JP6811010B2 - Filler added to resin, resin material and method of adjusting its elastic modulus and manufacturing method - Google Patents

Description

The present invention relates to a filler added to a resin, a resin material, a method for adjusting the elastic modulus thereof, and a manufacturing method.

Fillers are particles or powdery substances added to plastics (resins), rubber, paints, etc. to improve strength, functionality, and reduce costs.

Conventionally, as a technique of using fine particles as a filler added to a resin, a method of melt-kneading a molten polymer and metal fine particles using a kneader or the like, a metal-silane coupling agent-polymer (mixing treatment agent) ), A method of forming a chemical bond between the polymer and the resin, and using a protective agent or a silane coupling agent as a surface treatment agent to disperse metal fine particles, etc., and the resin. There are known methods for increasing the compatibility of the particles.

Patent Documents 1 to 3 propose techniques for using a protective agent or a silane coupling agent as a surface treatment agent.

Japanese Unexamined Patent Publication No. 2008-239882 Japanese Unexamined Patent Publication No. 2013-218836 Japanese Unexamined Patent Publication No. 2014-205905 Japanese Unexamined Patent Publication No. 2012-14419 Japanese Unexamined Patent Publication No. 2012-117173

However, in the conventionally proposed technology, the correlation between the molecular weight of the surface treatment agent and the ratio with the metal fine particles and the elastic modulus of the resin material to which the filler is added has not been examined, and the details have not been examined. No findings were obtained.

The present inventors have studied the support of metal fine particles covalently bonded to a low molecular weight surface treatment agent on a particulate carrier of an inorganic material or a carbon material, or an organic carrier such as a fiber (Patent Documents). 4, 5), its use as a filler added to the resin, and its elasticity have not been studied.

The present invention has been made in view of the above circumstances, and the elastic modulus of the resin material is adjusted based on the correlation between the surface treatment agent for the fine particles and the elastic modulus of the resin material to which the fine particles are added. That is the issue.

As a new finding, the present inventor found a correlation between the molecular weight of the surface treatment agent of fine particles and the elastic modulus of the resin, and specifically, found that the lower the molecular weight of the surface treatment agent, the higher the elastic modulus. , The present invention has been completed.

That is, the filler of the present invention is a filler added to a resin, which is fine particles having a surface treatment agent on the surface, and is characterized in that the molecular weight of the surface treatment agent is less than 100,000.

In this filler, the mass ratio of the fine particles in the filler to the surface treatment agent (fine particles: surface treatment agent) is preferably 55:45 or more.

In this filler, the surface treatment agent is preferably a compound covalently bonded to fine particles.

The resin material of the present invention contains the above filler.

In this resin material, the rate of increase in elastic modulus due to the addition of a filler to the resin is preferably 1% or more.

The method for adjusting the elastic modulus of the resin material of the present invention is that when fine particles having a surface treatment agent having a molecular weight of less than 100,000 are added to the resin as a filler, the molecular weight of the surface treatment agent and / or the fine particles and the surface treatment agent are used. It is characterized by adjusting the mass ratio.

The method for producing a resin material of the present invention is a method for producing a resin material in which fine particles having a surface treatment agent having a molecular weight of less than 100,000 are added to the resin as a filler, and includes the following steps:
A step of acquiring in advance calibration curve data showing the tendency of the molecular weight of the surface treatment agent and the elastic modulus of the resin material to increase monotonically as the molecular weight decreases, and storing the data in a computer storage means;
A step of determining the molecular weight of the surface treatment agent corresponding to the target elastic modulus based on the calibration curve data stored in the storage means;
A step of producing a resin material by adding fine particles having a surface treatment agent having a determined molecular weight to the resin as a filler.

According to the present invention, as a correlation between the molecular weight of the surface treatment agent of fine particles and the elastic modulus of the resin, the elastic modulus is improved as the surface treatment agent has a lower molecular weight, so that the elastic modulus of the resin material can be improved. At the same time, the elastic modulus of the resin can be adjusted at a high level.

The present invention will be described in detail below.

As the fine particles used in the filler of the present invention, various fine particles can be used, and either an inorganic material or an organic material may be used. Examples of the shape of the fine particles include a spherical shape, a needle shape, a plate shape, a fibrous shape, an amorphous shape, and the like. As for the size of the fine particles, micrometer to nanometer size fine particles can be used.

Examples of the inorganic substances include metals, metal oxides, hydroxides, carbonates, sulfates, silicates, nitrides, carbons, potassium titanate, basic magnesium sulfate inorganic fibers (MOS), and lead zirconate titanate. , Aluminum silicate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, boron, various magnetic powders, slag fiber, zeolite and the like.

Examples of the metal include transition metals of the 8th to 12th groups, for example, Au, Ag, Cu, Ni, Pd, Pt, Co, Rh, Ir, Ru, Zn, Fe and the like. These may be used alone or in combination of two or more.

As the shape of the metal fine particles, nanoparticles can be used. As a method for synthesizing nanoparticles capable of atomizing metal fine particles as a core metal into nano-sized particles, a physical method, a vapor phase method, a liquid phase method, and other chemical methods are known.

Examples of the metal oxide include silica, alumina, zirconia, titanium oxide, magnesium oxide, antimony oxide, zinc oxide, cesium oxide, lanthanum oxide, yttrium oxide, tungsten oxide, vanadium oxide, cadmium oxide, tantalum oxide, and niobium oxide. , Tin oxide, bismuth oxide, cerium oxide, copper oxide, iron oxide, indium oxide, boron oxide, calcium oxide, barium oxide, thorium oxide, indium tin oxide, ferrite and the like. These may be used alone or in combination of two or more. Further, two or more kinds of metal fine particles and metal oxide fine particles may be used in combination.

Examples of the hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and the like.

Examples of the carbonate include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite and the like.

Examples of the sulfate include calcium sulfate, barium sulfate, gypsum fiber and the like.

Examples of the silicate include calcium silicate, wollastonite, zonotrite, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balun and the like. Can be mentioned.

Examples of the nitride include aluminum nitride, boron nitride, silicon nitride and the like.

Examples of the carbons include carbon black, graphite, carbon fiber, carbon balun, activated charcoal, bamboo charcoal, charcoal, carbon nanotubes, carbon nanohorns, fullerenes and the like.

Examples of the organic substance include polyamide resins such as nylon 6, nylon 12, and nylon 66, fluororesins such as polytetrafluoroethylene and polyvinylidene fluoride, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, natural rubber, and isoprene. Examples thereof include rubbers such as rubber and acrylic rubber, polymer compounds such as starch, cellulose, carboxymethyl cellulose and silicone-based polymers, and hollow polymers using polymer compounds.

The method for producing the filler of the present invention is not limited, and a method for producing fine particles from nano size to micro size, for example, a chemical or physical synthesis method by bottom-up and downsizing can be used. ..

The surface treatment agent used in the filler of the present invention is a compound having an action of suppressing aggregation of fine particles, enhancing dispersion stability in a dispersion medium or a resin, and enhancing affinity and adhesion to the dispersion medium and the resin. Can be used.

The surface treatment agent used in the filler of the present invention is an organic substance used in chemical and physical synthesis methods by bottom-up and downsizing. The surface treatment agent is preferably an organic substance having a functional group shared, coordinated or hydrogen-bonded to the fine particles, which affects the dispersibility of the fine particles and the affinity with the resin.

The surface treatment agent modifies the surface of the formed fine particles and maintains a stable dispersed state. Examples of the surface treatment agent include water or aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorophatic hydrocarbons (methane derivatives, ethane derivatives, ethylene derivatives), alcohols, esters, ethers, and ketones. Classes, glycol ethers (cellosolves), alicyclic hydrocarbons, aliphatic hydrocarbons, dispersible or soluble in organic solvents such as mixtures of aliphatic or aromatic hydrocarbons, shared in fine particles, coordination or hydrogen Examples thereof include low molecular weight compounds having functional groups to be bonded, polymers, surfactants and the like.

Low molecular weight compounds that can be used as surface treatment agents include carboxyl groups, carboxylate groups, amino groups, hydroxyl groups, thiol groups, phosphino groups, carbonyl groups, aldehyde groups, ester groups, ketone groups, urea groups, and carbamate groups. Examples thereof include compounds having a functional group such as a dithiocarbamic acid group, a dithiocarboxylic acid group, a nitro group, a sulfonic acid group, a sulfoxide group, a phosphoric acid group and a phosphonic acid group.

Compounds with a carboxyl group include, for example, acetic acid, propanoic acid, butyric acid, valerate, caproic acid, heptanic acid, capric acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, olein. Organic acids such as acids, linoleic acids, linolenic acids, arachidic acids, sorbic acids, avietic acids and benzoic acids, and alkali metal salts such as sodium salts, potassium salts and lithium salts of these compounds, calcium salts, strontium salts and bariums. Examples thereof include alkaline earth metal salts such as salts and radium salts, and carboxylate compounds such as magnesium salts, beryllium salts, ammonium salts and lower alkanolamine salts. Examples of compounds having an amino group include trimethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, n-octylamine, tert-octylamine and nonylamine. Examples thereof include decylamine, undecylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, phenethylamine, piperidine, pyrrolidine, pyrrole, saccharin and the like. Compounds with hydroxyl groups include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol. , Hexadecanol, octadecanol, phenol, benzyl alcohol, citronellol, terpineol, retinol, hydroxycitronellal, butylhydroxyanisole, borneol, methanol, menthol, linalol, tocopherol and the like. Examples of compounds having a thiol group include propanethiol, butanethiol, pentanthiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tetradecanethiol, hexadecanethiol, octadecanethiol, and thiophenol. , Thiol benzoic acid and the like. Compounds with a phosphine group include, for example, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine. , Triphenylphosphine, tri-n-octylphosphine, tridecylphosphine, tridodecylphosphine, tritetradecylphosphine, trioctadecylphosphine and the like.

Further, it may be a compound containing a plurality of functional groups in one molecule of the surface treatment agent. Examples of the low molecular weight compound containing at least two functional groups include oxalic acid, phthalic acid, fumaric acid, maleic acid, succinic acid, sebacic acid, glutaric acid and the like as compounds having a carboxyl group. Alkali metal salts such as sodium salt, potassium salt and lithium salt of these compounds, alkaline earth metal salts such as calcium salt, strontium salt, barium salt and radium salt, and magnesium salt, beryllium salt, ammonium salt and lower alkanol. Examples thereof include carboxylate compounds such as amine salts. Examples of the compound having an amino group include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, pyrazine and the like. Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, glycerin, diglycerin, glucose, xylitol, sclarose, sorbitol, mannitol, xylose, trehalose, ramnorth, ribose, rutin, tannic acid, ascorbic acid, hesperidin and the like. .. Examples of compounds having a thiol group include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, and 1,7-heptandithiol. , 1,8-octanedithiol, 1,9-nonandithiol, 1,10-decandithiol, 1,11-undecandithiol, 1,12-dodecandithiol, 1,14-tetradecandithiol, 1,16-hexadecanedithiol, Examples thereof include 1,18-octadecanedithiol. Compounds having a phosphino group include, for example, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2,2'-. Bis (diphenylphosphino) -1,1'-binaphthyl and the like can be mentioned.

Further, as a low molecular weight compound having two or more of any one of a carboxyl group, a carboxylate group, an amino group, a hydroxyl group, a thiol group and a phosphino group, for example, citric acid, lactic acid, apple acid, tartrate acid, glycolic acid, glyceric acid, etc. Tartronic acid, gluconic acid, ferulic acid, mevalonic acid, hydroacrylic acid, gallic acid, vanillin, alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, Serine, treonine, tryptophan, tyrosine, valine, cysteine, cystine, betaine, nicotinic acid, pantothenic acid, folic acid, biotin, theanine, aspartame, neotheme, ethylenediaminetetraacetic acid, natamic acid, mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid, ethanol Amin, diethanolamine, triethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2- (2-aminoethylamino) ethanol, thiamine, glucosamine, 2-mercaptoethanol, 1-mercapto-2, Examples thereof include 3-propanediol, cysteamine, diphenyl-2-pyridylphosphine, trishydroxymethylphosphine and the like, and further, alkali metal salts such as sodium salt, potassium salt and lithium salt of these compounds, calcium salt, strontium salt and barium. Examples thereof include alkaline earth metal salts such as salts and radium salts, and carboxylate compounds such as magnesium salts, beryllium salts, ammonium salts and lower alkanolamine salts.

The surface treatment agent is preferably a compound having a functional group covalently bonded to the fine particles. In the covalent bond, since the surface treatment agent is strongly bonded to the fine particles as compared with the coordination bond, it is possible to have a stronger interaction between the fine particles and the resin via the surface treatment agent. Furthermore, as the bond between the surface treatment agent and the resin, covalent bonds, coordination bonds, hydrogen bonds, π-π interactions between aromatic rings, and van der Waals forces acting between alkyl chains are considered. Of these, covalent bonds are preferred. Further, when the interaction between the fine particles and the resin is to be strengthened, it is preferable that the bond between the surface treatment agent and the fine particles is a covalent bond and the bond between the surface treatment agent and the resin is a covalent bond.

As the surface treatment agent covalently bonded to the metal, those represented by the following formula (I) can be used (see the contents disclosed in Japanese Patent No. 5439468 and Japanese Patent No. 5438994).

In the formula, X ¹ represents any of the following (A) to (C), and m represents an integer of 1 to 5.
(A) (CH ₂ ) _n COOH or a salt thereof, or a corresponding carboxylate ion (n indicates an integer of 0 to 3).
(B) (CH ₂ ) _n OH or a salt thereof, or a corresponding alkoxide ion (n indicates an integer of 0 to 3).
(C) Saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms In addition to the surface treatment agents for low molecular weight compounds as described above, carboxyl groups, carboxylate groups, amino groups, hydroxyl groups, thiol groups, phosphino groups, and carbonyl groups. It has functional groups such as group, aldehyde group, ester group, ketone group, urea group, carbamic acid group, dithiocarbamic acid group, dithiocarboxylic acid group, nitro group, sulfonic acid group, sulfoxide group, phosphoric acid group and phosphonic acid group. Polymer surface treatment agents can also be used.

As the surface treatment agent having an amino group, for example, polyvinylpyrrolidone, polovinylpolypyrrolidone, polyethyleneimine, polypropyleneimine, polyallylamine, polypyrrole and the like can be used, preferably poly (1-vinyl-2-pyrrolidone) and the like. Can be mentioned.

Examples of the surface treatment agent having a carboxyl group or a carboxylate group include cellulose-based polymers such as carboxymethyl cellulose and sodium carboxymethyl cellulose, acrylic acid-based polymers such as sodium polyacrylate and ammonium polyacrylate, alginate, and sodium alginate. , Natural polymers such as sodium caseinate and nysin, and the like.

Examples of the surface treatment agent having a hydroxyl group include polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyglycerin, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl starch, pectin, chitin, chitosan, xanthan gum, guar gum, and hydroxypropyl. Guar gum, locust bean gum, tammalid gum, tragand gum, agarose, amylose, amylopectin, hyaluronic acid, mannan, glucomannan, curdran, dextran, levan, gellan gum, arabic gum, tara gum, karaya gum, cyclodextrin, carrageenan cyclodextrin, polysorbate, lactoferrin And so on.

Polymer surface treatment agents have a high dispersion stabilizing effect, and polymers such as those exemplified above are water or aromatic hydrocarbons, chlorinated aromatic hydrocarbons, and chlorophatic hydrocarbons (methane derivatives, Ethane derivatives, ethylene derivatives), alcohols, esters, ethers, ketones, glycol ethers (cellosolves), alicyclic hydrocarbons, aliphatic hydrocarbons, mixtures of aliphatic or aromatic hydrocarbons, etc. It can be dispersed or dissolved in an organic solvent.

Further, two or more kinds of surface treatment agents may be used in combination of a low molecular weight compound and a low molecular weight compound, a high molecular weight compound and a high molecular weight compound, and a low molecular weight compound and a high molecular weight compound.

Further, the surface treatment agent used in the filler of the present invention includes a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a quaternary ammonium salt, an alkylamine salt, an alkylphosphonate, and an alkylsulfonate. Etc. can be used.

Examples of the silane coupling agent include methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, pentyltrimethoxysilane, and n-hexyl. Trimethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, n-decyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, styrylethyltrimethoxysilane, phenetyltri Methoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, phenyltrimethoxysilane, benzyltrimethoxysilane, 3- (pentafluorophenyl) propyltrimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, Chlorophenyltrimethoxysilane, (chloromethyl) phenylethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-bromopropyltrimethoxysilane, 3-iodopropyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, vinyl -Tris (β-methoxyethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanuppropyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, 3-cyanopropyltrimethoxysilane , Γ-Aminopropyltrialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane and the like.

Examples of the titanate coupling agent include tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, butyl titanate dimer, tetraoctyl titanate, isopropyltrioctanoyl titanate, isopropyltriisostearoyl titanate, and isopropyldiacryloyl isostearoyl. Titanate, isopropyldimethacryloyl isostearol titanate, isopropyltris (dodecylbenzenesulfonyl) titanate, isopropyltris (p-cumylphenyl) titanate, isopropyltris [2-N- (2-aminoethyl) aminoethyl] titanate, isopropyltris (dioctylphospho) Notitanate), isopropyltris (dioctylpyrophosphono) titanate, bis (p-cumylphenyl) carbonylmethylene titanate, diisostearoylethylene titanate and the like.

Aluminate coupling agents include diisopropylate aluminum oleyl acetoacetate, isopropylate (acrylate) aluminum oleyl acetoacetate, isopropilate (acetoacetate) aluminum oleyl acetoacetate, isopropylate (dibutyl phosphate) aluminum oleyl acetoacetate, isopropylate. Examples thereof include (dibutylpyrrophosphate) aluminum oleylacetate, isopropylate (dodecylbenzenesulfonate) aluminum oleylacetate, and isopropylate (laurylsulfate) aluminum oleylacetate.

Examples of the quaternary ammonium salt include octyltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, lauryltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, trioctylmethylammonium chloride, and tristearylmethylammonium chloride. Tetraoctylammonium chloride, decyldimethylbenzylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, benzethonium chloride, cetylpyridinium chloride, alkylisoquinolium chloride, octyltrimethylammonium bromide, stearyltrimethylammonium bromide, bromide Cetyltrimethylammonium, lauryltrimethylammonium bromide, dioctyldimethylammonium bromide, distearyldimethylammonium bromide, trioctylmethylammonium bromide, tristearylmethylammonium bromide, tetraoctylammonium bromide, decyldimethylbenzylammonium bromide, Examples thereof include lauryldimethylbenzylammonium bromide, stearyldimethylbenzylammonium bromide, benzethonium bromide, cetylpyridinium bromide, and alkylisoquinolium bromide.

Examples of alkylamine salts include octylamine, decylamine, laurylamine, stearylamine, coconut oil amine, dioctylamine, distearylamine, trioctylamine, tristearylamine, dioctylmethylamine and the like as inorganic acids such as hydrochloric acid, nitrate and sulfuric acid. , Neutralization products neutralized with carboxylic acids such as acetic acid and the like.

As the surface treatment agent used in the filler of the present invention, it is preferable to use one having a smaller molecular size (three-dimensional structure) and a low molecular weight. As a result, the elastic modulus, tensile strength, compressive strength, etc. of the resin material can be increased, and the durability can be improved. It is considered that this is because the resin and the fine particles of the filler directly interact with each other to improve the strength while maintaining the affinity with the surface treatment agent.

The molecular weight of the surface treatment agent used in the filler of the present invention is less than 100,000, preferably 10,000 or less, more preferably 1,000 or less, still more preferably 200 or less. That is, in order for the core metal and the resin to interact effectively, it is preferable that the surface treatment agent has a small molecular weight. When a polymer having a molecular weight distribution is used as the surface treatment agent in the present invention, the molecular weight is measured by, for example, gel permeation chromatography (GPC) by comparing with a standard substance having a known molecular weight. The number average molecular weight is taken into account.

The filler of the present invention preferably has a mass ratio of fine particles in the filler to the surface treatment agent (fine particles: surface treatment agent) of 55:45 or more, more preferably 60:40 or more, and further preferably 70:30. The above is particularly preferably 80:20 or more. The higher the proportion of fine particles in the filler, the stronger the interaction between the fine particles and the resin.

The resin material of the present invention contains the above filler. This resin material can be produced by adding a filler to the resin according to a conventional method and kneading if necessary.

The filler can be used as a dispersion of fine particles or a dry fine particle, and when used as a dispersion of fine particles, it is used as a dispersion of fine particles of water or aromatic hydrocarbons, aromatic hydrocarbons chloride, and aliphatic hydrocarbons chloride. (Methane derivatives, ethane derivatives, ethylene derivatives), alcohols, esters, ethers, ketones, glycol ethers (cellosolves), alicyclic hydrocarbons, aliphatic hydrocarbons, aliphatic or aromatic hydrocarbons It can be used as a dispersion of an organic solvent such as a mixture of. Further, when used as dry fine particles, the dispersion liquid of the fine particles can be used as dry fine particles obtained by performing operations such as filtration, centrifugation, distillation under reduced pressure, and drying under reduced pressure.

Examples of the method for producing the resin material include a method in which a dispersion of the above filler or a dried filler is added to the resin and kneaded. Alternatively, a method may be mentioned in which a filler is added to a resin dissolved in a solvent, melt-kneaded, and then the solvent is distilled off to obtain a resin composition in which the filler is uniformly dispersed. Further, a method of obtaining a resin composition by mixing a filler and a resin monomer and then polymerizing the resin monomer can be mentioned. Further, a method of mixing and stirring the dispersion liquid of the filler and the solvent containing the resin and quickly distilling off only the solvent under high temperature and reduced pressure to obtain a resin composition in which the filler is uniformly dispersed can be mentioned.

Examples of the resin used in the resin material of the present invention include acrylics such as methyl poly (meth) acrylate, ethyl poly (meth) acrylate, and methyl (meth) acrylate-butyl (meth) acrylate copolymer. Polymeric polyester resins such as resins, polyethylene, polypropylene, polymethylpentene, cyclic olefin polymers and other polyolefin resins, polycarbonate resins, polyethylene terephthalates, polybutylene terephthalates and polyethylene naphthalates, polyurethanes, polythiourethanes, polystyrenes and polyamides. , Polyethylene, Polyamideimide, Polyetherimide, Acrylonitrile-styrene copolymer, Polyether sulphon, Polysulphon, Cellulosic resins such as triacetyl cellulose, Polyvinyl acetate, Ethylene-vinyl acetate copolymer, Polyvinylpyrrolidone, Polychloride Thermoplastic resins such as vinylidene, polyether ether ketone, polyacetal, polyvinyl alcohol, polyphenylene ether, polyvinylidene fluoride, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, nylon, liquid crystal polymer, urethane, thiourethane, urea, melamine , Acrylic melamine, episulfide, epoxy, allyl, silicone, phenol, urea, heat-curable resins such as unsaturated polyesters, acrylics such as acrylic acid of polyhydric alcohols and simple such as 2-hydroxyethyl methacrylate or methacrylic acid ester. Functional or polyfunctional (meth) acrylate compounds, polyfunctional urethane (meth) acrylate compounds such as those synthesized from diisocyanates and polyhydric alcohols and hydroxyesters of acrylic acid or methacrylic acid, polys having acrylate-based functional groups Examples thereof include ultraviolet curable resins such as ether, polyester, epoxy, alkyd, spiroacetal, polybutadiene, and polythiolpolyene.

The resin material of the present invention can be used in all fields in which the resin material is used because the strength such as elasticity is improved by adding a filler using a surface treatment agent having a small molecular weight. Due to the properties of metal fine particles, such as conductivity, antistatic property, magnetism, flame retardancy, antibacterial property, and antioxidant property, automobile members, conductive materials, printed wiring boards, various laminated boards, displays, paints, and construction Materials, packaging materials, adhesives, cushioning materials, heat insulating materials, foam bodies, food and beverage containers, cosmetic containers, toys, wrap films, agricultural films, optical functional films, magnetic tapes, photographic films, packaging films, electromagnetic waves It can be suitably used for shield films, fibers, medical instruments, dental materials and the like. In particular, when used in food and beverage containers, cosmetic containers, medical instruments, and dental materials, it is preferable to use a surface treatment agent having high biosafety.

Further, the surface treatment agent used in the filler of the present invention enhances the conductivity, antistatic property, viscosity thickening, light resistance, heat resistance, water resistance, refractive index, antibacterial property, etc. of the resin material depending on its characteristics. It is also possible.

The resin material of the present invention preferably has an increase rate of elastic modulus of 1% or more, more preferably 4% or more, still more preferably 10% or more, and particularly preferably 13% or more due to the addition of a filler to the resin. Is.

In this way, the present inventor has found a correlation between the molecular weight of the surface treatment agent of fine particles and the elastic modulus of the resin, and specifically, the present inventor has found a new finding that the lower the molecular weight of the surface treatment agent, the higher the elastic modulus. It was. Based on this new finding, according to the present invention, when fine particles having a surface treatment agent having a molecular weight of less than 100,000 are added to the resin as a filler, the molecular weight of the surface treatment agent and / or the fine particles and the surface treatment agent A method of adjusting the elastic modulus of a resin material, which adjusts the mass ratio, is provided.

A method for producing a resin material in which fine particles having a surface treatment agent having a molecular weight of less than 100,000 are added to the resin as a filler, which comprises the following steps (A), (B), and (C). A manufacturing method is provided.

(A) In advance, the data of the calibration curve (curve or straight line) showing the tendency of the molecular weight of the surface treatment agent and the elastic modulus of the resin material to increase monotonically as the molecular weight decreases is acquired and stored in a computer. Process of storing in means

In this step (A), a calibration curve is created based on the elastic modulus data measured using a plurality of surface treatment agents having known molecular weights and different from each other. For example, from the data of the molecular weight of the surface treatment agent and the measured elastic modulus, regression analysis such as nonlinear regression is performed by the least squares method, etc., and calibration is performed as a regression equation showing the relationship between the molecular weight of the surface treatment agent and the elastic modulus data. You can get a line. The computer stores a control unit equipped with a CPU, ROM, RAM, etc. for driving and controlling each component, a storage unit that stores a program for operating each component, and a storage unit and a mouse that also store calibration curve data. , An input unit such as a keyboard, and an output unit such as a display may be provided. The calibration curve acquired in advance is stored in the computer as a graph or a relational expression, and is displayed on a display or the like as desired. The calibration curve data can be provided to the user as, for example, a database including variations depending on the type of resin and metal or metal oxide fine particles, or as commercial software.

(B) A step of determining the molecular weight of the surface treatment agent corresponding to the target elastic modulus based on the calibration curve data stored in the storage means.

In this step (B), the user of the calibration curve determines the molecular weight of the surface treatment agent corresponding to the target elastic modulus based on the data of the calibration curve, and selects an appropriate surface treatment agent according to the molecular weight. select. By collating the elastic modulus of the target resin material with the calibration curve, the molecular weight of the surface treatment agent corresponding to the target elastic modulus can be determined. This result is displayed on a computer display or the like, if desired.
(C) A step of producing a resin material by adding fine particles having a surface treatment agent having a determined molecular weight to the resin as a filler.

In this step (C), the user of the calibration curve can obtain a resin material having a desired elastic modulus by using fine particles having a surface treatment agent selected in step (B) on the surface.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The ratio (mass ratio) of the fine particles in the filler to the surface treatment agent was determined using a thermogravimetric analyzer (manufactured by Seiko Instruments, TG / DTA6200).

The ultraviolet-visible absorption spectrum was measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, V-550).

The infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR-6100).

The elastic modulus of the resin material was measured using a thermomechanical analyzer (TMA / SS6200, manufactured by Seiko Instruments).
1. 1. Synthesis of Metal Fine Particles Typical synthesis examples of the metal fine particles used in the following examples are as follows.
<Synthesis example 1>
(1) Synthesis of compound 1 Compound 1 represented by the following formula was synthesized.

4-Aminobenzoic acid (50.02 g, 0.36 mol) was added to a 42% aqueous tetrafluoroboric acid solution (152.45 g, 0.73 mol) and stirred. A 40% aqueous sodium nitrite solution (62.89 g, 0.36 mol) was added dropwise at 10 to 15 ° C. for 30 minutes, stirred for 10 minutes, and then purified by filtration, recrystallization, etc. to obtain a white powder. ..
Infrared absorption spectrum 2291 cm ^-1 : N ≡ N ⁺ expansion and contraction vibration, 1728 cm ^-1 : C = O expansion and contraction vibration, 808 cm ^-1 : CH out-of-plane bending vibration (2) Synthesis of gold nanoparticles Tetrachloro gold (III) Acid tetrahydrate (1.00 g, 2.43 mmol) was dissolved in ion-exchanged water (99.5 mL) and N ₂ was allowed to flow for 15 minutes for degassing. Under N ₂ atmosphere, compound 1 (0.573 g, 2.43 mmol) was added, stirred for 5 minutes, and then sodium borohydride (0.0459 g, 1.21 mmol) dissolved in 80.5 mL of ion-exchanged water was added at 5-10 ° C. It was added dropwise in 2 hours. After the dropping, the mixture was stirred for 1 hour to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a black-purple aqueous dispersion having a gold content of 50 g / L. The average particle size of the gold nanoparticles was determined using a transmission electron microscope (H-7500, manufactured by Hitachi, Ltd.).
Ultraviolet-visible absorption spectrum peak wavelength 550 nm, average particle size 19 nm

<Synthesis example 2>
Tetrachlorogold (III) acid tetrahydrate (0.042 g, 0.102 mmol) was dissolved in ion-exchanged water (25.0 mL), and N ₂ was allowed to flow for 15 minutes for degassing. N ₂ atmosphere, tetra -n- octyl bromide (0.131 g, 0.240 mmol) in toluene was dissolved solution (25.0 mL) was added as a phase transfer catalyst, and stirred for 1 hour. Further, a toluene solution (25.0 mL) in which n-octylamine (0.143 g, 1.106 mmol) was dissolved was added, and the mixture was stirred for 5 minutes. Sodium borohydride (0.059 g, 1.560 mmol) dissolved in 25.0 mL of ion-exchanged water was added dropwise at room temperature in 30 minutes. After the dropping, the mixture was stirred for 24 hours and the toluene layer was separated to obtain a purple dispersion in which gold nanoparticles were dispersed. The obtained toluene dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with toluene to obtain a purple dispersion having a gold content of 10 g / L. The average grain size of gold nanoparticles is determined from the peak wavelength of surface plasmon resonance measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-550). J. Phys. Chem. C 2007, 111, 14664-14669 It was calculated based on the above formula.
Ultraviolet-visible absorption spectrum peak wavelength 527 nm, average particle size 38 nm

<Synthesis example 3>
(1) Synthesis of compound 2 Compound 2 represented by the following formula was synthesized.

4-Decilaniline (8.00 g, 0.034 mol), 100 mL of acetic acid, and 100 mL of propionic acid were added to a 42% aqueous tetrafluoroboric acid solution (80.0 g, 0.38 mol) and stirred. 4.44% sodium nitrite aqueous solution (80.0 g, 0.051 mol) was added dropwise at 3 to 5 ° C. for 30 minutes, and after stirring for 2 hours, 300 mL of ion-exchanged water was added to purify by filtration, washing with water, recrystallization, etc. By doing so, a white powder was obtained.
Infrared absorption spectrum 2917cm ^-1: C-H stretching vibration, 2847cm ^-1: C-H stretching vibration, 2297cm ^-1: N≡N ⁺ stretching vibration, 820cm ^-1: C-H out-of-plane deformation vibration (2) gold Synthesis of Nanoparticles Tetrachlorogold (III) acid tetrahydrate (0.209 g, 0.507 mmol) was dissolved in ion-exchanged water (16.0 mL) and N ₂ was allowed to flow for 15 minutes for degassing. In an N ₂ atmosphere, a toluene solution (30.0 mL) in which Compound 2 (0.337 g, 1.014 mmol) was dissolved was added, and the mixture was stirred for 2 hours, then the toluene layer was separated and washed with water twice. Sodium borohydride (0.0461 g, 1.219 mmol) dissolved in 8.0 mL of ion-exchanged water was added dropwise at room temperature in 40 minutes. After the dropping, the mixture was stirred for 1 hour and the toluene layer was separated to obtain a purple dispersion in which gold nanoparticles were dispersed. The obtained toluene dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with toluene to obtain a purple dispersion having a gold content of 10 g / L. The average grain size of gold nanoparticles is determined from the peak wavelength of surface plasmon resonance measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-550). J. Phys. Chem. C 2007, 111, 14664-14669 It was calculated based on the above formula.
Ultraviolet-visible absorption spectrum peak wavelength 535 nm, average particle size 55 nm

<Synthesis example 4>
Tetrachlorogold (III) acid tetrahydrate (0.264 g, 0.641 mmol) was dissolved in ion-exchanged water (1490 mL), and N ₂ was allowed to flow for 30 minutes for degassing. In an N ₂ atmosphere, 59.6 mL of a 0.2 M aqueous sodium citrate solution was added dropwise at room temperature in 30 minutes. After the dropping, the mixture was stirred at 80 ° C. for 25 minutes to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a purple aqueous dispersion having a gold content of 10 g / L. The average particle size of the gold nanoparticles was determined using a transmission electron microscope (H-7500, manufactured by Hitachi, Ltd.).
Ultraviolet-visible absorption spectrum peak wavelength 529 nm, average particle size 15 nm

<Synthesis example 5>
Tetrachlorogold (III) acid tetrahydrate (0.333 g, 0.809 mmol) was dissolved in ion-exchanged water (770 mL), and N ₂ was allowed to flow for 15 minutes for degassing. Under N ₂ atmosphere, sodium polyacrylate (Made by Aldrich, molecular weight ~ 5100, 0.228 g) was added, stirred for 30 minutes, and then sodium borohydride (0.0038 g, 0.100 mmol) dissolved in 100 mL of ethanol was added to room temperature. Below, it was dropped in 80 minutes. After the dropping, the mixture was stirred for 1 hour to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a purple aqueous dispersion having a gold content of 10 g / L. The average grain size of gold nanoparticles is determined from the peak wavelength of surface plasmon resonance measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-550). J. Phys. Chem. C 2007, 111, 14664-14669 It was calculated based on the above formula.
Ultraviolet-visible absorption spectrum peak wavelength 536 nm, average particle size 57 nm

<Synthesis example 6>
Tetrachlorogold (III) acid tetrahydrate (1.00 g, 2.43 mmol) was dissolved in ion-exchanged water (2427 mL), and N ₂ was allowed to flow for 30 minutes for degassing. Under N ₂ atmosphere, polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight: about 40,000, 0.808 g) was added, and after stirring for 30 minutes, sodium borohydride (0.0114 g, 0.301 mmol) dissolved in 303 mL of ethanol was added. The mixture was added dropwise at room temperature for 80 minutes. After the dropping, the mixture was stirred for 1 hour to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a purple aqueous dispersion having a gold content of 10 g / L. The average particle size of the gold nanoparticles was determined using a transmission electron microscope (H-7500, manufactured by Hitachi, Ltd.).
Ultraviolet-visible absorption spectrum peak wavelength 537 nm, average particle size 37 nm

<Synthesis example 7>
Tetrachlorogold (III) acid tetrahydrate (0.314 g, 0.762 mmol) was dissolved in ion-exchanged water (765 mL), and N ₂ was allowed to flow for 20 minutes for degassing. Sodium carboxymethyl cellulose (manufactured by Kanto Chemical Co., Inc., molecular weight 90,000, 0.3068 g) was added under an N ₂ atmosphere, and after stirring for 30 minutes, sodium borohydride (0.0036 g, 0.0952 mmol) dissolved in 94 mL of ethanol was added at room temperature. Below, it was dropped in 120 minutes. After the dropping, the mixture was stirred for 1 hour to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a purple aqueous dispersion having a gold content of 10 g / L. The average grain size of gold nanoparticles is determined from the peak wavelength of surface plasmon resonance measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-550). J. Phys. Chem. C 2007, 111, 14664-14669 It was calculated based on the above formula.
Ultraviolet-visible absorption spectrum peak wavelength 540 nm, average particle size 64 nm

<Synthesis Example 8>
Silver nitrate (0.2592 g, 1.53 mmol) was dissolved in ion-exchanged water (150 mL) and N ₂ was allowed to flow for 20 minutes for degassing. Under N ₂ atmosphere, compound 1 (0.108 g, 0.458 mmol) was added, stirred for 5 minutes, and then sodium borohydride (0.0058 g, 0.153 mmol) dissolved in 45 mL of ion-exchanged water was added at 5-10 ° C., 2 Dropped in time. After the dropping, the mixture was stirred for 1 hour to obtain a black-yellow dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a black-yellow aqueous dispersion having a silver content of 10 g / L. The average particle size of the silver nanoparticles was determined using a transmission electron microscope (TEM).
Ultraviolet-visible absorption spectrum peak wavelength 420 nm, average particle size 16 nm

<Synthesis example 9>
Copper (II) nitrate trihydrate (1.20 g, 4.97 mmol) was dissolved in ion-exchanged water (400 mL) and N ₂ was allowed to flow for 20 minutes for degassing. Compound 1 (0.35 g, 1.48 mmol) was added under N ₂ atmosphere, and the mixture was stirred for 5 minutes, and then sodium borohydride (0.094 g, 2.48 mmol) dissolved in 100 mL of ion-exchanged water was added at room temperature for 2 hours. Dropped. After the dropping, the mixture was stirred for 1 hour to obtain a black-yellow dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a black-yellow aqueous dispersion having a copper content of 10 g / L. The average particle size of the copper nanoparticles was determined using a particle size measurement system (ELSZ-2, manufactured by Otsuka Electronics Co., Ltd.).
Ultraviolet-visible absorption spectrum peak wavelengths 261 nm, 268 nm, average particle size 377 nm

<Synthesis Example 10>
Hexachloroplatinic (IV) acid hexahydrate (0.344 g, 0.664 mmol) was dissolved in ion-exchanged water (500 mL), and N ₂ was allowed to flow for 10 minutes for degassing. Under N ₂ atmosphere, polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight: about 40,000, 2.934 g) was added, and after stirring for 30 minutes, 500 mL of ethanol was added, and while maintaining the N ₂ atmosphere, 100 ° C. for 2 hours. Stirring gave a black dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a black aqueous dispersion having a platinum content of 10 g / L. The average particle size of platinum nanoparticles was determined using a transmission electron microscope (H-7500, manufactured by Hitachi, Ltd.).
Ultraviolet-visible absorption spectrum peak wavelength 249 nm, average particle size 7 nm

<Synthesis Example 11>
Tetrachlorogold (III) acid tetrahydrate (0.314 g, 0.762 mmol) was dissolved in ion-exchanged water (765 mL), and N ₂ was allowed to flow for 20 minutes for degassing. Sodium carboxymethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 100,000 to 110,000, 0.3068 g) was added under an N ₂ atmosphere, and after stirring for 30 minutes, sodium borohydride (0.0036 g, 0.0952 mmol) dissolved in 94 mL of ethanol was added. ) Was added dropwise at room temperature in 120 minutes. After the dropping, the mixture was stirred for 1 hour to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a purple aqueous dispersion having a gold content of 10 g / L. The average grain size of gold nanoparticles is determined from the peak wavelength of surface plasmon resonance measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-550). J. Phys. Chem. C 2007, 111, 14664-14669 It was calculated based on the above formula.
Ultraviolet-visible absorption spectrum peak wavelength 537 nm, average particle size 59 nm

<Synthesis Example 12>
Tetrachlorogold (III) acid tetrahydrate (0.209 g, 0.507 mmol) was dissolved in ion-exchanged water (32 mL), and N ₂ was allowed to flow for 15 minutes for degassing. Sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight approx. 250,000 to 700,000, 0.239 g) was added under an N ₂ atmosphere, and after stirring for 30 minutes, sodium borohydride (0.0024 g) dissolved in 63 mL of ethanol was added. , 0.063 mmol) was added dropwise at room temperature in 80 minutes. After the dropping, the mixture was stirred for 1 hour to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a purple aqueous dispersion having a gold content of 10 g / L. The average grain size of gold nanoparticles is determined from the peak wavelength of surface plasmon resonance measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-550). J. Phys. Chem. C 2007, 111, 14664-14669 It was calculated based on the above formula.
Ultraviolet-visible absorption spectrum peak wavelength 535 nm, average particle size 55 nm

<Synthesis Example 13>
Tetrachlorogold (III) acid tetrahydrate (0.209 g, 0.507 mmol) was dissolved in ion-exchanged water (32 mL), and N ₂ was allowed to flow for 15 minutes for degassing. Sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight about 2820000 to 3760000, 0.239 g) was added under N ₂ atmosphere, and after stirring for 30 minutes, sodium borohydride (0.0024 g) dissolved in 63 mL of ethanol was added. , 0.063 mmol) was added dropwise at room temperature in 80 minutes. After the dropping, the mixture was stirred for 1 hour to obtain a purple dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a purple aqueous dispersion having a gold content of 10 g / L. The average grain size of gold nanoparticles is determined from the peak wavelength of surface plasmon resonance measured using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-550). J. Phys. Chem. C 2007, 111, 14664-14669 It was calculated based on the above formula.
Ultraviolet-visible absorption spectrum peak wavelength 540 nm, average particle size 64 nm

<Synthesis Example 14>
Silver nitrate (3.935 g, 23.16 mmol) was dissolved in ion-exchanged water (1150 mL) and N ₂ was allowed to flow for 10 minutes for degassing. Sodium polyacrylate (Made by Aldrich, molecular weight ~ 5100, 1.090 g) was added under N ₂ atmosphere, stirred for 20 minutes, and then dissolved in 170 mL of ion-exchanged water. Sodium borohydride (0.1313 g, 3.471 mmol). Was added dropwise at 5 to 10 ° C. for 40 minutes. After the dropping, the mixture was stirred for 30 minutes to obtain a black-yellow dispersion. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a black-yellow aqueous dispersion having a silver content of 50 g / L. The average particle size of silver nanoparticles was determined using a particle size measurement system (ELSZ-2, manufactured by Otsuka Electronics Co., Ltd.).
Ultraviolet-visible absorption spectrum peak wavelength 434 nm, average particle size 205 nm

<Synthesis Example 15>
Silver oxide (12.80 g, 55.23 mmol) was dissolved in ethanol (1445 mL) and N ₂ was allowed to flow for 30 minutes for degassing. N ₂ atmosphere, polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., about 40000,4.80g molecular weight) was added and allowed to stir for 20 min, 80-90 ° C., stirred for 30 minutes, a black dispersion was obtained. The obtained dispersion was purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and the concentration was adjusted with ion-exchanged water to obtain a black aqueous dispersion having a silver content of 50 g / L. The average particle size of silver nanoparticles was determined using a particle size measurement system (ELSZ-2, manufactured by Otsuka Electronics Co., Ltd.).
Ultraviolet-visible absorption spectrum peak wavelength 401 nm, average particle size 255 nm

<Synthesis Example 16>
Silica fine particles with a particle size of 5 to 20 μm (Wako Gel C-500HG, 5.00 g, manufactured by Wako Pure Chemical Industries, Ltd.) were dispersed by adding them to methanol (127 mL), and a 28% aqueous ammonia solution (5.10 g) was added. The temperature was stirred for 1 hour. N-octyltrimethoxysilane (molecular weight 173, 0.360 g when bonded to the surface of silica fine particles) is dissolved in methanol (9.1 mL), an aqueous hydrochloric acid solution (0.083 g) with pH 4 is added, and the mixture is stirred for 1 hour to add water. After decomposition, the mixture was added dropwise to a methanol dispersion of silica fine particles at room temperature for 1 hour. After the dropping, the mixture was stirred at 40 ° C. for 24 hours, purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and then dried and dehydrated to obtain silica fine particles in which n-octylrimethoxysilane was bonded to the surface. .. As a result of measuring the infrared absorption spectrum of the obtained silica fine particles, expansion and contraction vibration derived from the methylene group was confirmed. Therefore, it was confirmed that the silica fine particles had a surface coated with n-octyltrimethoxysilane.
Infrared absorption spectrum 2937cm ^-1 : CH expansion and contraction vibration, 2863cm ^-1 : CH expansion and contraction vibration

<Synthesis example 17>
Silica fine particles with a particle size of 5 to 20 μm (Wako Gel C-500HG, 5.00 g, manufactured by Wako Pure Chemical Industries, Ltd.) were dispersed by adding them to methanol (127 mL), and a 28% aqueous ammonia solution (5.10 g) was added. The temperature was stirred for 1 hour. N-octadecyltrimethoxysilane (molecular weight 314, 0.575 g when bonded to the surface of silica fine particles) is dissolved in methanol (14.6 mL), an aqueous hydrochloric acid solution (0.083 g) with pH 4 is added, and the mixture is stirred for 1 hour to add water. After decomposition, the mixture was added dropwise to a methanol dispersion of silica fine particles at room temperature for 1 hour. After the dropping, the mixture was stirred at 40 ° C. for 24 hours, purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and then dried and dehydrated to obtain silica fine particles in which n-octadecyltrimethoxysilane was bonded to the surface. .. As a result of measuring the infrared absorption spectrum of the obtained silica fine particles, expansion and contraction vibration derived from the methylene group was confirmed. Therefore, it was confirmed that the silica fine particles had a surface coated with n-octadecyltrimethoxysilane.
Infrared absorption spectrum 2928cm ^-1 : CH expansion and contraction vibration, 2855cm ^-1 : CH expansion and contraction vibration

<Synthesis Example 18>
Silica fine particles with a particle size of 5 to 20 μm (Wako Gel C-500HG, 5.00 g, manufactured by Wako Pure Chemical Industries, Ltd.) were dispersed by adding them to methanol (127 mL), and a 28% aqueous ammonia solution (5.10 g) was added. The temperature was stirred for 1 hour. Sodium polyacrylate (manufactured by Aldrich, molecular weight ~ 5100, 1.090 g) dissolved in methanol (30 mL) was added dropwise to a methanol dispersion of silica fine particles at room temperature for 1 hour. After the dropping, the mixture was stirred at 40 ° C. for 24 hours, purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and then dried to obtain silica fine particles.

<Synthesis Example 19>
Silica fine particles with a particle size of 5 to 20 μm (Wako Gel C-500HG, 5.00 g, manufactured by Wako Pure Chemical Industries, Ltd.) were dispersed by adding them to methanol (127 mL), and a 28% aqueous ammonia solution (5.10 g) was added. The temperature was stirred for 1 hour. Polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight: about 40,000, 1.200 g) dissolved in methanol (30 mL) was added dropwise to a methanol dispersion of silica fine particles at room temperature for 1 hour. After the dropping, the mixture was stirred at 40 ° C. for 24 hours, purified by filtration, centrifugation, washing with water, washing with a solvent, etc., and then dried to obtain silica fine particles.

2. 2. Elastic modulus of resin material containing filler and rate of increase in elastic modulus The rate of increase in elastic modulus (%) is the elastic modulus of the resin material to which the filler was added in each example and each comparative example (Comparative Example 1, Comparative Example 5, It was calculated by the following formula from the elastic modulus of the resin to which the filler was not added in Comparative Example 6).
Increase rate of elastic modulus (%) = (elastic modulus of resin material with filler added-elastic modulus of resin without filler added) / elastic modulus of resin without filler x 100

<Examples 1 to 10>
Dry fine particles of metal nanoparticles were obtained by performing operations such as filtration, centrifugation, distilling under reduced pressure, and drying under reduced pressure on each of the metal nanoparticle dispersions of Synthesis Examples 1 to 10. The composition I was obtained by mixing 30% by mass of Bis-GMA (bisphenol A / glycidylmethacrylic acid), 70% by mass of TEDMA (triethylene glycol dimethacrylate), and 1% by mass of BPO (benzoyl peroxide). 5% by mass of dry powder fine particles of each metal nanoparticle was added as a filler. Further, as Composition II, 30% by mass of Bis-GMA, 70% by mass of TEDMA, and 0.5% by mass of DMPT (N, N-dimethyl-p-toluidine) were mixed. Compositions I and II are mixed in a thermomechanical analyzer (TMA) sample pan at a ratio of 1: 1 (mass%) and then cured in a nitrogen atmosphere at 23 ° C. for 30 minutes to fill the filler (metal nanoparticles). ) Was produced. The cured methacrylic resin was measured using TMA (manufactured by Seiko Instruments, TMA / SS6200) at 25 ° C., 0 to 1400 mN, and 100 mN / min, and the elastic modulus was obtained from the obtained stress / strain curve. The results are shown in Table 1.

<Comparative Examples 1 to 4>
In Comparative Example 1, the dry powder fine particles of the metal nanoparticles were not added, in Comparative Example 2, the gold nanoparticles of Synthesis Example 11, the gold nanoparticles of Synthesis Example 12 in Comparative Example 3, and the gold nanoparticles of Synthesis Example 13 in Comparative Example 4. A methacryl resin was prepared in the same manner as in Examples 1 to 10 except that the above was used, and the elasticity was measured. The results are shown in Table 1.

From Table 1, as compared with Comparative Example 1, the gold nanoparticles using the surface treatment agent having a molecular weight of less than 100,000 in Examples 1 to 7 had an elastic modulus of 7.95 or more and elasticity at a filler addition concentration of 2.5% by mass. The rate of increase was 1% or more, and it was confirmed that the elastic modulus was improved by adding gold nanoparticles. In particular, in the gold nanoparticles using the surface treatment agent having a molecular weight of 10,000 or less in Examples 1 to 5, the elastic modulus is 8.56 or more and the elastic modulus increase rate is 9% or more at a filler addition concentration of 2.5% by mass. Therefore, a significant improvement in elastic modulus was observed. Further, in the gold nanoparticles using the surface treatment agent having a molecular weight of 1000 or less in Examples 1 to 4, the elastic modulus is 8.68 or more and the increase rate of the elastic modulus is 10% or more, and the elastic modulus is significantly improved. It was seen. Among them, the gold nanoparticles using the surface treatment agents having a molecular weight of 200 or less in Examples 1 and 2 had an elastic modulus of 8.88 or more and an increase rate of the elastic modulus of 13% or more, and the elastic modulus was significantly improved. ..

On the other hand, the elastic modulus of the methacrylic resin to which gold nanoparticles using the surface treatment agent having a molecular weight of 100,000 or more in Comparative Examples 2 to 4 was added decreased, and showed a value lower than that of Comparative Example 1 without the filler. Further, when Example 7 (molecular weight: 90000) and Comparative Example 2 (molecular weight: 100,000 to 110,000) having different molecular weights of sodium carboxymethyl cellulose as the surface treatment agent are compared, the elastic modulus of Comparative Example 2 having a high molecular weight is small, and further. Even when the surface treatment agent is sodium polyacrylate, the higher the molecular weight, the more elastic it is in the order of Example 5 (molecular weight: ~ 5100), Comparative Example 3 (molecular weight: 250,000 to 700,000), and Comparative Example 4 (282000 to 3760000). We confirmed the tendency for the rate to decrease.

From the above results, it was confirmed that the elastic modulus of the methacryl resin, which is a thermosetting resin, was improved by adding gold nanoparticles using a surface treatment agent having a molecular weight of less than 100,000 as a filler. The results showed that the lower the molecular weight of the surface treatment agent for the particles, the higher the elastic modulus.

Furthermore, when comparing the bonds between the fine particles and the surface treatment agent in the range where the molecular weight of the surface treatment agent is about the same, the elastic modulus is improved in Example 1 as compared with Example 2, and the elastic modulus is improved as compared with Example 4. Since the elastic modulus is improved in Example 3, the gold nanoparticles in which the fine particles and the surface treatment agent are covalently bonded are more effective in improving the elastic modulus than the gold nanoparticles in the coordination bond. confirmed. From the above results, it was confirmed that the elastic modulus was most improved in Example 1 using gold nanoparticles in which the molecular weight of the surface treatment agent was 200 or less and the bond between the fine particles and the surface treatment agent was a covalent bond.

Further, in Examples 8 and 9, it was confirmed that the elastic modulus of the methacrylic resin was improved by adding the silver and copper nanoparticles in which the surface treatment agent having a molecular weight of 200 or less was covalently bonded as a filler. .. Further, in Example 10, it was confirmed that the elastic modulus of the methacrylic resin was improved by adding platinum nanoparticles using a surface treatment agent having a molecular weight of less than 100,000 as a filler.

<Examples 11 to 16>
The silver nanoparticle dispersions of Synthesis Examples 8 and 14 to 15 were subjected to operations such as filtration, centrifugation, distillation under reduced pressure, and drying under reduced pressure to obtain dried fine particles of silver nanoparticles. When 0.8 g of tetrahydrofuran was added to 0.2 g of polyvinylidene chloride and dissolved, the obtained dry fine particles were added and dispersed so that the filler addition concentration was 5 or 10% by mass with respect to polyvinylidene chloride. The obtained dispersion was dispensed into a glass petri dish, and then the solvent was removed while drying at 40 ° C. to prepare a polyvinylidene chloride resin to which silver nanoparticles were added as a filler. The produced polyvinylidene chloride resin was measured using TMA (manufactured by Seiko Instruments, TMA / SS6200) under the conditions of 25 ° C, 0 to 1400 mN, and 100 mN / min, and the elastic modulus was obtained from the obtained stress / strain curve. It was. The results are shown in Table 2.

<Comparative example 5>
Polyvinylidene chloride resin was prepared in the same manner as in Examples 11 to 16 except that dry powder fine particles of silver nanoparticles were not added, and the elastic modulus was measured. The results are shown in Table 2.

From Table 2, under the condition of the filler addition concentration of 5% by mass, the silver nanoparticles using the surface treatment agent having a molecular weight of less than 100,000 in Examples 11 to 13 had an elastic modulus of 1.84 or more and elasticity as compared with Comparative Example 5. The rate of increase was 3% or more, and it was confirmed that the elastic modulus was improved by adding silver nanoparticles. In particular, the silver nanoparticles using the surface treatment agents having a molecular weight of 10,000 or less in Examples 11 and 12 have an elastic modulus of 1.86 or more and an increase rate of the elastic modulus of 4% or more, further improving the elastic modulus. Was allowed to do. Further, in Example 11 using silver nanoparticles having a molecular weight of 200 or less and the bond between the fine particles and the surface treatment agent being a covalent bond, the elastic modulus was 2.34 or more and the increase rate of the elastic modulus was 30% or more. A remarkable improvement in elastic modulus was observed.

Further, under the condition that the filler addition concentration is 10% by mass, the silver nanoparticles using the surface treatment agent having a molecular weight of less than 100,000 in Examples 14 to 16 have an elastic modulus of 1.91 or more and an elastic modulus as compared with Comparative Example 5. The rate of increase was 7% or more, and it was confirmed that the elastic modulus was improved by adding silver nanoparticles. In particular, the silver nanoparticles using the surface treatment agents having a molecular weight of 10,000 or less in Examples 14 and 15 have an elastic modulus of 1.99 or more and an increase rate of the elastic modulus of 11% or more, further improving the elastic modulus. Was allowed to do. Further, in Example 14 using silver nanoparticles having a molecular weight of 200 or less and a covalent bond between the fine particles and the surface treatment agent, the elastic modulus was 2.85 or more and the increase rate of the elastic modulus was 60% or more. A significant improvement in elastic modulus was observed.

From the above results, it was confirmed that the elastic modulus of silver nanoparticles using a surface treatment agent having a molecular weight of less than 100,000 can be improved by adding it to polyvinylidene chloride resin, which is a thermoplastic resin, as a filler. The results showed that the lower the molecular weight of the surface treatment agent for silver nanoparticles, the higher the elastic modulus.

<Examples 6 and 17-21>
Regarding the gold nanoparticles using polyvinylpyrrolidone as a surface treatment agent of Synthesis Example 6, the obtained dispersion is purified by filtration, centrifugation, washing with water, solvent washing, etc., and then filtered, centrifuged, distilled under reduced pressure, dried under reduced pressure, etc. By performing the above operation, dry fine particles of gold nanoparticles having different mass ratios of fine particles in gold nanoparticles: surface treatment agent were obtained. Each of the obtained gold nanoparticles was added to the methacrylic resin composition in the same manner as in Example 6, and the cured sample was subjected to TMA (manufactured by Seiko Instruments, TMA / SS6200) at 25 ° C., 0 to 1400 mN, 100 mN /. The measurement was performed under the min condition, and the elastic modulus was obtained from the obtained stress / strain curve. The results are shown in Table 3.

From Table 3, as compared with Comparative Example 1, in the case of the gold nanoparticles of the filler in which the mass ratio of the fine particles: surface treatment agent of Examples 6 and 17 to 19 was 60:40 or more, the filler addition concentration was 2.5% by mass. The elastic modulus was 7.98 or more, the increase rate of the elastic modulus was 1% or more, and it was confirmed that the elastic modulus was improved by adding the gold nanoparticles. Further, in the gold nanoparticles having a mass ratio of the fine particles: surface treatment agent of Examples 6 and 17 to 18 of 70:30 or more, the elastic modulus was 8.20 or more and the elastic modulus was 8.20 or more at a filler addition concentration of 2.5% by mass. The increase rate was 4% or more, and it was confirmed that the elastic modulus was significantly improved by adding the gold nanoparticles. In particular, in the gold nanoparticles having a mass ratio of fine particles: surface treatment agent of 80:20 or more in Examples 6 and 17, the elastic modulus was 8.28 or more and the increase rate of the elastic modulus was 8.28 or more at a filler addition concentration of 2.5% by mass. Was 5% or more, and it was confirmed that the elastic modulus was significantly improved by adding gold nanoparticles. On the other hand, in Examples 20 and 21, no improvement in elastic modulus was observed in the gold nanoparticles having a mass ratio of fine particles: surface treatment agent of 50:50 or less.

From the above results, it was confirmed that the elastic modulus of the methacrylic resin was improved by adding a filler having a mass ratio of fine particles: surface treatment agent of 60:40 or more in the metal nanoparticles. That is, it was confirmed that the elastic modulus was improved as the proportion of the surface treatment agent in the filler was small and the proportion of the fine particles was large because the fine particles and the resin strongly interacted with each other.

<Examples 22 to 25>
When 1.6 g of tetrahydrofuran was added to 0.4 g of polystyrene to dissolve it, each of the silica fine particles of Synthesis Examples 16 to 19 was added to the polystyrene resin so that the addition concentration of the filler containing silica was 5% by mass and dispersed. did. The obtained dispersion was dispensed into a glass petri dish, and then the solvent was removed while drying at 40 ° C. to prepare a polystyrene resin to which silica fine particles were added as a filler. The polystyrene resin produced was measured using TMA (manufactured by Seiko Instruments, TMA / SS6200) at 25 ° C., 0 to 1400 mN, and 100 mN / min, and the elastic modulus was determined from the obtained stress / strain curve. The results are shown in Table 4.

<Comparative Example 6>
Polystyrene resin was prepared and the elastic modulus was measured in the same manner as in Examples 22 to 25 except that the filler of the silica fine particles was not added. The results are shown in Table 4.

From Table 4, as compared with Comparative Example 6, in the silica fine particles using the surface treatment agent having a molecular weight of less than 100,000 in Examples 22 to 25, the elastic modulus was 3.60 or more and the elastic modulus was increased at a filler addition concentration of 5% by mass. It was confirmed that the modulus was 3% or more, and the elastic modulus of the polystyrene resin was improved by adding a filler containing silica as a metal oxide as fine particles. In particular, the silica fine particles using the surface treatment agent having a molecular weight of 10000 or less in Examples 22 to 24 have an elastic modulus of 3.75 or more and an increase rate of the elastic modulus of 7% or more at a filler addition concentration of 5% by mass. A remarkable improvement in elastic modulus was observed. Further, in the silica fine particles using the surface treatment agent having a molecular weight of 1000 or less in Examples 22 to 23, the elastic modulus was 4.07 or more and the increase rate of the elastic modulus was 16% or more at a filler addition concentration of 5% by mass. A significant improvement in elastic modulus was observed. Among them, the silica fine particles using the surface treatment agent having a molecular weight of 200 or less in Example 22 have an elastic modulus of 4.53 or more and an increase rate of the elastic modulus of 29% or more at a filler addition concentration of 5% by mass, and are elastic. The rate has improved significantly.

From the above results, the elastic modulus of polystyrene resin, which is a thermoplastic resin, is improved by adding silica fine particles using a surface treatment agent having a molecular weight of less than 100,000 as a filler to silica fine particles, which are metal oxide fine particles. It was confirmed that the lower the molecular weight of the surface treatment agent, the higher the elastic modulus. Further, from the comparison between Examples 22 and 23, it was confirmed that the elastic modulus of the polystyrene resin was improved as the molecular weight of the silane coupling agent was lower.

The magnitude of the increase rate of elastic modulus differs depending on the type of fine particles and resin, but regardless of the type of fine particles and the type of resin such as thermoplasticity and thermosetting, the molecular weight, molecular size (three-dimensional structure), and fine particles of the surface treatment agent : It was possible to improve the elastic modulus by controlling the mass ratio of the surface treatment agent and the bond between the surface treatment agent and the fine particles.

3. 3. Evaluation of antibacterial properties of resin materials containing fillers <Examples 26 to 31>
In the same manner as in Examples 11 to 16, polyvinylidene chloride resin to which silver nanoparticles were added as a filler was prepared, and the antibacterial property was determined by measuring the bacteriostatic activity value. Specifically, a polyvinylidene chloride resin prepared by using Staphylococcus aureus subsp. Aureus NBRC 12732 as a strain and preparing 0.1 mL of a bacterial solution adjusted to a viable cell count of 2.5 × 10 ⁴ cells / mL in a normal bouillon medium. It was inoculated into (1 cm × 1 cm) and cultured at 37 ° C. for 18 hours. After washing out the bacteria with physiological saline, a dilution series was prepared, and the viable cell count was counted to determine the bacteriostatic activity value. The bacteriostatic activity value was calculated by the following formula, and a bacteriostatic activity value of 2.2 or more was determined to have antibacterial activity as an index of antibacterial activity. The results are shown in Table 5.
Bacteriostatic activity value = log [number of control viable cells after 18 hours] -log [number of viable cells of each sample after 18 hours]

From Table 5, it was confirmed that the polyvinylidene chloride resin to which the silver nanoparticles of Examples 26 to 31 were added had a bacteriostatic activity value of 2.2 or more and had antibacterial properties.

4. Measurement of surface resistance of resin material containing filler <Examples 32 to 37>
A polyvinylidene chloride resin to which silver nanoparticles were added as a filler was prepared in the same manner as in Examples 11 to 16 except that the filler addition concentration was changed to 20 or 50% by mass, and a surface resistance tester (manufactured by Mitsubishi Chemical Analytech, Ltd., The surface resistance value was determined by measurement using Loresta GP). The results are shown in Table 6.

<Comparative Example 7>
The surface resistance value of the polyvinylidene chloride resin was determined in the same manner as in Examples 32 to 37 except that silver nanoparticles were not added. The results are shown in Table 6.

From Table 6, the polyvinylidene chloride resin to which the silver nanoparticles of Comparative Example 7 was not added did not show conductivity and antistatic property, whereas the polyvinylidene chloride to which the silver nanoparticles of Examples 32 to 37 were added was not found. Regarding the vinylidene chloride resin, the surface resistance value was ^10-2 to 10 ⁶ Ω / □, and it was confirmed that it had conductivity and antistatic properties.

Claims (6)

A filler added to the resin
Fine particles having a surface treatment agent (excluding silane coupling agents, metal-based coupling agents, and fatty acids) on the surface.
The surface treatment agent has a molecular weight of less than 100,000 and
The surface treatment agent is a low molecular weight compound, a polymer or a surfactant having a functional group shared, coordinated or hydrogen bonded to fine particles.
The particle size of the fine particles is 1 nm or more and less than 1 mm.
A filler having a mass ratio (fine particles / surface treatment agent) of the fine particles to the surface treatment agent of 55/45 or more . The filler according to claim 1, wherein the surface treatment agent is a compound covalently bonded to fine particles . A resin material containing the filler according to claim 1 or 2 . The resin material according to claim 3, wherein the rate of increase in elastic modulus due to the addition of a filler to the resin is 1% or more . When adding fine particles having a surface treatment agent having a molecular weight of less than 100,000 to the resin as a filler, the molecular weight of the surface treatment agent is adjusted and / or the mass ratio of the fine particles to the surface treatment agent (fine particles / surface treatment agent). ) To 55/45 or more to adjust the elastic modulus of the resin material . A method for producing a resin material in which fine particles having a surface treatment agent having a molecular weight of less than 100,000 are added to the resin as a filler, and the method for producing the resin material includes the following steps:
A step of acquiring in advance calibration curve data showing the tendency of the molecular weight of the surface treatment agent and the elastic modulus of the resin material to increase monotonically as the molecular weight decreases, and storing the data in a computer storage means;
A step of determining the molecular weight of the surface treatment agent corresponding to the target elastic modulus based on the calibration curve data stored in the storage means;
A step of adjusting the mass ratio (fine particles / surface treatment agent) of fine particles to a surface treatment agent having a determined molecular weight to 55/45 or more;
A step of producing a resin material by adding fine particles having the surface treatment agent on the surface to the resin as a filler.