days ・ Control 7 resin solution 3 hours

Comparative Example 1
In order to seal the functional components incorporated in the silica particles with the thermoplastic polyester resin, first, an attempt was made to prepare a solvent solution of PET NES-2040 (thermoplastic polyester resin, polyethylene terephthalate, manufactured by Unitica).

Japan Society of Color Material Magazine Vol. 42, No. 11, p501-505 (1969, by Toyo Spinning Co., Ltd.) lists methyl ethyl ketone (MEK) as a true solvent for terephthalic acid-based linear polyester. NES-2040 4 g is added to 96 g of MEK, and 60 Stirring was carried out at ° C. for 1 week, but no dissolution of PET NES-2040 was observed.

Comparative Example 2
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) are dissolved in 13.5 g of MEK, and the pot life at 23 ° C. is 100 mPa · s or less. A resin solution for 5 hours was prepared.

In Example 1, instead of the unsaturated polyester resin A, 9 g of the MEK solution of the above epoxy resin composition (solid volume Vr: 3.6 mL) was added dropwise, and then vacuum dried at room temperature for 5 hours. MEK was removed. Then, it was heat-cured at 60 ° C. for 10 hours to obtain 21 g of function-expressing particles encapsulating (incorporating) 42% IPBC (IPBC / silica particles / epoxy resin = 5/5/2).

When 5 g of the function-expressing particles were dispersed in 95 g of sorbesso (paint solvent) and allowed to stand at room temperature for 30 days, the IPBC concentration in the sorbesso after filtering the function-expressing particles was measured by HPLC, and the eluted IPBC was incorporated. However, it was 72% of IPBC.

It is probable that the reason why the leaching proceeded to this point was that the IPBC mass transferred into the MEK during the lapse of time until the MEK was distilled off, in addition to the reason that the thickness of the resin layer became thin.

Claims (15)

Porous inorganic particles and
The functional components incorporated into the pores of the porous inorganic particles and
Contains a resin that seals the functional component in the pores,
The resin is a cured product obtained by curing a vinyl monomer solution containing a curable resin.
The vinyl monomer solution does not contain a solvent, but contains the curable resin and the vinyl monomer.
The pore volume of the porous inorganic particles is 1.0 mL / g or more and 3.0 mL / g or less.
The blending ratio of the vinyl monomer is 35% by mass or more and 55% by mass or less with respect to the total amount of the curable resin and the vinyl monomer.
A function-developing particle, wherein the ratio of the volume of the resin to the oil-absorbable volume of the porous inorganic particles is 0.30 or more. Porous inorganic particles and
The functional components incorporated into the pores of the porous inorganic particles and
Contains a resin that seals the functional component in the pores,
The resin is a cured product obtained by curing a vinyl monomer solution containing a curable resin.
The vinyl monomer solution does not contain a solvent, but contains the curable resin and the vinyl monomer.
The average value of the maximum lengths of the porous inorganic particles is 0.5 μm or more and 50 μm or less.
The porous inorganic particles consist of a group consisting of calcium silicate, barium silicate, magnesium silicate, zeolite, calcium phosphate, barium phosphate, magnesium phosphate, zirconium phosphate, apatite, silicon oxide, alumina, and magnesium oxide. Formed from at least one inorganic material selected,
The blending ratio of the vinyl monomer is 35% by mass or more and 55% by mass or less with respect to the total amount of the curable resin and the vinyl monomer.
A function-developing particle, wherein the ratio of the volume of the resin to the oil-absorbable volume of the porous inorganic particles is 0.30 or more. The functional expression particle according to claim 1 or 2, wherein the curable resin is at least one selected from the group consisting of an unsaturated polyester resin, an epoxy acrylate resin, and a urethane acrylate resin. The functional expression particle according to any one of claims 1 to 3, wherein the curable resin is an unsaturated polyester resin. The functional expression particle according to any one of claims 1 to 4, wherein the functional component is a water-insoluble component. The functional expression particle according to any one of claims 1 to 4, wherein the functional component is a water-soluble component. The functional expression particle according to any one of claims 1 to 6, wherein the ratio of the total mass of the functional component and the resin to the mass of the porous inorganic particles is 1.60 or more. The functional expression particle according to any one of claims 1 to 7, wherein the ratio of the mass of the functional component to the mass of the resin is 2.25 or less. The functional expression according to any one of claims 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. particle. The functional expression according to any one of claims 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. particle. A liquid containing a functional component is blended with 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, and the functional component is mixed with the porous inorganic particles. Step of incorporating quality-inorganic particles into the pores (1),
The ratio of the total volume of the functional component and the vinyl monomer solution of the vinyl monomer solution containing the curable resin to the porous inorganic particles to the oil-absorbable volume of the porous inorganic particles is 0.75 or less. As described above, the step (2) of blending and incorporating the vinyl monomer solution into the pores of the porous inorganic particles, and
Step (3) of sealing the functional component in the pores by curing the vinyl monomer solution.
With
The vinyl monomer solution does not contain a solvent, but contains the curable resin and the vinyl monomer.
The pore volume of the porous inorganic particles is 1.0 mL / g or more and 3.0 mL / g or less.
A method for producing functional particles, wherein the blending ratio of the vinyl monomer is 35% by mass or more and 55% by mass or less with respect to the total amount of the curable resin and the vinyl monomer. A liquid containing a functional component is blended with 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, and the functional component is mixed with the porous inorganic particles. Step of incorporating quality-inorganic particles into the pores (1),
The ratio of the total volume of the functional component and the vinyl monomer solution of the vinyl monomer solution containing the curable resin to the porous inorganic particles to the oil-absorbable volume of the porous inorganic particles is 0.75 or less. As described above, the step (2) of blending and incorporating the vinyl monomer solution into the pores of the porous inorganic particles, and
Step (3) of sealing the functional component in the pores by curing the vinyl monomer solution.
With
The vinyl monomer solution does not contain a solvent, but contains the curable resin and the vinyl monomer.
The average value of the maximum lengths of the porous inorganic particles is 0.5 μm or more and 50 μm or less.
The porous inorganic particles consist of a group consisting of calcium silicate, barium silicate, magnesium silicate, zeolite, calcium phosphate, barium phosphate, magnesium phosphate, zirconium phosphate, apatite, silicon oxide, alumina, and magnesium oxide. Formed from at least one inorganic material selected,
A method for producing functional particles, wherein the blending ratio of the vinyl monomer is 35% by mass or more and 55% by mass or less with respect to the total amount of the curable resin and the vinyl monomer. The method for producing functional-expressing particles according to claim 11 or 12, wherein the curable resin has a viscosity at 23 ° C. of 100 mPa · s or less. The vinyl monomer solution is a thermosetting resin composition.
Any one of claims 11 to 13, wherein the thermosetting resin composition has a normal temperature gelling time of 10 minutes or more as measured in accordance with JIS K6901-A method (2008). The method for producing functional particles according to the section. The vinyl monomer solution is a thermosetting resin composition.
Any one of claims 11 to 14, wherein the thermosetting resin composition has a normal temperature gelling time of 1 hour or less as measured in accordance with JIS K6901-A method (2008). The method for producing functional particles according to the section.