WO2017169802A1 - Dispersion de particules métalliques fines et film durci - Google Patents

Dispersion de particules métalliques fines et film durci Download PDF

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Publication number
WO2017169802A1
WO2017169802A1 PCT/JP2017/010491 JP2017010491W WO2017169802A1 WO 2017169802 A1 WO2017169802 A1 WO 2017169802A1 JP 2017010491 W JP2017010491 W JP 2017010491W WO 2017169802 A1 WO2017169802 A1 WO 2017169802A1
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Prior art keywords
meth
acrylate
acrylic
group
acid
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PCT/JP2017/010491
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English (en)
Japanese (ja)
Inventor
鉄也 原田
慎司 足立
北嶋　裕
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ハリマ化成株式会社
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Priority to JP2017532194A priority Critical patent/JP6196750B1/ja
Priority to CN201780000674.3A priority patent/CN107960085B/zh
Priority to KR1020177017648A priority patent/KR101811187B1/ko
Publication of WO2017169802A1 publication Critical patent/WO2017169802A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a metal fine particle dispersion and a cured film, and specifically, a metal fine particle dispersion in which metal fine particles are dispersed by a metal fine particle dispersant, and a cured film obtained by curing the metal fine particle dispersion.
  • a metal fine particle dispersion in which metal fine particles are dispersed by a metal fine particle dispersant, and a cured film obtained by curing the metal fine particle dispersion.
  • the cured film obtained by applying and curing the coating agent for example, mechanical properties, chemical resistance, high refractive index, antistatic properties, ultraviolet / infrared shielding properties, scratch resistance, etc.
  • Various metal fine particles are dispersed in order to impart the various physical properties described above and further as pigments.
  • the metal fine particles may aggregate depending on the metal fine particles to be blended, the solvent, the type of the binder resin, and the like. Therefore, in order to disperse the metal fine particles satisfactorily, it has been proposed to add a dispersant to the coating agent.
  • ZnO ultrafine particle toluene dispersion a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (containing 67 mol% of dipentaerythritol pentaacrylate), and Aronix M-5300 ( ⁇ -carboxycaprolactone monoacrylate) )
  • a high refractive index resin composition see Patent Document 1 (Example 6)
  • the cured film of the coating resin composition as described above is required to have adhesiveness with a base material, and in particular, is required to have moisture and heat resistance that can maintain the adhesiveness even in a humid heat environment. .
  • the coating resin composition further improvement in dispersibility is required, and the cured film is required to have excellent hardness and transparency depending on the application.
  • An object of the present invention is to provide a metal fine particle dispersion that is excellent in dispersion stability of metal fine particles and that can improve the heat-and-moisture adhesion, hardness and transparency of a cured film, and to cure the metal fine particle dispersion. It is in providing the cured film obtained by doing.
  • the present invention [1] is a metal fine particle dispersion containing metal fine particles, a dispersion medium, and a metal fine particle dispersant, wherein the metal fine particle dispersant comprises (A) two or more (meth) acryloyl groups. And an acid anhydride modified product of a polyfunctional (meth) acrylic compound having at least one hydroxyl group, and (B) a monofunctional (meth) acrylic compound having one (meth) acryloyl group,
  • the monofunctional (meth) acrylic compound contains a metal fine particle dispersion containing at least one of the compounds represented by the following (b1) to (b3).
  • (B1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
  • the present invention [3] includes (B) an acid anhydride of a caprolactone adduct of hydroxyalkyl (meth) acrylate wherein the monofunctional (meth) acrylic compound is represented by the above formula (2) and n is 2 to 5
  • the metal fine particle dispersion liquid according to the above [1] which contains a modified product.
  • the present invention [5] further contains a metal fine particle dispersion according to any one of the above [1] to [4], further comprising a binder, wherein the binder contains a (meth) acrylic resin. Yes.
  • the present invention [6] includes a cured film that is a cured product of the metal fine particle dispersion according to any one of [1] to [5] above.
  • the metal fine particle dispersion of the present invention is excellent in dispersion stability of metal fine particles, and can provide a cured film excellent in wet heat resistance, hardness and transparency.
  • the cured film of the present invention is excellent in wet heat resistance, hardness, and transparency.
  • the metal fine particle dispersion of the present invention contains metal fine particles, a dispersion medium, and a metal fine particle dispersant.
  • metal fine particles For example, aluminum oxide (alumina), titanium oxide (titania), zinc oxide, zirconium oxide (zirconia), tin oxide, yttrium oxide (yttria), bismuth oxide, antimony oxide, cerium oxide , Metal oxide fine particles such as indium oxide and silicon oxide (silicon dioxide, silica, etc.), for example, these metal oxides are doped with different elements such as gallium, antimony, tin, fluorine, phosphorus, aluminum, etc. And foreign element-doped metal oxide fine particles.
  • the crystal structure of these metal oxides is not particularly limited, and for example, any of cubic, tetragonal, orthorhombic, monoclinic, triclinic, hexagonal, trigonal, etc. There may be.
  • Preferred metal fine particles include aluminum oxide, zirconium oxide, and silicon dioxide.
  • the metal fine particles may be surface-treated by a known method if necessary.
  • These metal fine particles can be used alone or in combination of two or more.
  • the shape of the metal fine particle is not particularly limited, and examples thereof include a lump shape, a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, an indefinite shape, and a mixture thereof.
  • the particle diameter of the metal fine particles is measured as the primary particle diameter of the metal fine particles themselves, and is, for example, 200 nm or less, preferably 90 nm or less, more preferably 50 nm or less, and usually 1 nm or more, preferably 3 nm or more. It is.
  • the metal fine particles can be easily obtained, and the storage stability of the metal fine particle dispersion and the transparency of the cured film (described later) can be improved.
  • Examples of the dispersion medium include organic solvents, aqueous solvents, and reactive solvents.
  • organic solvent examples include petroleum hydrocarbon solvents such as hexane and mineral spirit, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.
  • petroleum hydrocarbon solvents such as hexane and mineral spirit
  • aromatic hydrocarbon solvents such as benzene, toluene
  • xylene such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.
  • Ketone solvents such as methyl acetate, ethyl acetate, butyl acetate, ⁇ -butyrolactone, propylene glycol monomethyl ether acetate and other ester solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Examples thereof include aprotic polar solvents such as N-methylpyrrolidone and pyridine.
  • aqueous solvent examples include water, alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol, and glycol ether solvents such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.
  • the reactive solvent examples include a compound having one or more ethylenically unsaturated bonds.
  • a compound having one ethylenically unsaturated bond in one molecule metal fine particle dispersion described later
  • Compound having two or more ethylenically unsaturated bonds in one molecule ((A) polyfunctional (meth) acrylic in metal fine particle dispersant described later And the like, excluding acid anhydride-modified products of compounds).
  • Examples of the compound having one ethylenically unsaturated bond per molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, Butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (me
  • Examples of the compound having two or more ethylenically unsaturated bonds in one molecule include a compound having two ethylenically unsaturated bonds in one molecule and a compound having three ethylenically unsaturated bonds in one molecule. Examples thereof include a compound having four ethylenically unsaturated bonds in one molecule, a compound having five ethylenically unsaturated bonds in one molecule, and a compound having six ethylenically unsaturated bonds in one molecule.
  • Examples of the compound having two ethylenically unsaturated bonds in one molecule include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.
  • Examples of the compound having three ethylenically unsaturated bonds in one molecule include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (acryloxyethyl).
  • Examples of the compound having four ethylenically unsaturated bonds in one molecule include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, and modified alkylene oxides thereof. Etc.
  • Examples of the compound having five ethylenically unsaturated bonds in one molecule include dipentaerythritol penta (meth) acrylate or their modified alkylene oxides.
  • Examples of the compound having 6 ethylenically unsaturated bonds in one molecule include dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (trade name “UA-306H” manufactured by Kyoeisha Chemical Co., Ltd.). ), Caprolactone-modified dipentaerythritol hexa (meth) acrylate or an alkylene oxide-modified product thereof.
  • the dispersion medium is also available as a commercial product.
  • examples of petroleum hydrocarbon solvents include AF Solvent Nos. 4 to 7 (above, Shin Nippon Oil Co., Ltd.) and the like.
  • examples of the group hydrocarbon solvent include Ink Solvent No. 0, Solvesso 100, 150, and 200 (manufactured by Shin Nippon Oil Co., Ltd.) manufactured by Exxon Chemical.
  • These dispersion media can be used alone or in combination of two or more.
  • the dispersion medium is preferably an organic solvent or an aqueous solvent, more preferably an organic solvent, more preferably methyl isobutyl ketone, from the viewpoints of adhesion to a substrate, hardness, and the like.
  • the dispersion medium is preferably a reactive solvent from the viewpoint of improving productivity during film formation, suppressing damage to the substrate, and supporting high-definition shapes, and more preferably phenoxyethyl (meta ) Acrylate, o-phenylphenoxyethyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) acrylate, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, tetraethylene Glycol di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, trimethylolpropane tri (meth) acrylate modified alkylene oxide, diglycerin tetra (meth) acrylate Diene pen modified with diene Erythritol penta (me
  • the metal fine particle dispersant is an additive for improving the dispersibility of the metal fine particles in the dispersion medium, and includes (A) an acid anhydride modified product of a polyfunctional (meth) acryl compound, and (B) a monofunctional ( A (meth) acrylic compound.
  • the (meth) acrylic compound is defined as an acrylic compound and / or a methacrylic compound.
  • (meth) acryl is defined as “acryl” and / or “methacryl”
  • (meth) acryloyl is also defined as “acryloyl” and / or “methacryloyl”.
  • Acrylate is also defined as” acrylate "and / or” methacrylate ".
  • An acid anhydride modified product of a polyfunctional (meth) acryl compound is specifically (A) a polyfunctional (meta) having two or more (meth) acryloyl groups and at least one hydroxyl group. ) An acid anhydride modified product of an acrylic compound (hereinafter referred to as a hydroxyl group-containing polyfunctional (meth) acrylic compound).
  • Hydroxyl group-containing polyfunctional (meth) acrylic compounds include, for example, polyols (for example, glycerin (hydroxyl group number 3), trimethylolpropane (hydroxyl group number 3), tris (2-hydroxyethyl) isocyanurate (hydroxyl group number 3), Known polyfunctional alcohols such as diglycerin (hydroxyl group number 4), ditrimethylolpropane (hydroxyl group number 4), pentaerythritol (hydroxyl group number 4), dipentaerythritol (hydroxyl group number 6), and tripentaerythritol (hydroxyl group number 8)) And adduct bodies (adducts) in which less than an equimolar amount of (meth) acrylic acid is added to the number of hydroxyl groups of the polyol.
  • polyols for example, glycerin (hydroxyl group number 3), trimethylolpropane (hydroxyl group number 3), tris (2-hydroxyethyl) isocyanur
  • Examples of the hydroxyl group-containing polyfunctional (meth) acrylic compound include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Trimethylolpropane di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, tris-2-hydroxyethylisocyanurate di (meth) acrylate, glycerin di (meth) acrylate, diglycerin di ( (Meth) acrylate, diglycerin tri (meth) acrylate, and adducts of these alkylene oxides (ethylene oxide, propylene oxide, etc.) Random adduct includes a block adduct.), And mixtures thereof.
  • hydroxyl group-containing polyfunctional (meth) acrylic compounds can be used alone or in combination of two or more.
  • Preferred examples of the hydroxyl group-containing polyfunctional (meth) acrylic compound include dipentaerythritol pentaacrylate.
  • the hydroxyl group-containing polyfunctional (meth) acrylic compound can be used in an appropriate ratio with the hydroxyl group-free polyfunctional (meth) acrylic compound described later.
  • Examples of the acid anhydride include dicarboxylic acid monoanhydride, tricarboxylic acid monoanhydride, and tetracarboxylic acid dianhydride.
  • dicarboxylic acid monoanhydride examples include oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12 to C18) succinic anhydride, tetrahydrophthalic anhydride, hymic anhydride, hexahydra Examples include phthalic anhydride, tetraprom phthalic anhydride, and tetrachlorophthalic anhydride.
  • tricarboxylic acid monoanhydride examples include trimellitic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and the like.
  • tetracarboxylic dianhydrides include pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2,5-oxotetrahydrofuryl) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
  • the acid anhydride examples include dicarboxylic acid monoanhydride and tetracarboxylic acid dianhydride, and more preferred examples include succinic anhydride, phthalic anhydride, and pyromellitic anhydride.
  • dicarboxylic acid monoanhydride is mentioned, From a viewpoint of the hardness of a cured film (after-mentioned), More preferably, a succinic anhydride and a phthalic anhydride are mentioned.
  • a hydroxyl group-containing polyfunctional (meth) acrylic acid anhydride modified product for example, a hydroxyl group-containing polyfunctional (meth) acrylic compound and an acid anhydride are blended, and if necessary, in a solvent. And react by heating.
  • the blending ratio of hydroxyl group-containing polyfunctional (meth) acrylic compound and acid anhydride is, for example, equivalent ratio of hydroxyl group-containing polyfunctional (meth) acrylic acid anhydride to carboxylic anhydride group relative to hydroxyl group (Carboxylic anhydride group / hydroxyl group) is, for example, 0.5 or more, preferably 0.67 or more, for example, 1 or less, preferably 0.91 or less.
  • the solvent examples include the above-described organic solvent (the above-described organic solvent as the dispersion medium), the above-described aqueous solvent (the above-described aqueous solvent as the dispersion medium), the above-described reactive solvent (the above-described reactive solvent as the dispersion medium), and the like. Is mentioned. These solvents can be used alone or in combination of two or more.
  • Preferred examples of the solvent include hydroxyl group-containing polyfunctional (meth) acrylic compounds and solvents that are inert to acid anhydrides, and specific examples include solvents having no carboxy group and no hydroxyl group.
  • an organic solvent is preferable, a ketone solvent is more preferable, and methyl isobutyl ketone is more preferable.
  • Examples of the catalyst include metals, organometallic compounds, metal halides, and amine compounds.
  • Examples of the metal include alkali metals such as sodium and potassium.
  • organometallic compound examples include the alkali metal alkoxides (alkali metal alkoxides) and derivatives thereof, such as alkylaluminum compounds such as triethylaluminum and derivatives thereof, such as alkoxytitanium compounds such as tetrabutyl titanate, 2-ethyl Examples thereof include organic tin compounds such as tin hexanoate, tin octylate, and dibutyltin laurate.
  • alkali metal alkoxides alkali metal alkoxides
  • derivatives thereof such as alkylaluminum compounds such as triethylaluminum and derivatives thereof, such as alkoxytitanium compounds such as tetrabutyl titanate, 2-ethyl
  • organic tin compounds such as tin hexanoate, tin octylate, and dibutyltin laurate.
  • metal halide examples include tin halides such as tin chloride (specifically, tin dichloride: SnCl 2 ).
  • amine compound examples include N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide and the like.
  • These catalysts can be used alone or in combination of two or more.
  • the catalyst is preferably an amine compound, more preferably N, N-dimethylbenzylamine, triethylamine, or tributylamine, and still more preferably triethylamine.
  • the mixing ratio of the catalyst is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of the hydroxyl group-containing polyfunctional (meth) acrylic compound and the acid anhydride. Yes, for example, 5 parts by mass or less, preferably 0.5 parts by mass or less.
  • a polymerization inhibitor can be added if necessary.
  • polymerization inhibitor examples include p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, catechol, tert-butylcatechol, 2,6-di-tert-butyl-hydroxytoluene, 4-tert-butyl-1,2-dihydroxy Phenolic compounds such as benzene and 2,2′-methylene-bis (4-methyl-6-tert-butylcatechol) such as phenothiazine, diphenylphenylenediamine, dinaphthylphenylenediamine, p-aminodiphenylamine, N-alkyl-N Aromatic amines such as' -phenylenediamine, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-acetoxy-1-oxy-2,2,6,6-tetramethylpiperidine, 4 -Benzoyloxy-1 Oxy-2,2,6,6-tetramethylpiperidine, 4-alkoxy-1-oxy-2,2,2,
  • polymerization inhibitors can be used alone or in combination of two or more.
  • the polymerization inhibitor is preferably p-methoxyphenol.
  • the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass with respect to 100 parts by mass in total of the hydroxyl group-containing polyfunctional (meth) acrylic compound and the acid anhydride.
  • Part or more for example, 1.0 part by weight or less, preferably 0.1 part by weight or less.
  • the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 140 ° C. or lower, Preferably, it is 110 degrees C or less.
  • the heating time is, for example, 4 hours or more, preferably 8 hours or more, for example, 20 hours or less, preferably 12 hours or less.
  • the hydroxyl group-containing polyfunctional (meth) acrylic compound can be modified with an acid anhydride, and (A) an acid anhydride modified product of the polyfunctional (meth) acrylic compound is obtained.
  • (A) As an acid anhydride modified body of a polyfunctional (meth) acryl compound more specifically, for example, phthalic acid modified product of dipentaerythritol pentaacrylate, phthalic acid modified product of pentaerythritol triacrylate, dipentaerythritol Examples thereof include succinic acid-modified products of pentaacrylate and succinic acid-modified products of pentaerythritol triacrylate.
  • the acid value of the acid anhydride modified product of the polyfunctional (meth) acrylic compound is, for example, 20 mgKOH / g or more, preferably 73 mgKOH / g or more, more preferably 80 mgKOH / g or more, for example, 500 mgKOH. / G or less, preferably 300 mgKOH / g or less.
  • the hydroxyl value of the acid anhydride modified product of the polyfunctional (meth) acrylic compound (A) exceeds, for example, 0 mgKOH / g, preferably 1 mgKOH / g or more, for example, 350 mgKOH / g or less, preferably Is 230 mg KOH / g or less.
  • the blending ratio of the acid anhydride modified product of the polyfunctional (meth) acrylic compound is, for example, 1 part by mass or more, preferably 5 parts by mass or more, more preferably 7 parts per 100 parts by mass of the metal fine particles.
  • it is 200 parts by mass or less, preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and particularly preferably 50 parts by mass or less.
  • the monofunctional (meth) acryl compound is specifically a compound having one (meth) acryloyl group, and contains at least one of the compounds represented by the following (b1) to (b3). ing.
  • (B1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
  • the compound represented by (b1) is a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
  • R 1 represents a hydrogen atom or a methyl group, and n represents 1 to 10.
  • R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
  • n is the average number of moles of caprolactone added per mole of (meth) acrylic acid, and is 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. Preferably, it is 3 or less.
  • Such a caprolactone adduct of (meth) acrylic acid can be obtained by subjecting (meth) acrylic acid to an addition reaction (ring-opening addition) with ⁇ -caprolactone.
  • (Meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.
  • ⁇ -caprolactone is not particularly limited, and a commercially available product can be used as it is.
  • the method of reacting (meth) acrylic acid and ⁇ -caprolactone (ring-opening addition) is not particularly limited, and is a known method (for example, those described in JP-A-62-135521, JP-A-60-67446, etc.). Method).
  • (meth) acrylic acid and ⁇ -caprolactone are blended, and if necessary, heated and stirred in the presence of a catalyst and a solvent.
  • the blending ratio of (meth) acrylic acid and ⁇ -caprolactone depends on the molecular weight of the target product (compound represented by the above formula (1)), that is, the average addition mole number n of ⁇ -caprolactone to (meth) acrylic acid. Is set as appropriate.
  • ⁇ -caprolactone is, for example, 1 mol or more, preferably 2 mol or more, for example, 10 mol or less, preferably 5 mol or less, more preferably 3 mol or less.
  • ⁇ -caprolactone is, for example, 50 parts by mass or more, preferably 150 parts by mass or more, for example, 10000 parts by mass or less, preferably 2000 parts by mass. Or less.
  • the reaction temperature is, for example, 80 ° C. or higher, preferably 120 ° C. or higher, for example, 240 ° C. or lower, in an inert gas or an inert gas-oxygen gas mixed atmosphere. Preferably, it is 200 degrees C or less.
  • the reaction time is, for example, 4 hours or more, preferably 6 hours or more, for example, 20 hours or less, preferably 12 hours or less.
  • the catalyst examples include Lewis acids such as aluminum chloride and stannic chloride, and acid catalysts such as Bronsted acid such as sulfuric acid, paratoluenesulfonic acid, benzenesulfonic acid, and sulfonic acid type ion exchange resin. .
  • These catalysts can be used alone or in combination of two or more.
  • the catalyst is preferably sulfuric acid, paratoluenesulfonic acid, or benzenesulfonic acid from the viewpoint of solubility in the reaction solution.
  • the mixing ratio of the catalyst is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, for example, 50 parts by mass or less, preferably 20 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. It is as follows.
  • solvent examples include aromatic hydrocarbons such as benzene, toluene and xylene.
  • the mixing ratio of the solvent is not particularly limited, and is appropriately set according to the purpose and application.
  • the ⁇ -caprolactone adduct of (meth) acrylic acid can be produced without a solvent.
  • the above-described polymerization inhibitor can be added as necessary.
  • the polymerization inhibitor is preferably p-methoxyphenol.
  • the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of (meth) acrylic acid and ⁇ -caprolactone. 1.0 parts by mass or less, preferably 0.1 parts by mass or less.
  • the caprolactone adduct of (meth) acrylic acid can also be obtained, for example, by an esterification reaction (condensation polymerization) between (meth) acrylic acid and ⁇ -hydroxycaproic acid obtained by ring opening of caprolactone.
  • caprolactone adduct of (meth) acrylic acid can also be obtained as a commercial product.
  • examples of such commercially available products include Aronix M-5300 ( ⁇ -carboxycaprolactone monoacrylate, manufactured by Toagosei Co., Ltd.).
  • the acid value of the caprolactone adduct of (meth) acrylic acid represented by the above formula (1) is, for example, 45 mgKOH / g or more, preferably 135 mgKOH / g or more, for example, 310 mgKOH / g or less. .
  • the compound represented by (b2) is an acid anhydride modified product of a caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the following formula (2).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents at least one selected from the group consisting of an ethylene group, a propylene group, and a tetramethylene group
  • n represents 1 to 10 is shown.
  • R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
  • R 2 is an ethylene group, at least one member selected from the group consisting of propylene and tetramethylene groups, preferably exhibit an ethylene group.
  • n is the average number of moles of caprolactone added per mole of hydroxyalkyl (meth) acrylate, 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. is there.
  • hydroxyalkyl (meth) acrylate and ⁇ -caprolactone are reacted (ring-opening addition) to obtain hydroxyalkyl (meth) acrylate represented by the above formula (2).
  • hydroxyalkyl (meth) acrylate represented by the above formula (2) is reacted with an acid anhydride.
  • hydroxyalkyl (meth) acrylate examples include hydroxyalkyl (meth) acrylates having a hydroxyalkyl group having 2 to 4 carbon atoms. Specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxy Examples thereof include propyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • hydroxyalkyl (meth) acrylates can be used alone or in combination of two or more.
  • the hydroxyalkyl (meth) acrylate is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 carbon atoms, more preferably 2-hydroxyethyl (meth) acrylate.
  • ⁇ -caprolactone is not particularly limited, and a commercially available product can be used as it is.
  • the method for reacting (ring-opening addition) hydroxyalkyl (meth) acrylate with ⁇ -caprolactone is not particularly limited, and a known method (for example, the method described in JP-A-10-7774 or the like) should be adopted. Can do.
  • hydroxyalkyl (meth) acrylate and ⁇ -caprolactone are blended, and if necessary, heated and stirred in the presence of the above catalyst and the above solvent.
  • the blending ratio of hydroxyalkyl (meth) acrylate and ⁇ -caprolactone is the molecular weight of the target product (compound represented by the above formula (2)), that is, the average addition mole number n of ⁇ -caprolactone to hydroxyalkyl (meth) acrylate. It is set accordingly.
  • ⁇ -caprolactone is, for example, 1 mol or more, preferably 2 mol or more, for example, 10 mol or less, preferably 5 mol or less.
  • ⁇ -caprolactone is, for example, 90 parts by mass or more, preferably 190 parts by mass or more, for example, 1000 parts by mass or less, preferably 500 parts by mass with respect to 100 parts by mass of hydroxyalkyl (meth) acrylate. It is below mass parts.
  • reaction temperature is, for example, 60 ° C. or higher, preferably 90 ° C. or higher, for example, 140 ° C. or lower, preferably oxygen gas or an inert gas-oxygen gas mixture atmosphere. 120 ° C. or lower.
  • reaction time is 4 hours or more, for example, Preferably, it is 8 hours or more, for example, is 20 hours or less, Preferably, it is 12 hours or less.
  • the above-described polymerization inhibitor can be added as necessary.
  • the polymerization inhibitor is preferably p-methoxyphenol.
  • the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of hydroxyalkyl (meth) acrylate and ⁇ -caprolactone. 1.0 parts by mass or less, preferably 0.1 parts by mass or less.
  • the caprolactone adduct of hydroxyalkyl (meth) acrylate can also be obtained as a commercial product.
  • commercially available products include Plaxel FA-1, Plaxel FA-2, Plaxel FA-2D, Plaxel FA-3, Plaxel FA-4, Plaxel FA-5, Plaxel FA-10L, Plaxel FM-1, Plaxel FM-2, Plaxel FM-2D, Plaxel FM-3, Plaxel FM-4, Plaxel FM-5 (all manufactured by Daicel Chemical Industries, Ltd.) (PLACCEL is a registered trademark) and the like.
  • caprolactone adducts of hydroxyalkyl (meth) acrylate can be used alone or in combination of two or more.
  • the acid anhydride examples include the acid anhydrides described above ((A) acid anhydrides used in the production of acid anhydride-modified products of polyfunctional (meth) acrylic compounds).
  • dicarboxylic acid monoanhydrides are used.
  • succinic anhydride and phthalic anhydride are more preferable, and succinic anhydride is more preferable.
  • the hydroxyalkyl (meth) acrylate caprolactone adduct and the acid anhydride for example, the hydroxyalkyl (meth) acrylate caprolactone adduct and acid anhydride are blended, and if necessary, a solvent, Heating is performed in the presence of a catalyst or the like.
  • the solvent examples include the above-described organic solvent (the above-described organic solvent as the dispersion medium), the above-described aqueous solvent (the above-described aqueous solvent as the dispersion medium), the above-described reactive solvent (the above-described reactive solvent as the dispersion medium), and the like. Is mentioned. These solvents can be used alone or in combination of two or more.
  • a solvent Preferably, the solvent which is inactive with respect to the caprolactone adduct and acid anhydride of hydroxyalkyl (meth) acrylate is mentioned, Specifically, the solvent which does not have a carboxy group and a hydroxyl group is mentioned.
  • an organic solvent is preferable, a ketone solvent is more preferable, and methyl isobutyl ketone is more preferable.
  • the catalyst examples include the above-mentioned catalyst ((A) a catalyst used in the production of an acid anhydride-modified product of a polyfunctional (meth) acrylic compound). These catalysts can be used alone or in combination of two or more.
  • the catalyst is preferably an amine compound, more preferably N, N-dimethylbenzylamine, triethylamine or tributylamine, and still more preferably triethylamine.
  • the blending ratio of the hydroxyalkyl (meth) acrylate caprolactone adduct and the acid anhydride is, for example, the equivalent ratio of the carboxylic anhydride group in the acid anhydride to the hydroxyl group in the caprolactone adduct of hydroxyalkyl (meth) acrylate.
  • Carboxylic anhydride group / hydroxyl group is, for example, 0.5 or more, preferably 0.67 or more, for example, 1 or less, preferably 0.91 or less.
  • the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 140 ° C. or lower, preferably Is 110 ° C. or lower.
  • the heating time is, for example, 4 hours or more, preferably 8 hours or more, for example, 20 hours or less, preferably 12 hours or less.
  • the acid value of the acid anhydride modified product of the caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the above formula (2) is, for example, 40 mgKOH / g or more, preferably 60 mgKOH / g or more. It is 280 mgKOH / g or less, preferably 150 mgKOH / g or less.
  • the compound represented by (b3) is an acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3).
  • R 1 represents a hydrogen atom or a methyl group, m represents 2 to 4, and n represents 1 to 10.
  • R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
  • m is 2 or more, 4 or less, preferably 3 or less.
  • the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) has oxyalkylene (C m H 2m O) having 2 to 4 carbon atoms.
  • Examples of the oxyalkylene having 2 to 4 carbon atoms include oxyethylene (—CH 2 CH 2 O—), oxytrimethylene (—CH 2 CH 2 CH 2 O—), and oxytetramethylene (—CH 2 CH 2 CH 2 CH Linear oxyalkylene such as 2 O—), for example, oxypropylene (—CH 2 CH (CH 3 ) O—), oxybutylene (—CH 2 CH (CH 2 CH 3 ) O—, —CH (CH 3 And branched oxyalkylene such as CH (CH 3 ) O—), preferably linear oxyalkylene, and more preferably oxyethylene.
  • oxyethylene —CH 2 CH 2 O—
  • oxytrimethylene —CH 2 CH 2 CH 2 O—
  • oxytetramethylene —CH 2 CH 2 CH 2 CH Linear oxyalkylene such as 2 O—
  • oxypropylene —CH 2 CH (CH 3 ) O—
  • oxybutylene —CH 2 CH (CH 2 CH
  • n is the average number of moles of alkylene oxide added per mole of (meth) acrylic acid, and is 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. is there.
  • (Meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.
  • alkylene oxide examples include alkylene oxides having 2 to 4 carbon atoms, and specific examples include cyclic ether compounds having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, trimethylene oxide (oxetane) and butylene oxide. It is done.
  • alkylene oxides can be used alone or in combination of two or more.
  • addition form is not particularly limited, and may be, for example, random addition or block addition.
  • the alkylene oxide is preferably ethylene oxide or propylene oxide, and more preferably ethylene oxide.
  • the method for adding alkylene oxide to (meth) acrylic acid is not particularly limited, and a known method can be employed.
  • (meth) acrylic acid and alkylene oxide are blended, and if necessary, heated and stirred in the presence of the above catalyst and the above solvent.
  • the blending ratio of (meth) acrylic acid and alkylene oxide is appropriately determined according to the molecular weight of the target product (compound represented by the above formula (3)), that is, the average addition mole number n of alkylene oxide to (meth) acrylic acid. Is set.
  • alkylene oxide is, for example, 1 mole or more, preferably 2 moles or more, for example, 10 moles or less, preferably 5 moles or less.
  • the alkylene oxide is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, for example, 5000 parts by mass or less, preferably 1500 parts by mass. It is as follows.
  • the reaction temperature is, for example, 40 ° C. or higher, preferably 100 ° C. or higher, for example, 240 ° C. or lower, preferably 200 ° C. or lower, in an inert gas-oxygen gas mixture atmosphere. It is.
  • the reaction time is, for example, 1 hour or more, preferably 3 hours or more, for example, 20 hours or less, preferably 12 hours or less.
  • alkylene oxide adduct of (meth) acrylic acid polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, polybutylene glycol mono (meta) ) Acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) ) Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as mono (meth) acrylate, for example, (mono) ethylene glycol mono (meth) Hydroxyl groups such as acrylate, (mono) propylene glycol mono (meth) acrylate, (mono) trimethylene glycol mono (meth) acrylate, (mono)
  • alkylene oxide adducts of (meth) acrylic acid can be used alone or in combination of two or more.
  • alkylene oxide adduct of (meth) acrylic acid examples include hydroxyl-terminated polyalkylene glycol mono (meth) acrylate, and more preferred is polyethylene glycol mono (meth) acrylate.
  • alkylene oxide adduct of (meth) acrylic acid can also be obtained as a commercial item.
  • commercially available products include Blemmer PE series, Blemmer AE series, Blemmer PP series, Blemmer AP series, Blemmer PEP series, Blemmer AEP series, Blemmer PET series, Blemmer AET series, Blemmer PPT series, Blemmer APT series ( All of them are made from Japanese fats and oils). These can be used alone or in combination of two or more.
  • the acid anhydride examples include the acid anhydrides described above ((A) acid anhydrides used in the production of acid anhydride-modified products of polyfunctional (meth) acrylic compounds).
  • dicarboxylic acid monoanhydrides are used.
  • succinic anhydride and phthalic anhydride are more preferable, and succinic anhydride is more preferable.
  • an alkylene oxide adduct of (meth) acrylic acid and an acid anhydride are blended, and if necessary, a solvent, Heating is performed in the presence of a catalyst or the like.
  • the solvent examples include the above-described organic solvent (the above-described organic solvent as a dispersion medium), the above-described aqueous solvent (the above-described aqueous solvent as a dispersion medium), and the like. These solvents can be used alone or in combination of two or more.
  • a solvent Preferably, the solvent which is inactive with respect to the alkylene oxide adduct and acid anhydride of (meth) acrylic acid is mentioned, Specifically, the solvent which does not have a carboxy group and a hydroxyl group is mentioned.
  • an organic solvent is preferable, a ketone solvent is more preferable, and methyl isobutyl ketone is more preferable.
  • the catalyst examples include the above-mentioned catalyst ((A) a catalyst used in the production of an acid anhydride-modified product of a polyfunctional (meth) acrylic compound). These catalysts can be used alone or in combination of two or more.
  • the catalyst is preferably an amine compound, more preferably N, N-dimethylbenzylamine, triethylamine or tributylamine, and still more preferably triethylamine.
  • the blending ratio of the caprolactone adduct and the acid anhydride of the alkylene oxide adduct of (meth) acrylic acid is, for example, a carboxylic anhydride group in the acid anhydride to a hydroxyl group in the alkylene oxide adduct of (meth) acrylic acid.
  • Equivalent ratio (carboxylic anhydride group / hydroxyl group) is, for example, 0.5 or more, preferably 0.67 or more, for example, 1 or less, preferably 0.91 or less.
  • the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 140 ° C. or lower, Preferably, it is 110 degrees C or less.
  • the heating time is, for example, 4 hours or more, preferably 8 hours or more, for example, 20 hours or less, preferably 12 hours or less.
  • the acid value of the acid anhydride modified product of the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) is, for example, 55 mgKOH / g or more, preferably 95 mgKOH / g or more. 400 mg KOH / g or less, preferably 300 mg KOH / g or less.
  • the (B) monofunctional (meth) acrylic compound is preferably a compound represented by (b1) from the viewpoint of improving the dispersion stability of the metal fine particle dispersion, and more preferably (B) the monofunctional (meth) acrylic compound. It is mentioned that the functional (meth) acrylic compound contains a caprolactone adduct of (meth) acrylic acid represented by the above formula (1) and n is 1 to 3.
  • the (B) monofunctional (meth) acrylic compound is preferably a compound represented by (b2) from the viewpoint of improving the hardness of a cured film (described later), more preferably (B) It is mentioned that the monofunctional (meth) acrylic compound contains an acid anhydride modified product of a caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the above formula (2) and having n of 2 to 5.
  • the (B) monofunctional (meth) acrylic compound is preferably a compound represented by (b3) from the viewpoint of improving the transparency of a cured film (described later), and more preferably (B).
  • the content ratio of the (A) acid anhydride-modified polyfunctional (meth) acrylic compound and the (B) monofunctional (meth) acrylic compound is based on 100 parts by mass of the total amount thereof.
  • the anhydride-modified polyfunctional (meth) acrylic compound is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, for example, 95 parts by mass or less.
  • the amount is preferably 90 parts by mass or less.
  • (B) monofunctional (meth) acrylic compound is 5 mass parts or more, for example, Preferably, it is 10 mass parts or more, for example, 95 mass parts or less, Preferably, it is 90 mass parts or less, More preferably, 85 parts by mass or less.
  • the above-mentioned metal fine particles, the above-mentioned dispersion medium, and the above-mentioned metal fine particle dispersant are blended together or sequentially, and mixed to obtain a metal fine particle dispersion.
  • the mixing ratio of each component in the metal fine particle dispersion is such that the metal fine particle dispersant is, for example, 1 part by mass or more, preferably 5 parts by mass or more, for example, 200 parts by mass or less, with respect to 100 parts by mass of the metal fine particles.
  • the amount is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less.
  • the metal fine particles are, for example, 0.5 parts by mass or more, preferably 2.5 parts by mass or more, for example, 50 parts by mass or less, preferably 40 parts by mass with respect to 100 parts by mass of the metal fine particle dispersion. Part or less, more preferably 30 parts by weight or less.
  • the mixing ratio of the dispersion medium is appropriately set according to the purpose and application.
  • 100 parts by mass of the metal fine particles for example, 50 parts by mass or more, preferably 150 parts by mass or more,
  • it is 2000 parts by mass or less, preferably 1000 parts by mass or less.
  • the metal fine particle dispersion can further contain a binder.
  • binder examples include synthetic resins such as (meth) acrylic resin, polyvinyl butyral resin, polyvinyl alcohol resin, vinyl acetate resin, and urethane resin. These binders can be used alone or in combination of two or more.
  • (meth) acrylic resin is preferably used from the viewpoint of improving adhesion (room temperature).
  • (Meth) acrylic resin can be obtained, for example, by polymerization of a monomer component containing alkyl (meth) acrylate.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) ) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate
  • the monomer component can contain other monomers copolymerizable with alkyl (meth) acrylate.
  • the other monomer examples include an aromatic ring-containing monomer, a hydroxyl group-containing monomer, and an anionic group-containing monomer.
  • aromatic ring-containing monomer examples include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) )
  • Aromatic ring-containing (meth) acrylates such as acrylate, and styrene monomers such as styrene and ⁇ -methylstyrene.
  • the content ratio is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 95% by mass or less, preferably with respect to the total amount of the monomer components. Is 80 mass% or less.
  • the (meth) acrylic resin containing an aromatic ring is obtained as a (meth) acrylic resin.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-methyl-2-hydroxyethyl (meth) acrylate, 2-hydroxy
  • hydroxyl group-containing (meth) acrylates such as propyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, preferably 2-hydroxyethyl (meth) acrylate.
  • the content ratio of the hydroxyl group-containing monomer is, for example, 0.1% by mass or more, preferably 1% by mass or more, based on the total amount of the monomer components. 50% by mass or less, preferably 30% by mass or less.
  • the monomer component contains a hydroxyl group-containing monomer
  • a (meth) acrylic resin containing a hydroxyl group is obtained as the (meth) acrylic resin.
  • examples of the anionic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.
  • Specific examples of the anionic group-containing monomer include, for example, carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and other ⁇ , ⁇ -unsaturated carboxylic acids or salts thereof, for example, Phosphoric acid group-containing (meth) acrylates such as acid phosphooxypolyoxypropylene glycol mono (meth) acrylate, acid phosphooxyethyl (meth) acrylate, mono (2-hydroxyethyl (meth) acrylate) phosphate Monomers, for example, sulfonic acid group-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid.
  • the content ratio of the anionic group-containing monomer is, for example, 0.1% by mass or more, preferably 1% by mass or more, based on the total amount of the monomer components, For example, it is 30% by mass or less, preferably 5% by mass or less.
  • the (meth) acrylic resin containing an anionic group is obtained as a (meth) acrylic resin.
  • isocyanatomethyl (meth) acrylate 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 1-methyl-2-isocyanatoethyl (meth)
  • Isocyanate group-containing monomers such as isocyanate group-containing (meth) acrylic monomers such as acrylate, 2-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, such as glycidyl (meth) acrylate, allyl glycidyl ether, etc.
  • Glycidyl group-containing monomers for example, vinyl ester monomers such as vinyl acetate and vinyl propionate.
  • Other monomers preferably include aromatic ring-containing monomers and hydroxyl group-containing monomers, and more preferably include both aromatic ring-containing monomers and hydroxyl group-containing monomers.
  • the monomer component contains an aromatic ring-containing monomer (that is, if the (meth) acrylic resin is a (meth) acrylic resin containing an aromatic ring), the moisture and heat resistance of the cured film (described later) is improved. Can be achieved.
  • the monomer component contains a hydroxyl group-containing monomer (that is, if the (meth) acrylic resin is a (meth) acrylic resin containing a hydroxyl group), it can be easily (meta) by the method described later.
  • a (meth) acryloyl group can be introduced into the side chain of the acrylic resin, and the moisture and heat resistance of a cured film (described later) can be improved.
  • the content of the anionic monomer is preferably 5% by mass or less, more preferably the monomer component, based on the total amount of the monomer components. Does not contain an anionic group-containing monomer.
  • the content ratio of the alkyl (meth) acrylate is, for example, 10% by mass or more with respect to the total amount of the monomer components, Preferably, it is 20 mass% or more, for example, 90 mass% or less, preferably 80 mass% or less.
  • the method for producing the (meth) acrylic resin is not particularly limited.
  • the above monomer components are mixed in the above ratio, and a known radical polymerization initiator (for example, an azo compound, Polymerization is carried out by heating in the presence of a peroxide compound or the like.
  • a known radical polymerization initiator for example, an azo compound, Polymerization is carried out by heating in the presence of a peroxide compound or the like.
  • the polymerization conditions vary depending on the monomer component prescription and the type of radical polymerization initiator.
  • the polymerization temperature is 30 ° C or higher, preferably 60 ° C or higher, for example, 150 ° C or lower, preferably 120 ° C. It is as follows.
  • the polymerization time is, for example, 2 hours or more, preferably 4 hours or more, for example, 20 hours or less, preferably 8 hours or less.
  • the weight average molecular weight (GPC measurement: polystyrene conversion) of the (meth) acrylic resin is, for example, 2000 or more, preferably 3000 or more, for example, 100000 or less, preferably 50000 or less, more preferably 15000 or less. .
  • the (meth) acrylic resin is preferably a (meth) acrylic resin having a (meth) acryloyl group in the side chain.
  • the (meth) acrylic resin having a (meth) acryloyl group in the side chain can be obtained, for example, by the following method.
  • the (meth) acrylic resin obtained by the above method may have a hydroxyl group. More specifically, when the monomer component that is a raw material of the (meth) acrylic resin contains a hydroxyl group-containing monomer, the (meth) acrylic resin obtained by the above polymerization has a hydroxyl group.
  • a (meth) acryloyl group is introduced into the side chain of the (meth) acrylic resin by reacting a (meth) acrylic resin having a hydroxyl group with an isocyanate group-containing (meth) acrylic monomer. can do.
  • isocyanate group-containing (meth) acrylic monomers examples include isocyanatomethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, and 1-methyl-2-isocyanatoethyl. (Meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate and the like.
  • isocyanate group-containing (meth) acrylic monomers can be used alone or in combination of two or more.
  • the isocyanate group-containing (meth) acrylic monomer is preferably 2-isocyanatoethyl (meth) acrylate.
  • the (meth) acrylic resin which has a hydroxyl group reacts with an isocyanate group containing (meth) acryl monomer
  • the (meth) acrylic resin which has a hydroxyl group, and isocyanate group containing (meth) An acrylic monomer is blended, and if necessary, heated in the presence of a known catalyst and solvent.
  • the blending ratio of the (meth) acrylic resin having a hydroxyl group and the isocyanate group-containing (meth) acrylic monomer is an isocyanate group-containing (meth) acrylic with respect to 1 mol of the hydroxyl group of the (meth) acrylic resin having a hydroxyl group.
  • the isocyanate group of a monomer is 0.1 mol or more, for example, Preferably, it is 0.8 mol or more, for example, 2.0 mol or less, Preferably, it is 1.2 mol or less.
  • the reaction conditions are, for example, in an air atmosphere, the reaction temperature is, for example, 40 ° C or higher, preferably 60 ° C or higher, for example, 200 ° C or lower, preferably 150 ° C or lower.
  • the reaction time is, for example, 1 hour or more, preferably 2 hours or more, for example, 20 hours or less, preferably 12 hours or less.
  • the above-described polymerization inhibitor can be added as necessary.
  • the polymerization inhibitor is preferably p-methoxyphenol.
  • the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.000 parts by mass with respect to 100 parts by mass as a total of the (meth) acrylic resin having a hydroxyl group and the isocyanate group-containing (meth) acrylic monomer.
  • it is 1.0 part by mass or less, preferably 0.1 part by mass or less.
  • the hydroxyl group of the (meth) acrylic resin having a hydroxyl group and the isocyanate group of the isocyanate group-containing (meth) acrylic monomer undergo urethane reaction.
  • an isocyanate group-containing (meth) acrylic monomer is bonded to the side chain of the (meth) acrylic resin, and a (meth) acryloyl group is introduced to the end of the side chain.
  • the method of introducing the (meth) acryloyl group into the side chain of the (meth) acrylic resin is not limited to the above method, and a known method can be adopted.
  • the (meth) acrylic resin when the monomer component contains an isocyanate group-containing monomer, the (meth) acrylic resin has an isocyanate group. Therefore, a (meth) acryloyl group can also be introduced into the side chain of the (meth) acrylic resin by subjecting a (meth) acrylic resin having an isocyanate group to a urethane reaction with a hydroxyl group-containing (meth) acrylate.
  • the (meth) acrylic resin when the monomer component contains an anionic group-containing monomer (for example, a carboxyl group-containing monomer), the (meth) acrylic resin has an anionic group (for example, a carboxyl group). Therefore, the (meth) acryloyl group can be introduced into the side chain of the (meth) acrylic resin by esterifying the (meth) acrylic resin having an anionic group and the glycidyl group-containing (meth) acrylate. .
  • an anionic group-containing monomer for example, a carboxyl group-containing monomer
  • the (meth) acrylic resin has an anionic group (for example, a carboxyl group). Therefore, the (meth) acryloyl group can be introduced into the side chain of the (meth) acrylic resin by esterifying the (meth) acrylic resin having an anionic group and the glycidyl group-containing (meth) acrylate. .
  • the (meth) acrylic resin when the monomer component contains a glycidyl group-containing monomer, the (meth) acrylic resin has a glycidyl group. Therefore, the side chain of the (meth) acrylic resin is obtained by esterifying a (meth) acrylic resin having a glycidyl group and an anionic group-containing (meth) acrylate (for example, a carboxyl group-containing (meth) acrylate). A (meth) acryloyl group can also be introduced into.
  • the (meth) acrylic resin blended as the binder has a (meth) acryloyl group in the side chain, it is possible to improve the wet heat resistance of the cured film (described later).
  • the (meth) acryloyl group equivalent of the (meth) acrylic resin having a (meth) acryloyl group in the side chain is, for example, 400 or more, preferably 800 or more, for example, 30000 or less, preferably 10,000 or less. .
  • (meth) acryl group equivalent is defined as the polymer mass per 1 mol of double bonds (double bond equivalent).
  • the content thereof is, for example, 1 part by mass or more, preferably 5 parts by mass or more, for example, 50 parts by mass or less, with respect to 100 parts by mass of the metal fine particle dispersion.
  • the amount is preferably 30 parts by mass or less.
  • the metal fine particle dispersion can contain a polymerization initiator as required.
  • polymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl- Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, Zofenon, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -
  • These polymerization initiators can be used alone or in combination of two or more.
  • the blending ratio of the polymerization initiator is, for example, 1 part by mass or more, preferably 3 parts by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass with respect to 100 parts by mass of the total amount of the metal fine particle dispersant. Or less.
  • the timing of blending the binder and the polymerization initiator is not particularly limited.
  • the binder and the polymerization initiator may be blended at the same time when the metal fine particles, the solvent, and the metal fine particle dispersant are mixed. Separately from the fine particle dispersant, a binder and a polymerization initiator may be blended together or sequentially.
  • the preparation of the metal fine particle dispersion is not particularly limited, and when mixing the metal fine particles, the solvent, and the metal fine particle dispersant (and the binder and polymerization initiator blended as necessary), for example, paint shaker, roll mill A known disperser such as a ball mill, an attritor, a sand mill, a bead mill, or an ultrasonic disperser can be used.
  • a metal fine particle dispersion as a coating agent (described later), from the viewpoint of improving the transparency of a cured film (described later), a ball mill and a bead mill are preferable, and a bead mill is more preferable. .
  • dispersion media such as zirconia beads and glass beads can be used.
  • the bead diameter of the dispersion medium is not particularly limited, but is, for example, 10 ⁇ m or more, for example, 500 ⁇ m or less, preferably 100 ⁇ m or less. Note that the filling rate of the dispersion medium is appropriately set according to the purpose and application.
  • the fine metal particles can be pulverized by the above-described dispersion medium, and the average particle diameter can be adjusted to the above range.
  • metal fine particles having an average particle diameter larger than the above range can be introduced into the disperser.
  • the metal fine particle dispersion includes, for example, a pigment, a desiccant, a rust inhibitor, a plasticizer, a coating film surface conditioner, an antioxidant, an ultraviolet absorber, and a dispersant excluding the metal fine particle dispersant described above.
  • Various additives such as nonionic surfactants such as sorbitan fatty acid esters and polyethylene glycol fatty acid esters can be added.
  • the mixture ratio of an additive is suitably set according to the objective and use.
  • the nonvolatile content of the metal fine particle dispersion is, for example, 0.5% by mass or more, preferably 3% by mass or more, for example, 70% by mass or less, Preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less.
  • the organic solvent and / or aqueous solvent can be distilled off from the metal fine particle dispersion by a known method, and only the reactive solvent may be contained as the dispersion medium. it can.
  • the nonvolatile content of the metal fine particle dispersion may be 100% by mass.
  • the metal fine particles have a particle diameter measured as an average particle diameter (average particle diameter) since the metal fine particles are present as primary particles or secondary particles, for example, 200 nm or less. Preferably, it is 50 nm or less, usually 1 nm or more, preferably 3 nm or more.
  • Such a metal fine particle dispersion contains the above-mentioned metal fine particle dispersant, it is possible to obtain a cured film that is excellent in dispersion stability of metal fine particles and that is excellent in wet heat resistance, hardness, and transparency. .
  • a metal fine particle dispersion is used as a coating agent, applied to a substrate by a known method and dried, and then irradiated with active energy rays to be cured.
  • the substrate is not particularly limited.
  • polycarbonate polymethyl methacrylate, polystyrene, polyester (polyethylene terephthalate, etc.), polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.
  • plastics such as metal, wood, paper, glass, and slate.
  • the coating method is not particularly limited. For example, roll coating, bar coating, doctor blade, Mayer bar, air knife, etc., coating using a commonly used device, screen printing, offset printing, etc.
  • Known coating methods such as flexographic printing, brush coating, spray coating, gravure coating, and reverse gravure coating are employed.
  • the drying temperature is, for example, 40 ° C. or more, preferably 60 ° C. or more, for example, 180 ° C. or less, preferably 140 ° C. or less
  • the drying time is, for example, 1 minute or more, preferably Is 2 minutes or more, for example, 60 minutes or less, preferably 30 minutes or less.
  • the film thickness after drying is, for example, 50 nm or more, preferably 500 nm or more, for example, 10 ⁇ m or less, preferably 7 ⁇ m or less.
  • active energy rays examples include ultraviolet rays and electron beams.
  • an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like as a light source is used.
  • the amount of ultraviolet irradiation, the amount of light of the ultraviolet irradiation device, the arrangement of the light source, etc. are adjusted as necessary.
  • a high-pressure mercury lamp for example, a substrate coated with a metal fine particle dispersion is transported at a speed of 5 to 50 m / min for one lamp having a luminous intensity of about 80 to 1000 mW / cm 2. Transport by.
  • the irradiation amount of ultraviolet rays is, for example, 100 to 10,000 mJ / cm 2 .
  • the base material coated with the metal fine particle dispersion is transported at a transport speed of 5 to 50 m / min by, for example, an electron beam accelerator having an acceleration voltage of 10 to 300 kV. .
  • the (meth) acryloyl group in the metal fine particle dispersant is cross-linked to form a three-dimensional structure.
  • the reactive solvent acts as a crosslinking agent. That is, the ethylenically unsaturated bond of the reactive solvent is cross-linked by irradiation with active energy rays.
  • the obtained cured film is obtained using the above-mentioned metal fine particle dispersion, it is excellent in moisture and heat resistance, hardness and transparency.
  • the cured film is suitably used in various industrial products, for example, as an optical component such as a light emitting diode (LED), a lens, and an optical device, such as a fine ceramic, for example, a functional film such as a conductive film and an optical film. Used.
  • an optical component such as a light emitting diode (LED), a lens
  • an optical device such as a fine ceramic
  • a functional film such as a conductive film and an optical film.
  • Synthesis examples 2-3 Except having changed into the compounding prescription shown in Table 1, it carried out similarly to the synthesis example 1, and obtained the solution (solid content 50%) of the acid anhydride modified body of (A) polyfunctional (meth) acrylic compound.
  • Aronix M403 Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture, manufactured by Toagosei Co., Ltd., dipentaerythritol pentaacrylate content 50-60% (B2) Acid anhydride modified product of caprolactone adduct of hydroxyalkyl (meth) acrylate Synthesis Example 4 In a 500 mL flask equipped with a stirrer, thermometer, reflux condenser, and gas mixture introduction tube, 143.5 parts of methyl isobutyl ketone (solvent), caprolactone adduct of hydroxyethyl acrylate (Dacel's PLACCEL FA-1 caprolactone average addition mole) Number: 1 mol) 100 parts, triethylamine (catalyst) 0.14 part and p-methoxyphenol (polymerization inhibitor) 0.07 part were charged and heated to 80 ° C. with stirring.
  • PLACCEL FA-1 trade name, manufactured by Daicel, caprolactone adduct of hydroxyethyl acrylate, caprolactone average addition mole number: 1 mol
  • PLACCEL FA-2D trade name, manufactured by Daicel, caprolactone adduct of hydroxyethyl acrylate, caprolactone average addition mole Number: 2 mol
  • Plaxel FA-10L trade name, manufactured by Daicel, caprolactone adduct of hydroxyethyl acrylate, caprolactone average addition mol number: 10 mol (b3) acid anhydride modified product of alkylene oxide adduct of (meth) acrylic acid Synthesis example 7 In a 500 mL flask equipped with a stirrer, a thermometer, a reflux condenser, and a gas mixture inlet tube, 186.2 parts of methyl isobutyl ketone (solvent), 100 parts of 2-hydroxyethyl acrylate (manufactured by Osaka Organic
  • BLEMMER AE-200 Trade name, manufactured by NOF Corporation, ethylene oxide adduct of acrylic acid, alkylene oxide average addition mole number: 4.5 mol
  • BLEMMER AP-400 Trade name, manufactured by NOF Corporation, propylene oxide adduct of acrylic acid , Alkylene oxide average addition mole number: 6 mol ⁇ Binder> Synthesis Example 10 100 parts of methyl isobutyl ketone was put into a flask equipped with a stirrer, a condenser, a thermometer, a nitrogen introducing tube and a dropping funnel, and the temperature was raised to 100 ° C. in a nitrogen atmosphere.
  • the monomer mixture was dropped into the flask containing methyl isobutyl ketone over 3 hours, and then aged for 3 hours.
  • reaction temperature was set to 80 ° C.
  • atmospheric condition was switched from a nitrogen atmosphere to an air atmosphere, 2-isocyanatoethyl acrylate (Karenz AOI, Showa Denko) 5 parts, methyl isobutyl ketone 5 parts, polymerization inhibitor 0.1 parts of p-methoxyphenol was added and reacted for 4 hours.
  • Synthesis Example 11 A solution (solid content 50%) of a (meth) acrylic resin having a (meth) acryloyl group in the side chain was obtained in the same manner as in Synthesis Example 10 except that the formulation was changed to the formulation shown in Table 4.
  • Example 1 The acid anhydride-modified solution (solid content 50%) of (A) polyfunctional (meth) acrylic compound obtained in Synthesis Example 1 was 16.8 parts, and (b1) caprolactone adduct of (meth) acrylic acid.
  • Aronix M-5300 (manufactured by Toa Gosei Chemical Co., Ltd., solid content 100%) becomes 1.4 parts, and zirconia as metal fine particles (UEP-100 Sanka Zirconium, manufactured by Daiichi Rare Element Co., Ltd., average primary particle size 15 nm)
  • UDP-100 Sanka Zirconium manufactured by Daiichi Rare Element Co., Ltd., average primary particle size 15 nm
  • methyl isobutyl ketone as a dispersion medium was 53.8 parts
  • IRGACURE 184 BASF 1-hydroxycyclohexyl phenyl ketone
  • PET polyethylene terephthalate
  • Examples 2 to 15 and Comparative Examples 1 to 5 A metal fine particle dispersion and a laminate of a substrate and a cured film were obtained in the same manner as in Example 1 except that the formulation was changed to the formulation shown in Tables 5-8.
  • the metal fine particle dispersion was allowed to stand at 23 ° C., and the dispersibility of the metal fine particles was visually confirmed.
  • the criteria for evaluation are as follows. A: No sediment was confirmed even after 3 months. B: A little sediment was confirmed after 3 months. C: A sediment was confirmed after 1 week. D: Precipitate was confirmed after 1 day.
  • Aronix M403 trade name Aronix M403, manufactured by Toagosei Co., Ltd., dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (dipentaerythritol pentaacrylate content 50-60%)
  • DA7301 Trade name Disparon DA-7301, manufactured by Enomoto Kasei Co., Ltd., 75% by weight solution of high molecular weight polyester acid amide amine salt (solvent: alkylcyclohexane / propylene glycol monomethyl ether acetate)
  • Aronix M5300 Trade name Aronix M-5300, manufactured by Toa Gosei Co., Ltd., ⁇ -carboxycaprolactone monoacrylate Zirconia: manufactured by Daiichi Rare Element Co., Ltd.
  • the metal fine particle dispersion and the cured film of the present invention are suitably used as functional films such as optical parts, fine ceramics, conductive films, and optical films.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une dispersion de particules métalliques fines qui comprend des particules métalliques fines, un milieu de dispersion et un agent dispersant pour des particules métalliques fines. L'agent dispersant pour particules métalliques fines comprend (A) un composé (méth)acrylique polyfonctionnel modifié par un anhydride d'acide ayant au moins deux groupes (méth)acryloyle et au moins un groupe hydroxyle et (B) un ou plusieurs composés (méth)acryliques monofonctionnels ayant chacun un groupe (méth)acryloyle. Les composés (méth)acryliques monofonctionnels comprennent au moins un composé choisi dans le groupe constitué par (b1) des adduits de caprolactone spécifiques de l'acide (méth)acrylique, (b2) des adduits de caprolactone spécifiques modifiés par un anhydride d'acide de (méth)acrylates d'hydroxyalkyle, et (b3) des adduits d'oxyde d'alkylène spécifiques modifiés par un anhydride d'acide de l'acide (méth)acrylique.
PCT/JP2017/010491 2016-03-31 2017-03-15 Dispersion de particules métalliques fines et film durci WO2017169802A1 (fr)

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JP2019112555A (ja) * 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化性組成物およびそれを用いたインデックスマッチング層および積層体

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JPH09316369A (ja) * 1996-03-28 1997-12-09 Dainippon Printing Co Ltd 抗菌性電離放射線硬化型塗料及び抗菌性透明フィルム
WO2007138946A1 (fr) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. Composition d'oxyde métallique, film durci et laminé
WO2014157588A1 (fr) * 2013-03-29 2014-10-02 Hoya株式会社 Composition de revêtement
JP2015044905A (ja) * 2013-08-27 2015-03-12 昭和電工株式会社 樹脂組成物、透明フィルム、その製造方法及び用途
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JP4229214B2 (ja) * 2006-11-09 2009-02-25 Ｄｉｃ株式会社 活性エネルギー線硬化型水性樹脂組成物、活性エネルギー線硬化型塗料、硬化塗膜の形成方法及び物品

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JPS62265249A (ja) * 1986-02-20 1987-11-18 ユニオン・カ−バイド・コ−ポレ−シヨン カルボキシルを末端基とするラクトンアクリレ−ト
JPH09316369A (ja) * 1996-03-28 1997-12-09 Dainippon Printing Co Ltd 抗菌性電離放射線硬化型塗料及び抗菌性透明フィルム
WO2007138946A1 (fr) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. Composition d'oxyde métallique, film durci et laminé
WO2014157588A1 (fr) * 2013-03-29 2014-10-02 Hoya株式会社 Composition de revêtement
JP2015044905A (ja) * 2013-08-27 2015-03-12 昭和電工株式会社 樹脂組成物、透明フィルム、その製造方法及び用途
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JP2019112555A (ja) * 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化性組成物およびそれを用いたインデックスマッチング層および積層体
JP7102727B2 (ja) 2017-12-25 2022-07-20 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化性組成物およびそれを用いたインデックスマッチング層および積層体
JP2022132323A (ja) * 2017-12-25 2022-09-08 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化性組成物およびそれを用いたインデックスマッチング層および積層体

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