WO2017169802A1 - Fine-metal-particle dispersion and cured film - Google Patents

Fine-metal-particle dispersion and cured film Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
acrylic
group
acid
Prior art date
Application number
PCT/JP2017/010491
Other languages
French (fr)
Japanese (ja)
Inventor
鉄也 原田
慎司 足立
北嶋　裕
Original Assignee
ハリマ化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ハリマ化成株式会社 filed Critical ハリマ化成株式会社
Priority to JP2017532194A priority Critical patent/JP6196750B1/en
Priority to CN201780000674.3A priority patent/CN107960085B/en
Priority to KR1020177017648A priority patent/KR101811187B1/en
Publication of WO2017169802A1 publication Critical patent/WO2017169802A1/en

Links

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • 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

A fine-metal-particle dispersion which comprises fine metal particles, a dispersion medium, and a dispersant for fine metal particles. The dispersant for fine metal particles comprises (A) an acid-anhydride-modified polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups and at least one hydroxyl group and (B) one or more monofunctional (meth)acrylic compounds each having one (meth)acryloyl group. The monofunctional (meth)acrylic compounds comprise at least one compound selected from the group consisting of (b1) specific caprolactone adducts of (meth)acrylic acid, (b2) acid-anhydride-modified specific caprolactone adducts of hydroxyalkyl (meth)acrylates, and (b3) acid-anhydride-modified specific alkylene oxide adducts of (meth)acrylic acid.

Description

金属微粒子分散液および硬化膜Metal fine particle dispersion and cured film
　本発明は、金属微粒子分散液および硬化膜に関し、具体的には、金属微粒子分散剤によって金属微粒子が分散されてなる金属微粒子分散液、および、その金属微粒子分散液を硬化して得られる硬化膜に関する。 TECHNICAL FIELD 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. About.
　従来、各種コーティング剤には、そのコーティング剤を塗布および硬化させて得られる硬化膜に、例えば、機械物性、耐薬品性、高屈折率、帯電防止性、紫外線・赤外線遮断性、耐擦傷性などの各種物性を付与するためや、さらには、顔料などとして、種々の金属微粒子が分散されている。 Conventionally, for various coating agents, 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.
　また、そのようなコーティング剤においては、配合される金属微粒子や、溶剤、バインダー樹脂の種類などによっては、金属微粒子が凝集する場合がある。そこで、金属微粒子を良好に分散させるため、コーティング剤に分散剤を添加することが、提案されている。 Further, in such a coating agent, 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.
　具体的には、例えば、ジペンタエリスリトールペンタアクリレートおよびジペンタエリスリトールヘキサアクリレートの混合物（ジペンタエリスリトールペンタアクリレートを６７モル％含有）とピロメリット酸二無水物とを反応させることにより、カルボキシル基含有（メタ）アクリレートを調製し、得られたカルボキシル基含有（メタ）アクリレートと、ＳｉＯｘ（ｘ：１＜ｘ＜２）の超微粒子エタノール分散液と、トルエンとを混合して、超微粒子を含む塗布用樹脂組成物を調製することが、提案されている（特許文献１（実施例１）参照）。 Specifically, for example, by reacting a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (containing 67 mol% of dipentaerythritol pentaacrylate) with pyromellitic dianhydride, a carboxyl group-containing ( Preparation of (meth) acrylate, the obtained carboxyl group-containing (meth) acrylate, SiOx (x: 1 <x <2) ultrafine ethanol dispersion, and toluene are mixed, and for coating containing ultrafine particles It has been proposed to prepare a resin composition (see Patent Document 1 (Example 1)).
　また、例えば、ＺｎＯ超微粒子トルエン分散液と、ジペンタエリスリトールペンタアクリレートおよびジペンタエリスリトールヘキサアクリレートの混合物（ジペンタエリスリトールペンタアクリレートを６７モル％含有）と、アロニックスＭ－５３００（ω－カルボキシカプロラクトンモノアクリレート）とを混合し、高屈折率樹脂組成物を調製することが、提案されている（特許文献１（実施例６）参照）。 Further, for example, ZnO ultrafine particle toluene dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (containing 67 mol% of dipentaerythritol pentaacrylate), and Aronix M-5300 (ω-carboxycaprolactone monoacrylate) ) To prepare a high refractive index resin composition (see Patent Document 1 (Example 6)).
特開平０８－２４４１７８号公報Japanese Patent Laid-Open No. 08-244178
　一方、上記したような塗布用樹脂組成物の硬化膜には、基材との密着性が要求されており、とりわけ、湿熱環境下においても密着性を維持できる耐湿熱密着性が要求されている。 On the other hand, 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. .
　また、塗布用樹脂組成物としては、さらなる分散性の向上が要求されており、また、その硬化膜には、用途に応じて、優れた硬度および透明性が要求される。 Further, as 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.
　本発明の目的は、金属微粒子の分散安定性に優れ、また、硬化膜の耐湿熱密着性、硬度および透明性の向上を図ることができる金属微粒子分散液、および、その金属微粒子分散液を硬化して得られる硬化膜を提供することにある。 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.
　本発明［１］は、金属微粒子と、分散媒と、金属微粒子分散剤とを含有する金属微粒子分散液であって、前記金属微粒子分散剤は、（Ａ）２つ以上の（メタ）アクリロイル基、および、少なくとも１つのヒドロキシル基を有する、多官能（メタ）アクリル化合物の酸無水物変性体と、（Ｂ）１つの（メタ）アクリロイル基を有する単官能（メタ）アクリル化合物とを含有し、前記単官能（メタ）アクリル化合物は、下記（ｂ１）～（ｂ３）で示される化合物の少なくとも１種を含有する、金属微粒子分散液を含んでいる。 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）下記式（１）で示される（メタ）アクリル酸のカプロラクトン付加物。 (B1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯ［Ｏ（ＣＨ２）５ＣＯ］ｎＯＨ　　　（１）
（式（１）中、Ｒ１は、水素原子、メチル基を示し、ｎは、１～１０を示す。）
　　（ｂ２）下記式（２）で示されるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体。 CH 2 = C (R 1) CO [O (CH 2) 5 CO] n OH (1)
(In the formula (1), R 1 represents a hydrogen atom or a methyl group, and n represents 1 to 10.)
(B2) An acid anhydride modified product of a caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the following formula (2).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２Ｏ［ＣＯ（ＣＨ２）５Ｏ］ｎＨ　　　（２）
（式（２）中、Ｒ１は、水素原子、メチル基を示し、Ｒ２は、エチレン基、プロピレン基およびテトラメチレン基からなる群から選択される少なくとも１種を示し、ｎは、１～１０を示す。）
　　（ｂ３）下記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体。 CH 2 = C (R 1 ) COOR 2 O [CO (CH 2 ) 5 O] n H (2)
(In 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, and n represents 1 to 10 is shown.)
(B3) An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯ（ＣｍＨ２ｍＯ）ｎＨ　　　（３）
（式（３）中、Ｒ１は、水素原子、メチル基を示し、ｍは、２～４を示し、ｎは、１～１０を示す。）
　本発明［２］は、（Ｂ）前記単官能（メタ）アクリル化合物が、上記式（１）で示され、ｎが１～３である（メタ）アクリル酸のカプロラクトン付加物を含有する、上記［１］に記載の金属微粒子分散液を含んでいる。 CH 2 = C (R 1) COO (C m H 2m O) n H (3)
(In the formula (3), R1 represents a hydrogen atom or a methyl group, m represents 2 to 4, and n represents 1 to 10.)
In the present invention [2], (B) the monofunctional (meth) acrylic compound contains a caprolactone adduct of (meth) acrylic acid represented by the above formula (1) and n is 1 to 3. The metal fine particle dispersion described in [1] is included.
　本発明［３］は、（Ｂ）前記単官能（メタ）アクリル化合物が、上記式（２）で示され、ｎが２～５であるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体を含有する、上記［１］に記載の金属微粒子分散液を含んでいる。 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.
　本発明［４］は、（Ｂ）前記単官能（メタ）アクリル化合物が、上記式（３）で示され、ｍが２～３であり、ｎが２～５である（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体を含有する、上記［１］に記載の金属微粒子分散液を含んでいる。 In the present invention [4], (B) the (meth) acrylic acid in which the monofunctional (meth) acrylic compound is represented by the above formula (3), m is 2 to 3, and n is 2 to 5 The metal fine particle dispersion according to [1] above, which contains an acid anhydride modified product of an alkylene oxide adduct.
　本発明［５］は、さらに、バインダーを含有し、前記バインダーが、（メタ）アクリル樹脂を含有する、上記［１］～［４］のいずれか一項に記載の金属微粒子分散液を含んでいる。 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.
　本発明［６］は、上記［１］～［５］のいずれか一項に記載の金属微粒子分散液の硬化物である、硬化膜を含んでいる。 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.
　本発明の金属微粒子分散液は、金属微粒子の分散安定性に優れ、また、耐湿熱密着性、硬度および透明性に優れる硬化膜を得ることができる。 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.
　そのため、本発明の硬化膜は、耐湿熱密着性、硬度および透明性に優れる。 Therefore, the cured film of the present invention is excellent in wet heat resistance, hardness, and transparency.
　本発明の金属微粒子分散液は、金属微粒子と、分散媒と、金属微粒子分散剤とを含有している。 The metal fine particle dispersion of the present invention contains metal fine particles, a dispersion medium, and a metal fine particle dispersant.
　金属微粒子としては、特に制限されないが、例えば、酸化アルミニウム（アルミナ）、酸化チタン（チタニア）、酸化亜鉛、酸化ジルコニウム（ジルコニア）、酸化スズ、酸化イットリウム（イットリア）、酸化ビスマス、酸化アンチモン、酸化セリウム、酸化インジウム、酸化ケイ素（二酸化ケイ素、シリカなど）などの金属酸化物の微粒子や、例えば、それら金属酸化物に、例えば、ガリウム、アンチモン、スズ、フッ素、リン、アルミニウムなどの異種元素をドープして得られる異種元素ドープ金属酸化物の微粒子などが挙げられる。これら金属酸化物の結晶構造は、特に制限されず、例えば、立方晶系、正方晶系、斜方晶系、単斜晶系、三斜晶系、六方晶系、三方晶系などのいずれであってもよい。 Although it does not restrict | limit especially as 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.
　金属微粒子として、好ましくは、酸化アルミニウム、酸化ジルコニウム、二酸化ケイ素が挙げられる。 Preferred metal fine particles include aluminum oxide, zirconium oxide, and silicon dioxide.
　また、金属微粒子は、必要により、公知の方法によって表面処理されていてもよい。 In addition, the metal fine particles may be surface-treated by a known method if necessary.
　これら金属微粒子は、単独使用または２種類以上併用することができる。 These metal fine particles can be used alone or in combination of two or more.
　金属微粒子の形状は、特に制限されず、例えば、塊状、球状、中空状、多孔質状、棒状、板状、繊維状、不定形状およびそれらの混合物などが挙げられる。 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.
　また、金属微粒子の粒径は、金属微粒子自体の一次粒子径として測定され、例えば、２００ｎｍ以下、好ましくは、９０ｎｍ以下、より好ましくは、５０ｎｍ以下であり、通常、１ｎｍ以上、好ましくは、３ｎｍ以上である。 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.
　金属微粒子の一次粒子径が上記範囲であれば、金属微粒子の入手が容易であり、また、金属微粒子分散液の保存安定性や、硬化膜（後述）の透明性の向上を図ることができる。 If the primary particle diameter of the metal fine particles is in the above range, 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.
　分散媒としては、例えば、有機溶剤、水系溶剤、反応性溶剤などが挙げられる。 Examples of the dispersion medium include organic solvents, aqueous solvents, and reactive solvents.
　有機溶剤としては、例えば、ヘキサン、ミネラルスピリットなどの石油系炭化水素溶剤、例えば、ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶剤、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノンなどのケトン系溶剤、例えば、酢酸メチル、酢酸エチル、酢酸ブチル、γ―ブチロラクトン、プロピレングリコールモノメチルエーテルアセテートなどのエステル系溶剤、例えば、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、Ｎ－メチルピロリドン、ピリジンなどの非プロトン性極性溶剤などが挙げられる。 Examples of the organic solvent 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. Ketone solvents such as methyl acetate, ethyl acetate, butyl acetate, γ-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.
　水系溶剤としては、例えば、水、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノールなどのアルコール系溶剤、例えば、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのグリコールエーテル系溶剤などが挙げられる。 Examples of the aqueous solvent 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.
　反応性溶剤としては、例えば、エチレン性不飽和結合を１つ以上有する化合物が挙げられ、具体的には、例えば、１分子中に１つのエチレン性不飽和結合を有する化合物（後述する金属微粒子分散剤における（Ｂ）単官能（メタ）アクリル化合物を除く。）、１分子中に２つ以上のエチレン性不飽和結合を有する化合物（後述する金属微粒子分散剤における（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体を除く。）などが挙げられる。 Examples of the reactive solvent include a compound having one or more ethylenically unsaturated bonds. Specifically, for example, a compound having one ethylenically unsaturated bond in one molecule (metal fine particle dispersion described later) (Excluding (B) monofunctional (meth) acrylic compound in the agent.) 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).
　１分子中に１つのエチレン性不飽和結合を有する化合物としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、へプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルへキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、１－メチル－２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、エトキシ－ジエチレングリコール（メタ）アクリレート、２－エチルヘキシル－カルビトール（メタ）アクリレート、ネオペンチルグリコールベンゾエート（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、エピクロロヒドリン（ＥＣＨ）変性フェノキシ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ｏ－フェニルフェノキシエチル（メタ）アクリレート、ｍ－フェノキシベンジル（メタ）アクリレート、ｐ－フェノキシベンジル（メタ）アクリレート、パラクミルフェノールエチレンオキサイド変性（メタ）アクリレート、スチレン、α―メチルスチレン、β―メチルスチレン、p-メチルスチレン、ビニルピロリドン、ビニルカプロラクタム、アクリロイルモルフォリンなどが挙げられる。 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 (meth) acrylate, lauryl (meth) acrylate, Thearyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 1-methyl-2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, 2-ethylhexyl-carbi Tall (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, epichloro Dorin (ECH) modified phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) acrylate, paracumylphenol ethylene Examples include oxide-modified (meth) acrylate, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, vinylpyrrolidone, vinylcaprolactam, acryloylmorpholine.
　１分子中に２つ以上のエチレン性不飽和結合を有する化合物としては、例えば、１分子中に２つのエチレン性不飽和結合を有する化合物、１分子中に３つのエチレン性不飽和結合を有する化合物、１分子中に４つのエチレン性不飽和結合を有する化合物、１分子中に５つのエチレン性不飽和結合を有する化合物、１分子中に６つのエチレン性不飽和結合を有する化合物などが挙げられる。 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.
　１分子中に２つのエチレン性不飽和結合を有する化合物としては、例えば、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレートなどのアルキレングリコールジ（メタ）アクリレート；ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレートなどのポリアルキレングリコールジ（メタ）アクリレート；１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ジシクロペンタジエンジ（メタ）アクリレート、ネオペンチルグリコールアジペートジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート；ペンタエリスリトールジ（メタ）アクリレート、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、ビスフェノールＡエチレンオキサイド（ＥＯ）付加ジアクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、イソシアヌレートジ（メタ）アクリレートまたはそれらのアルキレンオキシド変性体、ジビニルベンゼン、ブタンジオール－１，４－ジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテルジプロピレングリコールジビニルエーテル、ヘキサンジオールジビニルエーテル、トリエチレングリコールジビニルエーテル、フェニルグリシジルエーテルアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー（共栄社化学製の商品名「ＡＨ－６００」）、フェニルグリシジルエーテルアクリレートトルエンジイソシアネートウレタンプレポリマー（共栄社化学製の商品名「ＡＴ－６００」）などが挙げられる。 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. ) Acrylate; polyethylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate; -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dicyclopentadiene di (meth) acrylate , Neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate; pentaerythritol di (meth) ) Acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bisphenol A ethylene oxide (EO) addition diacrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphorus Acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate or their modified alkylene oxide, divinylbenzene, butane Diol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane pre Examples thereof include a polymer (trade name “AH-600” manufactured by Kyoeisha Chemical Co., Ltd.) and a phenylglycidyl ether acrylate toluene diisocyanate urethane prepolymer (trade name “AT-600” manufactured by Kyoeisha Chemical Co., Ltd.).
　１分子中に３つのエチレン性不飽和結合を有する化合物としては、例えば、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、またはそれらのアルキレンオキシド変性体、イソシアヌル酸アルキレンオキシド変性体のトリ（メタ）アクリレートなどが挙げられる。 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). ) Isocyanurate, or an alkylene oxide modified product thereof, a tri (meth) acrylate of an isocyanuric acid alkylene oxide modified product, and the like.
　１分子中に４つのエチレン性不飽和結合を有する化合物としては、例えば、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジグリセリンテトラ（メタ）アクリレートまたはそれらのアルキレンオキシド変性体などが挙げられる。 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.
　１分子中に５つのエチレン性不飽和結合を有する化合物としては、例えば、ジペンタエリスリトールペンタ（メタ）アクリレートまたはそれらのアルキレンオキシド変性体などが挙げられる。 Examples of the compound having five ethylenically unsaturated bonds in one molecule include dipentaerythritol penta (meth) acrylate or their modified alkylene oxides.
　１分子中に６つのエチレン性不飽和結合を有する化合物としては、例えば、ジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー（共栄社化学製の商品名「ＵＡ－３０６Ｈ」）、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレートまたはそれらのアルキレンオキシド変性体などが挙げられる。 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.
　また、分散媒は、市販品としても入手可能であり、具体的には、石油系炭化水素溶剤として、例えば、ＡＦソルベント４～７号（以上、新日本石油社製）などが挙げられ、芳香族炭化水素系溶剤として、例えば、インキソルベント０号、エクソン化学社製のソルベッソ１００、１５０、２００（以上、新日本石油社製）などが挙げられる。 The dispersion medium is also available as a commercial product. Specifically, 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.
　これら分散媒は、単独使用または２種類以上併用することができる。 These dispersion media can be used alone or in combination of two or more.
　分散媒として、基材への密着性、硬度などの観点から、好ましくは、有機溶剤、水系溶剤が挙げられ、より好ましくは、有機溶剤が挙げられ、さらに好ましくは、メチルイソブチルケトンが挙げられる。 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.
　また、分散媒として、成膜時の生産性向上、基材へのダメージ抑制、高精細形状への対応などの観点から、好ましくは、反応性溶剤が挙げられ、より好ましくは、フェノキシエチル（メタ）アクリレート、ｏ－フェニルフェノキシエチル（メタ）アクリレート、ｍ－フェノキシベンジル（メタ）アクリレート、ｐ－フェノキシベンジル（メタ）アクリレート、スチレン、α―メチルスチレン、β―メチルスチレン、p-メチルスチレン、テトラエチレングリコールジ（メタ）アクリレート、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、トリメチロールプロパントリ（メタ）アクリレートのアルキレンオキシド変性体、ジグリセリンテトラ（メタ）アクリレートのアルキレンオキシド変性体、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートが挙げられる。 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, α-methylstyrene, β-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 (meth) acrylate, dipentaerythritol hexa (meth) acrylate.
　金属微粒子分散剤は、分散媒中における金属微粒子の分散性を向上させるための添加剤であって、（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体と、（Ｂ）単官能（メタ）アクリル化合物とを含有している。 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.
　なお、（メタ）アクリル化合物とは、アクリル化合物および／またはメタクリル化合物と定義される。 The (meth) acrylic compound is defined as an acrylic compound and / or a methacrylic compound.
　また、「（メタ）アクリル」も、上記と同じく、「アクリル」および／または「メタクリル」と定義され、「（メタ）アクリロイル」も「アクリロイル」および／または「メタクリロイル」と定義され、「（メタ）アクリレート」も「アクリレート」および／または「メタクリレート」と定義される。 Also, “(meth) acryl” is defined as “acryl” and / or “methacryl”, and “(meth) acryloyl” is also defined as “acryloyl” and / or “methacryloyl”. ) Acrylate "is also defined as" acrylate "and / or" methacrylate ".
　（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体は、具体的には、（Ａ）２つ以上の（メタ）アクリロイル基、および、少なくとも１つのヒドロキシル基を有する、多官能（メタ）アクリル化合物（以下、ヒドロキシル基含有－多官能（メタ）アクリル化合物と略する場合がある。）の酸無水物変性体である。 (A) 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).
　ヒドロキシル基含有－多官能（メタ）アクリル化合物は、例えば、ポリオール（例えば、グリセリン（ヒドロキシル基数３）、トリメチロールプロパン（ヒドロキシル基数３）、トリス（２－ヒドロキシエチル）イソシアヌレート（ヒドロキシル基数３）、ジグリセリン（ヒドロキシル基数４）、ジトリメチロールプロパン（ヒドロキシル基数４）、ペンタエリスリトール（ヒドロキシル基数４）、ジペンタエリスリトール（ヒドロキシル基数６）、トリペンタエリスリトール（ヒドロキシル基数８）などの公知の多官能アルコール）に、そのポリオールのヒドロキシル基数に対して等モル未満の（メタ）アクリル酸が付加したアダクト体（付加物）である。 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.
　ヒドロキシル基含有－多官能（メタ）アクリル化合物としては、例えば、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ジトリメチロールプロパンジ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、トリス－２－ヒドロキシエチルイソシアヌレートジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ジグリセリンジ（メタ）アクリレート、ジグリセリントリ（メタ）アクリレート、およびこれらのアルキレンオキサイド（エチレンオキサイド、プロピレンオキサイドなど）付加物（ランダム付加物、ブロック付加物を含む。）、およびこれらの混合物が挙げられる。 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.
　これらヒドロキシル基含有－多官能（メタ）アクリル化合物は、単独使用または２種類以上併用することができる。 These hydroxyl group-containing polyfunctional (meth) acrylic compounds can be used alone or in combination of two or more.
　ヒドロキシル基含有－多官能（メタ）アクリル化合物として、好ましくは、ジペンタエリスリトールペンタアクリレートが挙げられる。 Preferred examples of the hydroxyl group-containing polyfunctional (meth) acrylic compound include dipentaerythritol pentaacrylate.
　なお、ヒドロキシル基含有－多官能（メタ）アクリル化合物は、後述するヒドロキシル基不含－多官能（メタ）アクリル化合物と、適宜の割合で併用することもできる。 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.
　酸無水物としては、ジカルボン酸一無水物、トリカルボン酸一無水物、テトラカルボン酸二無水物などが挙げられる。 Examples of the acid anhydride include dicarboxylic acid monoanhydride, tricarboxylic acid monoanhydride, and tetracarboxylic acid dianhydride.
　ジカルボン酸一無水物としては、例えば、無水シュウ酸、無水コハク酸、無水マレイン酸、無水フタル酸、無水２－アルキル（Ｃ１２～Ｃ１８）コハク酸、無水テトラヒドロフタル酸、ハイミック酸無水物、ヘキサヒドラフタル酸無水物、テトラプロムフタル酸無水物、テトラクロルフタル酸無水物などが挙げられる。 Examples of the dicarboxylic acid monoanhydride 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.
　トリカルボン酸一無水物としては、例えば、無水トリメリット酸、、シクロヘキサン－１，２，４－トリカルボン酸－１，２－無水物などが挙げられる。 Examples of the tricarboxylic acid monoanhydride include trimellitic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and the like.
　テトラカルボン酸二無水物としては、例えば、無水ピロメリット酸、ベンゾフェノテトラカルボン酸無水物、２，３，６，７－ナフタリンテトラカルボン酸２無水物、５－（２，５－オキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物などが挙げられる。 Examples of 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.
　これら酸無水物は、単独使用または２種類以上併用することができる。 These acid anhydrides can be used alone or in combination of two or more.
　酸無水物として、好ましくは、ジカルボン酸一無水物、テトラカルボン酸二無水物が挙げられ、より好ましくは、無水コハク酸、無水フタル酸、無水ピロメリット酸が挙げられる。また、酸無水物として、好ましくは、ジカルボン酸一無水物が挙げられ、硬化膜（後述）の硬度の観点から、より好ましくは、無水コハク酸、無水フタル酸が挙げられる。 Preferred examples of the acid anhydride include dicarboxylic acid monoanhydride and tetracarboxylic acid dianhydride, and more preferred examples include succinic anhydride, phthalic anhydride, and pyromellitic anhydride. Moreover, as an acid anhydride, Preferably, 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.
　ヒドロキシル基含有－多官能（メタ）アクリル化合物の酸無水物変性体を得るには、例えば、ヒドロキシル基含有－多官能（メタ）アクリル化合物と酸無水物とを配合し、必要により、溶剤中において、加熱して反応させる。 In order to obtain 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.
　ヒドロキシル基含有－多官能（メタ）アクリル化合物と酸無水物との配合割合は、例えば、ヒドロキシル基含有－多官能（メタ）アクリル化合物のヒドロキシル基に対する酸無水物の無水カルボン酸基との当量比（無水カルボン酸基／ヒドロキシル基）が、例えば、０．５以上、好ましくは、０．６７以上であり、例えば、１以下、好ましくは、０．９１以下である。 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.
　溶剤としては、例えば、上記した有機溶剤（分散媒として上記した有機溶剤）、上記した水系溶剤（分散媒として上記した水系溶剤）、上記した反応性溶剤（分散媒として上記した反応性溶剤）などが挙げられる。これら溶剤は、単独使用または２種類以上併用することができる。溶剤として、好ましくは、ヒドロキシル基含有－多官能（メタ）アクリル化合物および酸無水物に対して不活性である溶剤が挙げられ、具体的には、カルボキシ基および水酸基を有しない溶剤が挙げられる。そのような溶剤として、好ましくは、有機溶剤、より好ましくは、ケトン系溶剤、さらに好ましくは、メチルイソブチルケトンが挙げられる。 Examples of the solvent 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. As such a solvent, an organic solvent is preferable, a ketone solvent is more preferable, and methyl isobutyl ketone is more preferable.
　また、この反応では、必要により、触媒を添加することもできる。 In this reaction, a catalyst can be added if necessary.
　触媒としては、例えば、金属、有機金属化合物、金属ハロゲン化物、アミン化合物などが挙げられる。 Examples of the catalyst include metals, organometallic compounds, metal halides, and amine compounds.
　金属としては、ナトリウム、カリウムなどのアルカリ金属が挙げられる。 Examples of the metal include alkali metals such as sodium and potassium.
　有機金属化合物としては、例えば、上記したアルカリ金属のアルコキシド（アルカリ金属アルコキシド）およびその誘導体、例えば、トリエチルアルミニウムなどのアルキルアルミニウム化合物およびその誘導体、例えば、チタン酸テトラブチルなどのアルコキシチタン化合物、２－エチルヘキサン酸錫、オクチル酸錫、ジブチル錫ラウレートなどの有機錫化合物などが挙げられる。 Examples of the organometallic compound 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.
　金属ハロゲン化物としては、例えば、塩化錫（具体的には、二塩化錫：ＳｎＣｌ２）などの錫ハロゲン化物が挙げられる。 Examples of the metal halide include tin halides such as tin chloride (specifically, tin dichloride: SnCl 2 ).
　アミン化合物としては、例えば、Ｎ，Ｎ－ジメチルベンジルアミン、トリエチルアミン、トリブチルアミン、トリエチレンジアミン、ベンジルトリメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムブロマイド、テトラメチルアンモニウムブロマイド、セチルトリメチルアンモニウムブロマイドなどが挙げられる。 Examples of the amine compound include N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide and the like.
　これら触媒は、単独使用または２種類以上併用することができる。 These catalysts can be used alone or in combination of two or more.
　触媒として、好ましくは、アミン化合物が挙げられ、より好ましくは、Ｎ，Ｎ－ジメチルベンジルアミン、トリエチルアミン、トリブチルアミンが挙げられ、さらに好ましくは、トリエチルアミンが挙げられる。 The catalyst is preferably an amine compound, more preferably N, N-dimethylbenzylamine, triethylamine, or tributylamine, and still more preferably triethylamine.
　触媒の配合割合は、ヒドロキシル基含有－多官能（メタ）アクリル化合物と酸無水物との総量１００質量部に対して、例えば、０．０００１質量部以上、好ましくは、０．０１質量部以上であり、例えば、５質量部以下、好ましくは、０．５質量部以下である。 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.
　また、この反応では、必要により、重合禁止剤を添加することもできる。 In this reaction, a polymerization inhibitor can be added if necessary.
　重合禁止剤としては、例えば、ｐ－メトキシフェノール、ハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ｔｅｒｔ－ブチルカテコール、２，６－ジ－ｔｅｒｔ－ブチル－ヒドロキシトルエン、４－ｔｅｒｔ－ブチル－１，２－ジヒドロキシベンゼン、２，２’－メチレン－ビス（４－メチル－６－ｔｅｒｔ－ブチルカテコール）などのフェノール化合物、例えば、フェノチアジン、ジフェニルフェニレンジアミン、ジナフチルフェニレンジアミン、ｐ－アミノジフェニルアミン、Ｎ－アルキル－Ｎ’－フェニレンジアミンなどの芳香族アミン類、例えば、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン、４－アセトキシ－１－オキシ－２，２，６，６－テトラメチルピペリジン、４－ベンゾイロキシ－１－オキシ－２，２，６，６－テトラメチルピペリジン、４－アルコキシ－１－オキシ－２，２，６，６－テトラメチルピペリジン、ビス（１－オキシ－２，２，６，６－テトラメチルピペリジン－４－イル）セバケートの２，２，６，６－テトラメチルピペリジンのＮ－オキシル誘導体、Ｎ－ニトロソジフェニルアミン、ジエチルジチオカルバミン酸の銅塩、ｐ－ベンゾキノンなどが挙げられる。 Examples of the polymerization inhibitor 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-2,2,6,6-tetramethylpiperidine, bis (1-oxy-2,2,6,6-tetramethyl Examples include N-oxyl derivatives of 2,2,6,6-tetramethylpiperidine of piperidin-4-yl) sebacate, N-nitrosodiphenylamine, copper salt of diethyldithiocarbamic acid, p-benzoquinone, and the like.
　これら重合禁止剤は、単独使用または２種類以上併用することができる。 These polymerization inhibitors can be used alone or in combination of two or more.
　重合禁止剤として、好ましくは、ｐ－メトキシフェノールが挙げられる。 The polymerization inhibitor is preferably p-methoxyphenol.
　重合禁止剤の配合割合は、ヒドロキシル基含有－多官能（メタ）アクリル化合物と、酸無水物との総量１００質量部に対して、例えば、０．０００１質量部以上、好ましくは、０．０１質量部以上であり、例えば、１．０質量部以下、好ましくは、０．１質量部以下である。 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.
　また、反応条件としては、酸素雰囲気下、または、不活性ガス－酸素ガス混合気雰囲気下において、加熱温度が、例えば、６０℃以上、好ましくは、８０℃以上であり、例えば、１４０℃以下、好ましくは、１１０℃以下である。また、加熱時間が、例えば、４時間以上、好ましくは、８時間以上であり、例えば、２０時間以下、好ましくは、１２時間以下である。 As reaction conditions, in an oxygen atmosphere or an inert gas-oxygen gas mixture atmosphere, 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.
　これにより、ヒドロキシル基含有－多官能（メタ）アクリル化合物を酸無水物により変性させることができ、（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体が得られる。 Thereby, 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）多官能（メタ）アクリル化合物の酸無水物変性体として、より具体的には、例えば、ジペンタエリスリトールペンタアクリレートのフタル酸変性物、ペンタエリスリトールトリアクリレートのフタル酸変性物、ジペンタエリスリトールペンタアクリレートのコハク酸変性物、ペンタエリスリトールトリアクリレートのコハク酸変性物などが挙げられる。 (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.
　（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の酸価は、例えば、２０ｍｇＫＯＨ／ｇ以上、好ましくは、７３ｍｇＫＯＨ／ｇ以上、より好ましくは、８０ｍｇＫＯＨ／ｇ以上であり、例えば、５００ｍｇＫＯＨ／ｇ以下、好ましくは、３００ｍｇＫＯＨ／ｇ以下である。 (A) 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.
　また、（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の水酸基価は、例えば、０ｍｇＫＯＨ／ｇを超過し、好ましくは、１ｍｇＫＯＨ／ｇ以上であり、例えば、３５０ｍｇＫＯＨ／ｇ以下、好ましくは、２３０ｍｇＫＯＨ／ｇ以下である。 In addition, 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.
　（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の配合割合は、金属微粒子１００質量部に対して、例えば、１質量部以上、好ましくは、５質量部以上、より好ましくは、７質量部以上であり、例えば、２００質量部以下、好ましくは、１００質量部以下、さらに好ましくは、７０質量部以下、とりわけ好ましくは、５０質量部以下である。 (A) 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. For example, 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.
　（Ｂ）単官能（メタ）アクリル化合物は、具体的には、１つの（メタ）アクリロイル基を有する化合物であって、下記（ｂ１）～（ｂ３）で示される化合物の少なくとも１種を含有している。 (B) 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）下記式（１）で示される（メタ）アクリル酸のカプロラクトン付加物。 (B1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯ［Ｏ（ＣＨ２）５ＣＯ］ｎＯＨ　　　（１）
（式（１）中、Ｒ１は、水素原子、メチル基を示し、ｎは、１～１０を示す。）
　（ｂ２）下記式（２）で示されるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体。 CH 2 = C (R 1) CO [O (CH 2) 5 CO] n OH (1)
(In the formula (1), R 1 represents a hydrogen atom or a methyl group, and n represents 1 to 10.)
(B2) An acid anhydride modified product of a caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the following formula (2).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２Ｏ［ＣＯ（ＣＨ２）５Ｏ］ｎＨ　　　（２）
（式（２）中、Ｒ１は、水素原子、メチル基を示し、Ｒ２は、エチレン基、プロピレン基およびテトラメチレン基からなる群から選択される少なくとも１種を示し、ｎは、１～１０を示す。）
　（ｂ３）下記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体。 CH 2 = C (R 1 ) COOR 2 O [CO (CH 2 ) 5 O] n H (2)
(In 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, and n represents 1 to 10 is shown.)
(B3) An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯ（ＣｍＨ２ｍＯ）ｎＨ　　　（３）
（式（３）中、Ｒ１は、水素原子、メチル基を示し、ｍは、２～４を示し、ｎは、１～１０を示す。）
　以下において、上記（ｂ１）～（ｂ３）で示される化合物のそれぞれについて、詳述する。 CH 2 = C (R 1) COO (C m H 2m O) n H (3)
(In the formula (3), R1 represents a hydrogen atom or a methyl group, m represents 2 to 4, and n represents 1 to 10.)
Hereinafter, each of the compounds represented by the above (b1) to (b3) will be described in detail.
　（ｂ１）で示される化合物は、下記式（１）で示される（メタ）アクリル酸のカプロラクトン付加物である。 The compound represented by (b1) is a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯ［Ｏ（ＣＨ２）５ＣＯ］ｎＯＨ　　　（１）
（式（１）中、Ｒ１は、水素原子、メチル基を示し、ｎは、１～１０を示す。）
　上記式（１）において、Ｒ１は、水素原子および／またはメチル基を示し、好ましくは、水素原子を示す。 CH 2 = C (R 1) CO [O (CH 2) 5 CO] n OH (1)
(In the formula (1), R 1 represents a hydrogen atom or a methyl group, and n represents 1 to 10.)
In the above formula (1), R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
　また、上記式（１）において、ｎは、（メタ）アクリル酸１モルに対するカプロラクトンの平均付加モル数であり、１以上、好ましくは、２以上であり、１０以下、好ましくは、５以下、より好ましくは、３以下である。 In the above formula (1), 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.
　このような（メタ）アクリル酸のカプロラクトン付加物は、（メタ）アクリル酸にε－カプロラクトンを付加反応（開環付加）させることにより、得ることができる。 Such a caprolactone adduct of (meth) acrylic acid can be obtained by subjecting (meth) acrylic acid to an addition reaction (ring-opening addition) with ε-caprolactone.
　（メタ）アクリル酸は、アクリル酸および／またはメタアクリル酸であり、好ましくは、アクリル酸である。 (Meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.
　ε－カプロラクトンとしては、特に制限されず、市販品をそのまま使用することができる。 Ε-caprolactone is not particularly limited, and a commercially available product can be used as it is.
　（メタ）アクリル酸とε－カプロラクトンとを反応（開環付加）させる方法としては、特に制限されず、公知の方法（例えば、特開昭６２－１３５５２１、特開昭６０－６７４４６などに記載の方法）を採用することができる。 The method of reacting (meth) acrylic acid and ε-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).
　より具体的には、例えば、（メタ）アクリル酸とε－カプロラクトンとを配合し、必要により、触媒および溶剤の存在下において、加熱および撹拌する。 More specifically, for example, (meth) acrylic acid and ε-caprolactone are blended, and if necessary, heated and stirred in the presence of a catalyst and a solvent.
　（メタ）アクリル酸とε－カプロラクトンとの配合割合は、目的物（上記式（１）で示される化合物）の分子量、すなわち、（メタ）アクリル酸に対するε－カプロラクトンの平均付加モル数ｎに応じて適宜設定される。 The blending ratio of (meth) acrylic acid and ε-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 ε-caprolactone to (meth) acrylic acid. Is set as appropriate.
　例えば、（メタ）アクリル酸１モルに対して、ε－カプロラクトンが、例えば、１モル以上、好ましくは、２モル以上であり、例えば、１０モル以下、好ましくは、５モル以下、より好ましくは、３モル以下である。 For example, with respect to 1 mol of (meth) acrylic acid, ε-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.
　また、例えば、（メタ）アクリル酸１００質量部に対して、ε－カプロラクトンが、例えば、５０質量部以上、好ましくは、１５０質量部以上であり、例えば、１００００質量部以下、好ましくは、２０００質量部以下である。 Further, for example, with respect to 100 parts by mass of (meth) acrylic acid, ε-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.
　また、反応条件としては、不活性ガス、または、不活性ガス－酸素ガス混合気雰囲気下において、反応温度が、例えば、８０℃以上、好ましくは、１２０℃以上であり、例えば、２４０℃以下、好ましくは、２００℃以下である。また、反応時間は、例えば、４時間以上、好ましくは、６時間以上であり、例えば、２０時間以下、好ましくは、１２時間以下である。 As reaction conditions, 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.
　触媒としては、例えば、塩化アルミニウム、塩化第二スズなどのルイス酸、例えば、硫酸、パラトルエンスルホン酸、ベンゼンスルホン酸、スルホン酸型イオン交換樹脂などのブレンステッド酸などの酸触媒などが挙げられる。 Examples of the catalyst 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. .
　これら触媒は、単独使用または２種類以上併用することができる。 These catalysts can be used alone or in combination of two or more.
　触媒として、反応液に対する溶解性の観点から、好ましくは、硫酸、パラトルエンスルホン酸、ベンゼンスルホン酸が挙げられる。 The catalyst is preferably sulfuric acid, paratoluenesulfonic acid, or benzenesulfonic acid from the viewpoint of solubility in the reaction solution.
　触媒の配合割合は、（メタ）アクリル酸１００質量部に対して、例えば、０．１質量部以上、好ましくは、１質量部以上であり、例えば、５０質量部以下、好ましくは、２０質量部以下である。 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.
　溶剤としては、例えば、ベンゼン、トルエン、キシレンなどの芳香族炭化水素が挙げられる。 Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene.
　溶剤の配合割合は、特に制限されず、目的および用途に応じて、適宜設定される。 The mixing ratio of the solvent is not particularly limited, and is appropriately set according to the purpose and application.
　また、（メタ）アクリル酸のε－カプロラクトン付加物は、無溶剤でも製造できる。 Also, the ε-caprolactone adduct of (meth) acrylic acid can be produced without a solvent.
　なお、反応においては、必要により、上記した重合禁止剤を添加することもできる。 In the reaction, the above-described polymerization inhibitor can be added as necessary.
　重合禁止剤として、好ましくは、ｐ－メトキシフェノールが挙げられる。 The polymerization inhibitor is preferably p-methoxyphenol.
　重合禁止剤の配合割合は、（メタ）アクリル酸とε－カプロラクトンとの総量１００質量部に対して、例えば、０．０００１質量部以上、好ましくは、０．０１質量部以上であり、例えば、１．０質量部以下、好ましくは、０．１質量部以下である。 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 ε-caprolactone. 1.0 parts by mass or less, preferably 0.1 parts by mass or less.
　また、（メタ）アクリル酸のカプロラクトン付加物は、例えば、（メタ）アクリル酸と、カプロラクトンが開環したω－ヒドロキシカプロン酸とのエステル化反応（縮合重合）によっても得られる。 The caprolactone adduct of (meth) acrylic acid can also be obtained, for example, by an esterification reaction (condensation polymerization) between (meth) acrylic acid and ω-hydroxycaproic acid obtained by ring opening of caprolactone.
　また、（メタ）アクリル酸のカプロラクトン付加物は、市販品として入手することもできる。そのような市販品としては、例えば、アロニックスＭ－５３００（ω－カルボキシカプロラクトンモノアクリレート、東亜合成製）などが挙げられる。 Moreover, the caprolactone adduct of (meth) acrylic acid can also be obtained as a commercial product. Examples of such commercially available products include Aronix M-5300 (ω-carboxycaprolactone monoacrylate, manufactured by Toagosei Co., Ltd.).
　（ｂ１）上記式（１）で示される（メタ）アクリル酸のカプロラクトン付加物の酸価は、例えば、４５ｍｇＫＯＨ／ｇ以上、好ましくは、１３５ｍｇＫＯＨ／ｇ以上であり、例えば、３１０ｍｇＫＯＨ／ｇ以下である。 (B1) 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. .
　（ｂ２）で示される化合物は、下記式（２）で示されるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の、酸無水物変性体である。 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).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２Ｏ［ＣＯ（ＣＨ２）５Ｏ］ｎＨ　　　（２）
（式（２）中、Ｒ１は、水素原子、メチル基を示し、Ｒ２は、エチレン基、プロピレン基およびテトラメチレン基からなる群から選択される少なくとも１種を示し、ｎは、１～１０を示す。）
　上記式（２）において、Ｒ１は、水素原子および／またはメチル基を示し、好ましくは、水素原子を示す。 CH 2 = C (R 1 ) COOR 2 O [CO (CH 2 ) 5 O] n H (2)
(In 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, and n represents 1 to 10 is shown.)
In the above formula (2), R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
　また、上記式（２）において、Ｒ２は、エチレン基、プロピレン基およびテトラメチレン基からなる群から選択される少なくとも１種を示し、好ましくは、エチレン基を示す。 In the above formula (2), 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.
　また、上記式（２）において、ｎは、ヒドロキシアルキル（メタ）アクリレート１モルに対するカプロラクトンの平均付加モル数であり、１以上、好ましくは、２以上であり、１０以下、好ましくは、５以下である。 In the above formula (2), 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.
　（ｂ２）で示される化合物を得るには、例えば、まず、ヒドロキシアルキル（メタ）アクリレートとε－カプロラクトンとを反応（開環付加）させ、上記式（２）で示されるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物を得る。その後、上記式（２）で示されるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物と、酸無水物とを反応させる。 In order to obtain the compound represented by (b2), for example, first, hydroxyalkyl (meth) acrylate and ε-caprolactone are reacted (ring-opening addition) to obtain hydroxyalkyl (meth) acrylate represented by the above formula (2). To obtain an adduct of caprolactone. Thereafter, the caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the above formula (2) is reacted with an acid anhydride.
　ヒドロキシアルキル（メタ）アクリレートとしては、炭素数が２～４のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートが挙げられ、具体的には、例えば、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）クリレート、４－ヒドロキシブチル（メタ）アクリレートなどが挙げられる。 Examples of the hydroxyalkyl (meth) acrylate 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.
　これらヒドロキシアルキル（メタ）アクリレートは、単独使用または２種類以上併用することができる。 These hydroxyalkyl (meth) acrylates can be used alone or in combination of two or more.
　ヒドロキシアルキル（メタ）アクリレートとして、好ましくは、炭素数が２のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートが挙げられ、より好ましくは、２－ヒドロキシエチル（メタ）クリレートが挙げられる。 The hydroxyalkyl (meth) acrylate is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 carbon atoms, more preferably 2-hydroxyethyl (meth) acrylate.
　ε－カプロラクトンとしては、特に制限されず、市販品をそのまま使用することができる。 Ε-caprolactone is not particularly limited, and a commercially available product can be used as it is.
　ヒドロキシアルキル（メタ）アクリレートとε－カプロラクトンとを反応（開環付加）させる方法としては、特に制限されず、公知の方法（例えば、特開平１０－７７７４参照などに記載の方法）を採用することができる。 The method for reacting (ring-opening addition) hydroxyalkyl (meth) acrylate with ε-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.
　具体的には、例えば、ヒドロキシアルキル（メタ）アクリレートとε－カプロラクトンとを配合し、必要により、上記の触媒、および、上記の溶剤の存在下において、加熱および撹拌する。 Specifically, for example, hydroxyalkyl (meth) acrylate and ε-caprolactone are blended, and if necessary, heated and stirred in the presence of the above catalyst and the above solvent.
　ヒドロキシアルキル（メタ）アクリレートとε－カプロラクトンの配合割合は、目的物（上記式（２）で示される化合物）の分子量、すなわち、ヒドロキシアルキル（メタ）アクリレートに対するε－カプロラクトンの平均付加モル数ｎに応じて適宜設定される。 The blending ratio of hydroxyalkyl (meth) acrylate and ε-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 ε-caprolactone to hydroxyalkyl (meth) acrylate. It is set accordingly.
　例えば、ヒドロキシアルキル（メタ）アクリレート１モルに対して、ε－カプロラクトンが、例えば、１モル以上、好ましくは、２モル以上であり、例えば、１０モル以下、好ましくは、５モル以下である。 For example, with respect to 1 mol of hydroxyalkyl (meth) acrylate, ε-caprolactone is, for example, 1 mol or more, preferably 2 mol or more, for example, 10 mol or less, preferably 5 mol or less.
　また、例えば、ヒドロキシアルキル（メタ）アクリレート１００質量部に対して、ε－カプロラクトンが、例えば、９０質量部以上、好ましくは、１９０質量部以上であり、例えば、１０００質量部以下、好ましくは、５００質量部以下である。 Further, for example, ε-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.
　また、反応条件としては、酸素ガス、または、不活性ガス－酸素ガス混合気雰囲気下、反応温度が、例えば、６０℃以上、好ましくは、９０℃以上であり、例えば、１４０℃以下、好ましくは、１２０℃以下である。また、反応時間は、例えば、４時間以上、好ましくは、８時間以上であり、例えば、２０時間以下、好ましくは、１２時間以下である。 As reaction conditions, the 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. Moreover, 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.
　なお、反応においては、必要により、上記した重合禁止剤を添加することもできる。 In the reaction, the above-described polymerization inhibitor can be added as necessary.
　重合禁止剤として、好ましくは、ｐ－メトキシフェノールが挙げられる。 The polymerization inhibitor is preferably p-methoxyphenol.
　重合禁止剤の配合割合は、ヒドロキシアルキル（メタ）アクリレートとε－カプロラクトンの総量１００質量部に対して、例えば、０．０００１質量部以上、好ましくは、０．０１質量部以上であり、例えば、１．０質量部以下、好ましくは、０．１質量部以下である。 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 ε-caprolactone. 1.0 parts by mass or less, preferably 0.1 parts by mass or less.
　なお、ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物は、市販品として入手することもできる。そのような市販品としては、例えば、プラクセルＦＡ－１、プラクセルＦＡ－２、プラクセルＦＡ－２Ｄ、プラクセルＦＡ－３、プラクセルＦＡ－４、プラクセルＦＡ－５、プラクセルＦＡ－１０Ｌ、プラクセルＦＭ－１、プラクセルＦＭ－２、プラクセルＦＭ－２Ｄ、プラクセルＦＭ－３、プラクセルＦＭ－４、プラクセルＦＭ－５（いずれもダイセル化学社製）（プラクセル（ＰＬＡＣＣＥＬ）は登録商標）などが挙げられる。 In addition, the caprolactone adduct of hydroxyalkyl (meth) acrylate can also be obtained as a commercial product. Examples of such 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.
　これらヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物は、単独使用または２種類以上併用することができる。 These caprolactone adducts of hydroxyalkyl (meth) acrylate can be used alone or in combination of two or more.
　そして、上記のヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物と、酸無水物とを反応させることにより、ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体（すなわち、（ｂ２）で示される化合物）を得ることができる。 Then, by reacting the caprolactone adduct of hydroxyalkyl (meth) acrylate with an acid anhydride, the acid anhydride modified product of the caprolactone adduct of hydroxyalkyl (meth) acrylate (ie, shown in (b2)). Compound) can be obtained.
　酸無水物としては、上記した酸無水物（（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の製造において用いられる酸無水物）が挙げられ、好ましくは、ジカルボン酸一無水物が挙げられ、硬化膜（後述）の硬度の観点から、より好ましくは、無水コハク酸、無水フタル酸が挙げられ、さらに好ましくは、無水コハク酸が挙げられる。 Examples of the acid anhydride include the acid anhydrides described above ((A) acid anhydrides used in the production of acid anhydride-modified products of polyfunctional (meth) acrylic compounds). Preferably, dicarboxylic acid monoanhydrides are used. From the viewpoint of the hardness of the cured film (described later), succinic anhydride and phthalic anhydride are more preferable, and succinic anhydride is more preferable.
　そして、ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物と、酸無水物との反応では、例えば、ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物と酸無水物とを配合し、必要に応じて、溶剤、触媒などの存在下において、加熱する。 In the reaction of 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.
　溶剤としては、例えば、上記した有機溶剤（分散媒として上記した有機溶剤）、上記した水系溶剤（分散媒として上記した水系溶剤）、上記した反応性溶剤（分散媒として上記した反応性溶剤）などが挙げられる。これら溶剤は、単独使用または２種類以上併用することができる。溶剤として、好ましくは、ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物および酸無水物に対して不活性である溶剤が挙げられ、具体的には、カルボキシ基および水酸基を有しない溶剤が挙げられる。そのような溶剤として、好ましくは、有機溶剤、より好ましくは、ケトン系溶剤、さらに好ましくは、メチルイソブチルケトンが挙げられる。 Examples of the solvent 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. As 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. As such a solvent, an organic solvent is preferable, a ketone solvent is more preferable, and methyl isobutyl ketone is more preferable.
　触媒としては、例えば、上記した触媒（（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の製造において用いられる触媒）が挙げられる。これら触媒は、単独使用または２種類以上併用することができる。触媒として、好ましくは、アミン化合物が挙げられ、より好ましくは、Ｎ，Ｎ－ジメチルベンジルアミン、トリエチルアミン、トリブチルアミンが挙げられ、さらに好ましくは、トリエチルアミンが挙げられる。 Examples of the catalyst 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.
　ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物と酸無水物との配合割合は、例えば、ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物中のヒドロキシル基に対する酸無水物中の無水カルボン酸基との当量比（無水カルボン酸基／ヒドロキシル基）が、例えば、０．５以上、好ましくは、０．６７以上であり、例えば、１以下、好ましくは、０．９１以下である。 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.
　また、反応条件としては、酸素ガス、または、不活性ガス－酸素ガス混合気雰囲気下において、加熱温度が、例えば、６０℃以上、好ましくは、８０℃以上であり、例えば、１４０℃以下、好ましくは、１１０℃以下である。また、加熱時間が、例えば、４時間以上、好ましくは、８時間以上であり、例えば、２０時間以下、好ましくは、１２時間以下である。 As reaction conditions, in an atmosphere of oxygen gas or an inert gas-oxygen gas mixture, 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.
　これにより、ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体（すなわち、（ｂ２）で示される化合物）が得られる。 Thereby, an acid anhydride modified product of the caprolactone adduct of hydroxyalkyl (meth) acrylate (that is, a compound represented by (b2)) is obtained.
　（ｂ２）上記式（２）で示されるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体の酸価は、例えば、４０ｍｇＫＯＨ／ｇ以上、好ましくは、６０ｍｇＫＯＨ／ｇ以上であり、例えば、２８０ｍｇＫＯＨ／ｇ以下、好ましくは、１５０ｍｇＫＯＨ／ｇ以下である。 (B2) 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.
　（ｂ３）で示される化合物は、上記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物の、酸無水物変性体である。 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).
　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯ（ＣｍＨ２ｍＯ）ｎＨ　　　（３）
（式（３）中、Ｒ１は、水素原子、メチル基を示し、ｍは、２～４を示し、ｎは、１～１０を示す。）
　上記式（３）において、Ｒ１は、水素原子および／またはメチル基を示し、好ましくは、水素原子を示す。 CH 2 = C (R 1) COO (C m H 2m O) n H (3)
(In the formula (3), R1 represents a hydrogen atom or a methyl group, m represents 2 to 4, and n represents 1 to 10.)
In the above formula (3), R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
　また、上記式（３）において、ｍは、２以上であり、４以下、好ましくは、３以下である。 In the above formula (3), m is 2 or more, 4 or less, preferably 3 or less.
　すなわち、上記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物は、炭素数２～４のオキシアルキレン（ＣｍＨ２ｍＯ）を有している。 That is, 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.
　炭素数２～４のオキシアルキレンとしては、オキシエチレン（－ＣＨ２ＣＨ２Ｏ－）、オキシトリメチレン（－ＣＨ２ＣＨ２ＣＨ２Ｏ－）、オキシテトラメチレン（－ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ－）などの直鎖状オキシアルキレン、例えば、オキシプロピレン（－ＣＨ２ＣＨ（ＣＨ３）Ｏ－）、オキシブチレン（－ＣＨ２ＣＨ（ＣＨ２ＣＨ３）Ｏ－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）Ｏ－）などの分岐状オキシアルキレンなどが挙げられ、好ましくは、直鎖状オキシアルキレン、より好ましくは、オキシエチレンが挙げられる。 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.
　また、上記式（３）において、ｎは、（メタ）アクリル酸１モルに対するアルキレンオキサイドの平均付加モル数であり、１以上、好ましくは、２以上であり、１０以下、好ましくは、５以下である。 In the above formula (3), 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.
　（ｂ３）で示される化合物を得るには、例えば、まず、（メタ）アクリル酸と、アルキレンオキサイドとを反応（開環付加）させ、上記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物を得る。その後、上記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物と、酸無水物とを反応させる。 In order to obtain the compound represented by (b3), for example, first, (meth) acrylic acid and alkylene oxide are reacted (ring-opening addition), and the alkylene of (meth) acrylic acid represented by the above formula (3) is obtained. An oxide adduct is obtained. Thereafter, an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) is reacted with an acid anhydride.
　（メタ）アクリル酸は、アクリル酸および／またはメタアクリル酸であり、好ましくは、アクリル酸である。 (Meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.
　アルキレンオキサイドとしては、炭素数２～４のアルキレンオキサイドが挙げられ、具体的には、エチレンオキサイド、プロピレンオキサイド、トリメチレンオキサイド（オキセタン）、ブチレンオキサイドなどの炭素数２～４の環状エーテル化合物が挙げられる。 Examples of the alkylene oxide 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.
　これらアルキレンオキサイドは、単独使用または２種類以上併用することができる。 These alkylene oxides can be used alone or in combination of two or more.
　なお、アルキレンオキサイドが２種類以上併用される場合、その付加形態は特に制限されず、例えば、ランダム付加、ブロック付加などであってもよい。 In addition, when two or more types of alkylene oxide are used in combination, the addition form is not particularly limited, and may be, for example, random addition or block addition.
　アルキレンオキサイドとして、好ましくは、エチレンオキサイド、プロピレンオキサイドが挙げられ、より好ましくは、エチレンオキサイドが挙げられる。 The alkylene oxide is preferably ethylene oxide or propylene oxide, and more preferably ethylene oxide.
　（メタ）アクリル酸に、アルキレンオキサイドを付加させる方法としては、特に制限されず、公知の方法を採用することができる。 The method for adding alkylene oxide to (meth) acrylic acid is not particularly limited, and a known method can be employed.
　より具体的には、例えば、（メタ）アクリル酸とアルキレンオキサイドとを配合し、必要により、上記の触媒、および、上記の溶剤の存在下において、加熱および撹拌する。 More specifically, for example, (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.
　（メタ）アクリル酸とアルキレンオキサイドとの配合割合は、目的物（上記式（３）で示される化合物）の分子量、すなわち、（メタ）アクリル酸に対するアルキレンオキサイドの平均付加モル数ｎに応じて適宜設定される。 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.
　例えば、（メタ）アクリル酸１モルに対して、アルキレンオキサイドが、例えば、１モル以上、好ましくは、２モル以上であり、例えば、１０モル以下、好ましくは、５モル以下である。 For example, with respect to 1 mole of (meth) acrylic acid, 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.
　また、例えば、（メタ）アクリル酸１００質量部に対して、アルキレンオキサイドが、例えば、５０質量部以上、好ましくは、１００質量部以上であり、例えば、５０００質量部以下、好ましくは、１５００質量部以下である。 Further, for example, with respect to 100 parts by mass of (meth) acrylic acid, 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.
　また、反応条件としては、不活性ガス－酸素ガス混合気雰囲気下において、反応温度が、例えば、４０℃以上、好ましくは、１００℃以上であり、例えば、２４０℃以下、好ましくは、２００℃以下である。また、反応時間は、例えば、１時間以上、好ましくは、３時間以上であり、例えば、２０時間以下、好ましくは、１２時間以下である。 As the reaction conditions, 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.
　これにより、上記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物が得られる。 Thereby, an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) is obtained.
　（メタ）アクリル酸のアルキレンオキサイド付加物として、より具体的には、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、ポリトリメチレングリコールモノ（メタ）アクリレート、ポリブチレングリコールモノ（メタ）アクリレート、ポリテトラメチレングリコールモノ（メタ）アクリレート、ポリ（エチレングリコール－プロピレングリコール）モノ（メタ）アクリレート、ポリ（エチレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレートなどの水酸基末端ポリアルキレングリコールモノ（メタ）アクリレート、例えば、（モノ）エチレングリコールモノ（メタ）アクリレート、（モノ）プロピレングリコールモノ（メタ）アクリレート、（モノ）トリメチレングリコールモノ（メタ）アクリレート、（モノ）ブチレングリコールモノ（メタ）アクリレート、（モノ）テトラメチレングリコールモノ（メタ）アクリレートなどの水酸基末端モノアルキレングリコールモノ（メタ）アクリレートなどが挙げられる。 More specifically, as the 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) butylene glycol mono (meth) acrylate, (mono) tetramethylene glycol mono (meth) acrylate Examples thereof include terminal monoalkylene glycol mono (meth) acrylate.
　これら（メタ）アクリル酸のアルキレンオキサイド付加物は、単独使用または２種類以上併用することができる。 These alkylene oxide adducts of (meth) acrylic acid can be used alone or in combination of two or more.
　（メタ）アクリル酸のアルキレンオキサイド付加物として、好ましくは、水酸基末端ポリアルキレングリコールモノ（メタ）アクリレートが挙げられ、より好ましくは、ポリエチレングリコールモノ（メタ）アクリレートが挙げられる。 Preferred examples of the alkylene oxide adduct of (meth) acrylic acid include hydroxyl-terminated polyalkylene glycol mono (meth) acrylate, and more preferred is polyethylene glycol mono (meth) acrylate.
　なお、（メタ）アクリル酸のアルキレンオキサイド付加物は、市販品として入手することもできる。そのような市販品としては、例えば、ブレンマーＰＥシリーズ、ブレンマーＡＥシリーズ、ブレンマーＰＰシリーズ、ブレンマーＡＰシリーズ、ブレンマーＰＥＰシリーズ、ブレンマーＡＥＰシリーズ、ブレンマーＰＥＴシリーズ、ブレンマーＡＥＴシリーズ、ブレンマーＰＰＴシリーズ、ブレンマーＡＰＴシリーズ（いずれも、日本油脂製）などが挙げられる。これらは、単独使用または２種類以上併用することができる。 In addition, the alkylene oxide adduct of (meth) acrylic acid can also be obtained as a commercial item. Examples of such 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.
　そして、上記の（メタ）アクリル酸のアルキレンオキサイド付加物と、酸無水物とを反応させることにより、（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体（すなわち、（ｂ３）で示される化合物）を得ることができる。 Then, by reacting the alkylene oxide adduct of (meth) acrylic acid with an acid anhydride, the acid anhydride modified product of the alkylene oxide adduct of (meth) acrylic acid (ie, (b3)) Compound) can be obtained.
　酸無水物としては、上記した酸無水物（（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の製造において用いられる酸無水物）が挙げられ、好ましくは、ジカルボン酸一無水物が挙げられ、硬化物（後述）の硬度の観点から、より好ましくは、無水コハク酸、無水フタル酸が挙げられ、さらに好ましくは、無水コハク酸が挙げられる。 Examples of the acid anhydride include the acid anhydrides described above ((A) acid anhydrides used in the production of acid anhydride-modified products of polyfunctional (meth) acrylic compounds). Preferably, dicarboxylic acid monoanhydrides are used. From the viewpoint of the hardness of the cured product (described later), succinic anhydride and phthalic anhydride are more preferable, and succinic anhydride is more preferable.
　そして、（メタ）アクリル酸のアルキレンオキサイド付加物と、酸無水物との反応では、例えば、（メタ）アクリル酸のアルキレンオキサイド付加物と酸無水物とを配合し、必要に応じて、溶剤、触媒などの存在下において、加熱する。 And in the reaction of the alkylene oxide adduct of (meth) acrylic acid and the acid anhydride, for example, 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.
　溶剤としては、例えば、上記した有機溶剤（分散媒として上記した有機溶剤）、上記した水系溶剤（分散媒として上記した水系溶剤）などが挙げられる。これら溶剤は、単独使用または２種類以上併用することができる。溶剤として、好ましくは、（メタ）アクリル酸のアルキレンオキサイド付加物および酸無水物に対して不活性である溶剤が挙げられ、具体的には、カルボキシ基および水酸基を有しない溶剤が挙げられる。そのような溶剤として、好ましくは、有機溶剤、より好ましくは、ケトン系溶剤、さらに好ましくは、メチルイソブチルケトンが挙げられる。 Examples of the solvent 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. As 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. As such a solvent, an organic solvent is preferable, a ketone solvent is more preferable, and methyl isobutyl ketone is more preferable.
　触媒としては、例えば、上記した触媒（（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の製造において用いられる触媒）が挙げられる。これら触媒は、単独使用または２種類以上併用することができる。触媒として、好ましくは、アミン化合物が挙げられ、より好ましくは、Ｎ，Ｎ－ジメチルベンジルアミン、トリエチルアミン、トリブチルアミンが挙げられ、さらに好ましくは、トリエチルアミンが挙げられる。 Examples of the catalyst 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.
　（メタ）アクリル酸のアルキレンオキサイド付加物のカプロラクトン付加物と酸無水物との配合割合は、例えば、（メタ）アクリル酸のアルキレンオキサイド付加物中のヒドロキシル基に対する酸無水物中の無水カルボン酸基との当量比（無水カルボン酸基／ヒドロキシル基）が、例えば、０．５以上、好ましくは、０．６７以上であり、例えば、１以下、好ましくは、０．９１以下である。 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.
　また、反応条件としては、酸素雰囲気下、または、不活性ガス－酸素ガス混合気雰囲気下において、加熱温度が、例えば、６０℃以上、好ましくは、８０℃以上であり、例えば、１４０℃以下、好ましくは、１１０℃以下である。また、加熱時間が、例えば、４時間以上、好ましくは、８時間以上であり、例えば、２０時間以下、好ましくは、１２時間以下である。 As reaction conditions, in an oxygen atmosphere or an inert gas-oxygen gas mixture atmosphere, 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.
　これにより、（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体（すなわち、（ｂ３）で示される化合物）が得られる。 Thereby, an acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid (that is, a compound represented by (b3)) is obtained.
　（ｂ３）上記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体の酸価は、例えば、５５ｍｇＫＯＨ／ｇ以上、好ましくは、９５ｍｇＫＯＨ／ｇ以上であり、例えば、４００ｍｇＫＯＨ／ｇ以下、好ましくは、３００ｍｇＫＯＨ／ｇ以下である。 (B3) 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.
　これら（Ｂ）単官能（メタ）アクリル化合物は、単独使用または２種類以上併用することができる。 These (B) monofunctional (meth) acrylic compounds can be used alone or in combination of two or more.
　（Ｂ）単官能（メタ）アクリル化合物としては、金属微粒子分散液の分散安定性の向上を図る観点から、好ましくは、（ｂ１）で示す化合物が挙げられ、より好ましくは、（Ｂ）前記単官能（メタ）アクリル化合物が、上記式（１）で示され、ｎが１～３である（メタ）アクリル酸のカプロラクトン付加物を含有することが挙げられる。 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.
　また、（Ｂ）単官能（メタ）アクリル化合物としては、硬化膜（後述）の硬度の向上を図る観点から、好ましくは、（ｂ２）で示す化合物が挙げられ、より好ましくは、（Ｂ）前記単官能（メタ）アクリル化合物が、上記式（２）で示され、ｎが２～５であるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体を含有することが挙げられる。 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.
　また、（Ｂ）単官能（メタ）アクリル化合物としては、硬化膜（後述）の透明性の向上を図る観点から、好ましくは、（ｂ３）で示す化合物が挙げられ、より好ましくは、（Ｂ）前記単官能（メタ）アクリル化合物が、上記式（３）で示され、ｍが２～３であり、ｎが２～５である（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体を含有することが挙げられる。 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). An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid, wherein the monofunctional (meth) acrylic compound is represented by the above formula (3), m is 2 to 3, and n is 2 to 5 It may be included.
　金属微粒子分散剤において、（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体と、（Ｂ）単官能（メタ）アクリル化合物との含有割合は、それらの総量１００質量部に対して、（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体が、例えば、５質量部以上、好ましくは、１０質量部以上、より好ましくは、１５質量部以上であり、例えば、９５質量部以下、好ましくは、９０質量部以下である。また、（Ｂ）単官能（メタ）アクリル化合物が、例えば、５質量部以上、好ましくは、１０質量部以上であり、例えば、９５質量部以下、好ましくは、９０質量部以下、より好ましくは、８５質量部以下である。 In the metal fine particle dispersant, 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. (A) 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. Moreover, (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.
　そして、上記の金属微粒子と、上記の分散媒と、上記の金属微粒子分散剤とを、一括または順次配合し、混合することにより、金属微粒子分散液が得られる。 Then, 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.
　金属微粒子分散液における各成分の配合割合は、金属微粒子１００質量部に対して、金属微粒子分散剤が、例えば、１質量部以上、好ましくは、５質量部以上であり、例えば、２００質量部以下、好ましくは、１００質量部以下、さらに好ましくは、７０質量部以下である。また、金属微粒子分散液１００質量部に対して、金属微粒子が、例えば、０．５質量部以上、好ましくは、２．５質量部以上であり、例えば、５０質量部以下、好ましくは、４０質量部以下、より好ましくは、３０質量部以下である。 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.
　なお、分散媒の配合割合は、目的および用途に応じて、適宜設定されるが、例えば、金属微粒子１００質量部に対して、例えば、５０質量部以上、好ましくは、１５０質量部以上であり、例えば、２０００質量部以下、好ましくは、１０００質量部以下である。 The mixing ratio of the dispersion medium is appropriately set according to the purpose and application. For example, for 100 parts by mass of the metal fine particles, for example, 50 parts by mass or more, preferably 150 parts by mass or more, For example, it is 2000 parts by mass or less, preferably 1000 parts by mass or less.
　また、金属微粒子分散液は、さらに、バインダーを含有することができる。 In addition, the metal fine particle dispersion can further contain a binder.
　バインダーとしては、例えば、（メタ）アクリル樹脂、ポリビニルブチラール樹脂、ポリビニルアルコール樹脂、酢酸ビニル樹脂、ウレタン樹脂などの合成樹脂が挙げられる。これらバインダーは、単独使用または２種類以上併用することができる。 Examples of the binder 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.
　バインダーとして、密着性（常温）の向上を図る観点から、好ましくは、（メタ）アクリル樹脂が挙げられる。 As the binder, (meth) acrylic resin is preferably used from the viewpoint of improving adhesion (room temperature).
　（メタ）アクリル樹脂は、例えば、アルキル（メタ）アクリレートを含むモノマー成分の重合により、得ることができる。 (Meth) acrylic resin can be obtained, for example, by polymerization of a monomer component containing alkyl (meth) acrylate.
　アルキル（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、へプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルへキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、１－メチルトリデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート（ステアリル（メタ）アクリレート）、イソステアリル（メタ）アクリレート、エイコシル（メタ）アクリレート、ドコシル（メタ）アクリレート（ベヘニル（メタ）アクリレート）、テトラコシル（メタ）アクリレート、トリアコンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどの炭素数１～３０の直鎖状、分岐状または環状アルキルの（メタ）アクリレートなどが挙げられる。 Examples of the alkyl (meth) acrylate 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, decyl (meth) acrylate, dodecyl (meth) a Relate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, 1-methyltridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), isostearyl (meth) acrylate, 1 to 30 carbon atoms such as eicosyl (meth) acrylate, docosyl (meth) acrylate (behenyl (meth) acrylate), tetracosyl (meth) acrylate, triacontyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. Examples include linear, branched or cyclic alkyl (meth) acrylates.
　また、モノマー成分は、アルキル（メタ）アクリレートと共重合可能なその他のモノマーを含有することができる。 In addition, the monomer component can contain other monomers copolymerizable with alkyl (meth) acrylate.
　その他のモノマーとして、具体的には、例えば、芳香環含有モノマー、ヒドロキシル基含有モノマー、アニオン性基含有モノマーなどが挙げられる。 Specific examples of the other monomer include an aromatic ring-containing monomer, a hydroxyl group-containing monomer, and an anionic group-containing monomer.
　芳香環含有モノマーとしては、例えば、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、（メタ）アクリル酸フェノキシジエチレングリコール、ｏ－フェニルフェノキシエチル（メタ）アクリレート、フェノキシベンジル(メタ)アクリレートなどの芳香環含有（メタ）アクリレート、例えば、スチレン、α－メチルスチレンなどのスチレン系モノマーなどが挙げられる。 Examples of the aromatic ring-containing monomer 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 α-methylstyrene.
　モノマー成分が芳香環含有モノマーを含有する場合、その含有割合は、モノマー成分の総量に対して、例えば、１０質量％以上、好ましくは、２０質量％以上であり、例えば、９５質量％以下、好ましくは、８０質量％以下である。 When the monomer component contains an aromatic ring-containing monomer, 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.
　なお、モノマー成分が芳香環含有モノマーを含有する場合、（メタ）アクリル樹脂として、芳香環を含有する（メタ）アクリル樹脂が得られる。 In addition, when a monomer component contains an aromatic ring containing monomer, the (meth) acrylic resin containing an aromatic ring is obtained as a (meth) acrylic resin.
　ヒドロキシル基含有モノマーとしては、例えば、ヒドロキシメチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、１－メチル－２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートなどのヒドロキシル基含有（メタ）アクリレートが挙げられ、好ましくは、２－ヒドロキシエチル（メタ）アクリレートが挙げられる。 Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-methyl-2-hydroxyethyl (meth) acrylate, 2-hydroxy Examples include hydroxyl group-containing (meth) acrylates such as propyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, preferably 2-hydroxyethyl (meth) acrylate.
　モノマー成分がヒドロキシル基含有モノマーを含有する場合、ヒドロキシル基含有モノマーの含有割合は、モノマー成分の総量に対して、例えば、０．１質量％以上、好ましくは、１質量％以上であり、例えば、５０質量％以下、好ましくは、３０質量％以下である。 When the monomer component contains a hydroxyl group-containing monomer, 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.
　なお、モノマー成分がヒドロキシル基含有モノマーを含有する場合、（メタ）アクリル樹脂として、ヒドロキシル基を含有する（メタ）アクリル樹脂が得られる。 In addition, when the monomer component contains a hydroxyl group-containing monomer, a (meth) acrylic resin containing a hydroxyl group is obtained as the (meth) acrylic resin.
　アニオン性基含有モノマーにおいて、アニオン性基としては、例えば、カルボキシル基、リン酸基、スルホン酸基などが挙げられる。アニオン性基含有モノマーとして、具体的には、例えば、（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸などのα，β－不飽和カルボン酸またはその塩などのカルボキシル基含有モノマー、例えば、アシッドホスホオキシポリオキシプロピレングリコールモノ（メタ）アクリレート、アシッドホスホオキシエチル（メタ）アクリレート、モノ（２－ヒドロキシエチル（メタ）アクリレート）ホスフェートなどのリン酸基含有（メタ）アクリレートなどのリン酸基含有モノマー、例えば、２－アクリルアミド－２－メチルプロパンスルフォン酸などのスルホン酸基含有モノマーなどが挙げられる。 In the anionic group-containing monomer, 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 α, β-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.
　モノマー成分がアニオン性基含有モノマーを含有する場合、アニオン性基含有モノマーの含有割合は、モノマー成分の総量に対して、例えば、０．１質量％以上、好ましくは、１質量％以上であり、例えば、３０質量％以下、好ましくは、５質量％以下である。 When the monomer component contains an anionic group-containing monomer, 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.
　なお、モノマー成分がアニオン性基含有モノマーを含有する場合、（メタ）アクリル樹脂として、アニオン性基を含有する（メタ）アクリル樹脂が得られる。 In addition, when a monomer component contains an anionic group containing monomer, the (meth) acrylic resin containing an anionic group is obtained as a (meth) acrylic resin.
　さらに、その他のモノマーとしては、例えば、イソシアナトメチル（メタ）アクリレート、２－イソシアナトエチル（メタ）アクリレート、３－イソシアナトプロピル（メタ）アクリレート、１－メチル－２－イソシアナトエチル（メタ）アクリレート、２－イソシアナトプロピル（メタ）アクリレート、４－イソシアナトブチル（メタ）アクリレートなどのイソシアネート基含有（メタ）アクリルモノマーなどのイソシアネート基含有モノマー、例えば、グリシジル（メタ）アクリレート、アリルグリシジルエーテルなどのグリシジル基含有モノマー、例えば、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル系モノマーなどが挙げられる。 Further, as other monomers, for example, 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.
　これらその他のモノマーは、単独使用または２種類以上併用することができる。 These other monomers can be used alone or in combination of two or more.
　その他のモノマーとして、好ましくは、芳香環含有モノマー、ヒドロキシル基含有モノマーが挙げられ、より好ましくは、芳香環含有モノマーおよびヒドロキシル基含有モノマーの両方を含有することが挙げられる。 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.
　モノマー成分が、芳香環含有モノマーを含有していれば（すなわち、（メタ）アクリル樹脂が芳香環を含有する（メタ）アクリル樹脂であれば）、硬化膜（後述）の耐湿熱密着性の向上を図ることができる。 If 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.
　また、モノマー成分が、ヒドロキシル基含有モノマーを含有していれば（すなわち、（メタ）アクリル樹脂がヒドロキシル基を含有する（メタ）アクリル樹脂であれば）、後述の方法により、容易に（メタ）アクリル樹脂の側鎖に（メタ）アクリロイル基を導入することができ、硬化膜（後述）の耐湿熱密着性の向上を図ることができる。 Further, if 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.
　また、硬化膜（後述）の耐湿熱密着性の向上を図る観点から、好ましくは、アニオン性モノマーの含有割合は、モノマー成分の総量に対して５質量％以下であり、より好ましくは、モノマー成分がアニオン性基含有モノマーを含有しないことが挙げられる。 Further, from the viewpoint of improving the wet heat resistance of the cured film (described later), 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.
　また、モノマー成分が、上記その他のモノマー（アルキル（メタ）アクリレートを除くモノマー）を含有する場合、アルキル（メタ）アクリレートの含有割合は、モノマー成分の総量に対して、例えば、１０質量％以上、好ましくは、２０質量％以上であり、例えば、９０質量％以下、好ましくは、８０質量％以下である。 Moreover, when the monomer component contains the above-mentioned other monomers (monomers other than alkyl (meth) acrylate), 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.
　また、（メタ）アクリル樹脂を製造する方法は、特に制限されないが、例えば、公知の溶媒中において、上記のモノマー成分を上記割合で混合し、公知のラジカル重合開始剤（例えば、アゾ系化合物、パーオキサイド系化合物など）の存在下において加熱して、重合させる。 Further, the method for producing the (meth) acrylic resin is not particularly limited. For example, in a known solvent, 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.
　重合条件は、モノマー成分の処方やラジカル重合開始剤の種類などにより異なるが、例えば、重合温度が、３０℃以上、好ましくは、６０℃以上であり、例えば、１５０℃以下、好ましくは、１２０℃以下である。また、重合時間は、例えば、２時間以上、好ましくは、４時間以上であり、例えば、２０時間以下、好ましくは、８時間以下である。 The polymerization conditions vary depending on the monomer component prescription and the type of radical polymerization initiator. For example, 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.
　これにより、（メタ）アクリル樹脂が得られる。 Thereby, a (meth) acrylic resin is obtained.
　（メタ）アクリル樹脂の重量平均分子量（ＧＰＣ測定：ポリスチレン換算）は、例えば、２０００以上、好ましくは、３０００以上であり、例えば、１０００００以下、好ましくは、５００００以下、より好ましくは、１５０００以下である。 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. .
　また、（メタ）アクリル樹脂として、好ましくは、側鎖に（メタ）アクリロイル基を有する（メタ）アクリル樹脂が挙げられる。側鎖に（メタ）アクリロイル基を有する（メタ）アクリル樹脂は、例えば、以下の方法により得ることができる。 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.
　すなわち、上記の方法により得られる（メタ）アクリル樹脂は、ヒドロキシル基を有する場合がある。より具体的には、（メタ）アクリル樹脂の原料であるモノマー成分が、ヒドロキシル基含有モノマーを含有する場合、上記の重合により得られる（メタ）アクリル樹脂は、ヒドロキシル基を有する。 That is, 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.
　このような場合、例えば、ヒドロキシル基を有する（メタ）アクリル樹脂と、イソシアネート基含有（メタ）アクリルモノマーとを反応させることにより、（メタ）アクリル樹脂の側鎖に、（メタ）アクリロイル基を導入することができる。 In such a case, for example, 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.
　イソシアネート基含有（メタ）アクリルモノマーとしては、例えば、イソシアナトメチル（メタ）アクリレート、２－イソシアナトエチル（メタ）アクリレート、３－イソシアナトプロピル（メタ）アクリレート、１－メチル－２－イソシアナトエチル（メタ）アクリレート、２－イソシアナトプロピル（メタ）アクリレート、４－イソシアナトブチル（メタ）アクリレートなどが挙げられる。 Examples of isocyanate group-containing (meth) acrylic monomers 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.
　これらイソシアネート基含有（メタ）アクリルモノマーは、単独使用または２種類以上併用することができる。 These isocyanate group-containing (meth) acrylic monomers can be used alone or in combination of two or more.
　イソシアネート基含有（メタ）アクリルモノマーとして、好ましくは、２－イソシアナトエチル（メタ）アクリレートが挙げられる。 The isocyanate group-containing (meth) acrylic monomer is preferably 2-isocyanatoethyl (meth) acrylate.
　ヒドロキシル基を有する（メタ）アクリル樹脂と、イソシアネート基含有（メタ）アクリルモノマーとを反応させるには、特に制限されないが、例えば、ヒドロキシル基を有する（メタ）アクリル樹脂と、イソシアネート基含有（メタ）アクリルモノマーとを配合し、必要により公知の触媒および溶剤の存在下において、加熱する。 Although it does not restrict | limit especially in order to make the (meth) acrylic resin which has a hydroxyl group react with an isocyanate group containing (meth) acryl monomer, For example, 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.
　ヒドロキシル基を有する（メタ）アクリル樹脂と、イソシアネート基含有（メタ）アクリルモノマーとの配合割合は、ヒドロキシル基を有する（メタ）アクリル樹脂のヒドロキシル基１モルに対して、イソシアネート基含有（メタ）アクリルモノマーのイソシアネート基が、例えば、０．１モル以上、好ましくは、０．８モル以上であり、例えば、２．０モル以下、好ましくは、１．２モル以下である。 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.
　また、反応条件は、例えば、空気雰囲気下、反応温度が、例えば、４０℃以上、好ましくは、６０℃以上であり、例えば、２００℃以下、好ましくは、１５０℃以下である。また、反応時間は、例えば、１時間以上、好ましくは、２時間以上であり、例えば、２０時間以下、好ましくは、１２時間以下である。 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.
　なお、反応においては、必要により、上記した重合禁止剤を添加することもできる。 In the reaction, the above-described polymerization inhibitor can be added as necessary.
　重合禁止剤として、好ましくは、ｐ－メトキシフェノールが挙げられる。 The polymerization inhibitor is preferably p-methoxyphenol.
　重合禁止剤の配合割合は、ヒドロキシル基を有する（メタ）アクリル樹脂とイソシアネート基含有（メタ）アクリルモノマーとの総量１００質量部に対して、例えば、０．０００１質量部以上、好ましくは、０．０１質量部以上であり、例えば、１．０質量部以下、好ましくは、０．１質量部以下である。 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. For example, it is 1.0 part by mass or less, preferably 0.1 part by mass or less.
　これにより、ヒドロキシル基を有する（メタ）アクリル樹脂のヒドロキシル基と、イソシアネート基含有（メタ）アクリルモノマーのイソシアネート基とがウレタン反応する。 Thereby, 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.
　その結果、（メタ）アクリル樹脂の側鎖に、イソシアネート基含有（メタ）アクリルモノマーが結合され、側鎖末端に（メタ）アクリロイル基が導入される。 As a result, 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.
　なお、（メタ）アクリル樹脂の側鎖に（メタ）アクリロイル基を導入する方法は、上記の方法に制限されず、公知の方法を採用することができる。 In addition, 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.
　例えば、モノマー成分が、イソシアネート基含有モノマーを含有する場合、（メタ）アクリル樹脂は、イソシアネート基を有する。そのため、イソシアネート基を有する（メタ）アクリル樹脂と、ヒドロキシル基含有（メタ）アクリレートとをウレタン反応させることにより、（メタ）アクリル樹脂の側鎖に（メタ）アクリロイル基を導入することもできる。 For example, 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.
　また、例えば、モノマー成分がアニオン性基含有モノマー（例えば、カルボキシル基含有モノマーなど）を含有する場合、（メタ）アクリル樹脂は、アニオン性基（例えば、カルボキシル基など）を有する。そのため、アニオン性基を有する（メタ）アクリル樹脂と、グリシジル基含有（メタ）アクリレートとをエステル化反応させることにより、（メタ）アクリル樹脂の側鎖に（メタ）アクリロイル基を導入することもできる。 For example, 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. .
　また、例えば、モノマー成分がグリシジル基含有モノマーを含有する場合、（メタ）アクリル樹脂は、グリシジル基を有する。そのため、グリシジル基を有する（メタ）アクリル樹脂と、アニオン性基含有（メタ）アクリレート（例えば、カルボキシル基含有（メタ）アクリレートなど）とをエステル化反応させることにより、（メタ）アクリル樹脂の側鎖に（メタ）アクリロイル基を導入することもできる。 For example, 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.
　バインダーとして配合される（メタ）アクリル樹脂が、側鎖に（メタ）アクリロイル基を有していれば、硬化膜（後述）の耐湿熱密着性の向上を図ることができる。 If 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).
　側鎖に（メタ）アクリロイル基を有する（メタ）アクリル樹脂の、（メタ）アクリロイル基当量は、例えば、４００以上、好ましくは、８００以上であり、例えば、３００００以下、好ましくは、１００００以下である。 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. .
　なお、（メタ）アクリル基当量は、２重結合１ｍｏｌあたりのポリマー質量（２重結合当量）であると定義する。 In addition, (meth) acryl group equivalent is defined as the polymer mass per 1 mol of double bonds (double bond equivalent).
　金属微粒子分散液がバインダーを含有する場合、その含有割合は、金属微粒子分散液１００質量部に対して、例えば、１質量部以上、好ましくは、５質量部以上であり、例えば、５０質量部以下、好ましくは、３０質量部以下である。 When the metal fine particle dispersion contains a binder, 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.
　また、金属微粒子分散液は、必要に応じて、重合開始剤を含有することができる。 Further, the metal fine particle dispersion can contain a polymerization initiator as required.
　重合開始剤としては、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、１－シクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、４－メチルベンゾフェノン、ベンゾフェノン、２－ヒドロキシ－１－｛４－[４－（２－ヒドロキシ－２－メチルプロピオニル）－ベンジル]フェニル｝－２－メチル－プロパン－１－オンなどの光重合開始剤などが挙げられる。 Examples of the polymerization initiator 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) - benzyl] phenyl} -2-methyl - propan-1-one and the like photopolymerization initiator such as.
　これら重合開始剤は、単独使用または２種類以上併用することができる。 These polymerization initiators can be used alone or in combination of two or more.
　重合開始剤の配合割合は、金属微粒子分散剤の総量１００質量部に対して、例えば、１質量部以上、好ましくは、３質量部以上であり、例えば、１０質量部以下、好ましくは、７質量部以下である。 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.
　なお、上記のバインダーおよび重合開始剤を配合するタイミングは、特に制限されず、例えば、金属微粒子、溶剤および金属微粒子分散剤の混合時に、同時に配合してもよく、また、金属微粒子、溶剤および金属微粒子分散剤とは別途、バインダーおよび重合開始剤を一括または順次配合してもよい。 The timing of blending the binder and the polymerization initiator is not particularly limited. For example, 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.
　また、金属微粒子分散液の調製では、特に制限されず、金属微粒子、溶剤および金属微粒子分散剤（さらに、必要により配合されるバインダーおよび重合開始剤）を混合するときに、例えば、ペイントシェイカー、ロールミル、ボールミル、アトライター、サンドミル、ビーズミル、超音波分散機などの公知の分散機を用いることができる。 In addition, 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.
　金属微粒子分散液をコーティング剤（後述）として用いる場合には、硬化膜（後述）の透明性などの向上を図る観点から、好ましくは、ボールミル、ビーズミルが挙げられ、より好ましくは、ビーズミルが挙げられる。 When using 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. .
　分散機としてビーズミルを用いる場合には、ジルコニアビーズ、ガラスビーズなどの公知の分散メディアを用いることができる。 When using a bead mill as a disperser, known dispersion media such as zirconia beads and glass beads can be used.
　分散メディアのビーズ径は、特に制限されないが、例えば、１０μｍ以上であり、例えば、５００μｍ以下、好ましくは、１００μｍ以下である。なお、分散メディアの充填率は、目的および用途に応じて、適宜設定される。 The bead diameter of the dispersion medium is not particularly limited, but is, for example, 10 μm or more, for example, 500 μm or less, preferably 100 μm or less. Note that the filling rate of the dispersion medium is appropriately set according to the purpose and application.
　また、分散機としてビーズミルやボールミルを用いる場合には、上記の分散メディアにより金属微粒子を粉砕し、その平均粒子径を上記の範囲に調整することもできる。このような場合、分散機には、平均粒子径が上記の範囲よりも大きい金属微粒子を投入することができる。 In addition, when a bead mill or a ball mill is used as a disperser, 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. In such a case, metal fine particles having an average particle diameter larger than the above range can be introduced into the disperser.
　さらに、金属微粒子分散液には、例えば、顔料、乾燥剤、防錆剤、可塑剤、塗膜表面調整剤、酸化防止剤、紫外線吸収剤、さらには、上記した金属微粒子分散剤を除く分散剤（例えば、ソルビタン脂肪酸エステル、ポリエチレングリコール脂肪酸エステルなどのノニオン系界面活性剤など）などの各種添加剤を添加することができる。なお、添加剤の配合割合は、目的および用途に応じて、適宜設定される。 Further, 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. In addition, the mixture ratio of an additive is suitably set according to the objective and use.
　分散媒が有機溶剤および／または水系溶剤を含有する場合、金属微粒子分散液の不揮発分は、例えば、０．５質量％以上、好ましくは、３質量％以上であり、例えば、７０質量％以下、好ましくは、５０質量％以下、より好ましくは、４０質量％以下である。 When the dispersion medium contains an organic solvent and / or an aqueous solvent, 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.
　また、分散媒が反応性溶剤を含有する場合、金属微粒子分散液から、有機溶剤および／または水系溶剤を公知の方法で留去することができ、分散媒として反応性溶剤のみを含有することができる。 When the dispersion medium contains a reactive solvent, 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.
　また、このような場合において、反応性溶剤が不揮発成分である場合、金属微粒子分散液の不揮発分は、１００質量％であってもよい。 In such a case, when the reactive solvent is a nonvolatile component, the nonvolatile content of the metal fine particle dispersion may be 100% by mass.
　また、金属微粒子分散液中において、金属微粒子の粒径は、金属微粒子が一次粒子や二次粒子として存在しているので、これらの平均粒径（平均粒子径）として測定され、例えば、２００ｎｍ以下、好ましくは、５０ｎｍ以下であり、通常、１ｎｍ以上、好ましくは、３ｎｍ以上である。 Further, in the metal fine particle dispersion, 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.
　そして、このような金属微粒子分散液は、上記の金属微粒子分散剤を含むため、金属微粒子の分散安定性に優れ、また、耐湿熱密着性、硬度および透明性に優れる硬化膜を得ることができる。 And since 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. .
　硬化膜を得るには、例えば、金属微粒子分散液をコーティング剤として用い、公知の方法により基材に塗布および乾燥させた後、活性エネルギー線を照射して、硬化させる。 In order to obtain a cured film, for example, 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.
　基材としては、特に制限されず、例えば、ポリカーボネート、ポリメチルメタクリレート、ポリスチレン、ポリエステル（ポリエチレンテレフタレートなど）、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ノルボルネン系樹脂などのプラスチックや、例えば、金属、木材、紙、ガラス、スレートなどが挙げられる。 The substrate is not particularly limited. For example, polycarbonate, polymethyl methacrylate, polystyrene, polyester (polyethylene terephthalate, etc.), polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc. And plastics such as metal, wood, paper, glass, and slate.
　塗布方法としては、特に制限されず、例えば、ロールコーター、バーコーター、ドクターブレード、メイヤーバー、エアナイフなど、塗布の際に、一般的に使用される機器を用いた塗布や、スクリーン印刷、オフセット印刷、フレキソ印刷、はけ塗り、スプレー塗工、グラビア塗工、リバースグラビア塗工といった公知の塗布方法が採用される。 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.
　乾燥条件としては、乾燥温度が、例えば、４０℃以上、好ましくは、６０℃以上であり、例えば、１８０℃以下、好ましくは、１４０℃以下であり、乾燥時間が、例えば、１分以上、好ましくは、２分以上であり、例えば、６０分以下、好ましくは、３０分以下である。 As drying conditions, 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, and 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.
　また、乾燥後の膜厚は、例えば、５０ｎｍ以上、好ましくは、５００ｎｍ以上であり、例えば、１０μｍ以下、好ましくは、７μｍ以下である。 The film thickness after drying is, for example, 50 nm or more, preferably 500 nm or more, for example, 10 μm or less, preferably 7 μm or less.
　活性エネルギー線としては、例えば、紫外線、電子線などが挙げられる。 Examples of active energy rays include ultraviolet rays and electron beams.
　紫外線により硬化させる場合には、光源として、例えば、キセノンランプ、高圧水銀灯、メタルハライドランプなどを有する紫外線照射装置が用いられる。紫外線照射量、紫外線照射装置の光量、光源の配置などは、必要により適宜調整される。具体的には、高圧水銀灯を使用する場合には、例えば、金属微粒子分散液が塗布された基材を、光度８０～１０００ｍＷ／ｃｍ２程度の１灯に対して、搬送速度５～５０ｍ／分で搬送する。紫外線の照射量は、例えば、１００～１００００ｍＪ／ｃｍ２である。また、電子線により硬化させる場合には、金属微粒子分散液が塗布された基材を、例えば、１０～３００ｋＶの加速電圧を有する電子線加速装置にて、搬送速度５～５０ｍ／分で搬送する。 In the case of curing with ultraviolet rays, for example, 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. Specifically, when using 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 . In the case of curing with an electron beam, 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. .
　このような活性エネルギー線の照射によって、金属微粒子分散剤中の（メタ）アクリロイル基が架橋し、三次元構造を形成する。また、金属微粒子分散液が反応性溶剤を含有する場合、その反応性溶剤が架橋剤として作用する。すなわち、活性エネルギー線の照射によって、反応性溶剤のエチレン性不飽和結合が架橋する。 </ RTI> By irradiation with such active energy rays, the (meth) acryloyl group in the metal fine particle dispersant is cross-linked to form a three-dimensional structure. Moreover, when the metal fine particle dispersion contains a reactive solvent, 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.
　これにより、金属微粒子分散液の硬化物として、硬化膜が得られる。 Thereby, a cured film is obtained as a cured product of the metal fine particle dispersion.
　そして、得られる硬化膜は、上記の金属微粒子分散液を用いて得られるため、耐湿熱密着性、硬度および透明性に優れる。 And since 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.
　そのため、硬化膜は、例えば、発光ダイオード（ＬＥＤ）、レンズ、光学デバイスなどの光学部品、例えば、ファインセラミック、例えば、導電性フィルム、光学フィルムなどの機能性被膜などとして、各種産業製品において好適に用いられる。 Therefore, 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.
　次に、本発明を、実施例および比較例に基づいて説明するが、本発明は、下記の実施例によって限定されるものではない。なお、「部」および「％」は、特に言及がない限り、質量基準である。また、以下の記載において用いられる配合割合（含有割合）、物性値、パラメータなどの具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合（含有割合）、物性値、パラメータなど該当記載の上限値（「以下」、「未満」として定義されている数値）または下限値（「以上」、「超過」として定義されている数値）に代替することができる。 Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. “Part” and “%” are based on mass unless otherwise specified. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to.
　＜金属微粒子分散剤＞
　（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体
　　合成例１
　撹拌機、温度計、還流冷却管および混合気導入管が備わった１Ｌフラスコに、メチルイソブチルケトン（溶剤）３２７．２部、ジペンタエリスリトールペンタアクリレートおよびジペンタエリスリトールヘキサアクリレート混合物（東亞合成社製　アロニックスＭ４０３、ジペンタエリスリトールペンタアクリレート含有率５０～６０％）３００部、トリエチルアミン（触媒）０．３３部、および、ｐ－メトキシフェノール（重合禁止剤）０．１６部を仕込み、８０℃まで加熱撹拌した。 <Metal fine particle dispersant>
(A) Acid anhydride modified product of polyfunctional (meth) acryl compound Synthesis Example 1
Into a 1 L flask equipped with a stirrer, thermometer, reflux condenser and mixture gas inlet tube, 327.2 parts of methyl isobutyl ketone (solvent), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix made by Toagosei Co., Ltd.) M403, 300 parts of dipentaerythritol pentaacrylate content), 0.33 part of triethylamine (catalyst), and 0.16 part of p-methoxyphenol (polymerization inhibitor) were charged and heated to 80 ° C. with stirring. .
　次いで、無水コハク酸２７．２部を添加し、窒素－酸素混合気（酸素濃度７％）を導入して、８０℃で８時間保持した。その後、冷却し、固形分５０％、酸価２３ｍｇＫＯＨ／ｇの（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の溶液を得た。 Next, 27.2 parts of succinic anhydride was added, a nitrogen-oxygen mixture (oxygen concentration 7%) was introduced, and the mixture was kept at 80 ° C. for 8 hours. Then, it cooled and the solution of the acid anhydride modified body of (A) polyfunctional (meth) acrylic compound of 50% of solid content and an acid value of 23 mgKOH / g was obtained.
　　合成例２～３
　表１に示す配合処方に変更した以外は、合成例１と同様にして、（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の溶液（固形分５０％）を得た。 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　なお、表中の略号の詳細を下記する。 The details of the abbreviations in the table are as follows.
　アロニックスＭ４０３：ジペンタエリスリトールペンタアクリレートおよびジペンタエリスリトールヘキサアクリレート混合物、東亞合成社製、ジペンタエリスリトールペンタアクリレート含有率５０～６０％
　（ｂ２）ヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体
　　合成例４
　撹拌機、温度計、還流冷却管および混合気導入管が備わった５００ｍＬフラスコに、メチルイソブチルケトン（溶剤）１４３．５部、ヒドロキシエチルアクリレートのカプロラクトン付加物（ダイセル製　プラクセルＦＡ－１　カプロラクトン平均付加モル数：１モル）１００部、トリエチルアミン（触媒）０．１４部、および、ｐ－メトキシフェノール（重合禁止剤）０．０７部を仕込み、８０℃まで加熱撹拌した。 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.
　次いで、無水コハク酸４３．５部を添加し、窒素－酸素混合気（酸素濃度７％）を導入して、８０℃で８時間保持した。その後、冷却し、固形分５０％、酸価８５ｍｇＫＯＨ／ｇの（ｂ２）ヒドロキシエチル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体の溶液を得た。 Next, 43.5 parts of succinic anhydride was added, a nitrogen-oxygen mixture (oxygen concentration 7%) was introduced, and the mixture was kept at 80 ° C. for 8 hours. Thereafter, the mixture was cooled to obtain an acid anhydride modified product of caprolactone adduct of (b2) hydroxyethyl (meth) acrylate having a solid content of 50% and an acid value of 85 mgKOH / g.
　　合成例５～６
　表２に示す配合処方に変更した以外は、合成例４と同様にして、（ｂ２）ヒドロキシエチル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体の溶液（固形分５０％）を得た。 Synthesis Examples 5-6
Except having changed into the compounding prescription shown in Table 2, it carried out similarly to the synthesis example 4, and obtained the solution (solid content 50%) of the acid anhydride modified body of the caprolactone adduct of (b2) hydroxyethyl (meth) acrylate. .
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　なお、表中の略号の詳細を下記する。 The details of the abbreviations in the table are as follows.
　プラクセルＦＡ－１：商品名、ダイセル製、ヒドロキシエチルアクリレートのカプロラクトン付加物、カプロラクトン平均付加モル数：１モル
　プラクセルＦＡ－２Ｄ：商品名、ダイセル製、ヒドロキシエチルアクリレートのカプロラクトン付加物、カプロラクトン平均付加モル数：２モル
　プラクセルＦＡ－１０Ｌ：商品名、ダイセル製、ヒドロキシエチルアクリレートのカプロラクトン付加物、カプロラクトン平均付加モル数：１０モル
　（ｂ３）（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体
　　合成例７
　撹拌機、温度計、還流冷却管および混合気導入管が備わった５００ｍＬフラスコに、メチルイソブチルケトン（溶剤）１８６．２部、２－ヒドロキシエチルアクリレート（大阪有機化学工業製）１００部、トリエチルアミン（触媒）０．１９部、および、ｐ－メトキシフェノール（重合禁止剤）０．０９部を仕込み、８０℃まで加熱撹拌した。 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 Chemical Industry), triethylamine (catalyst) ) 0.19 part and 0.09 part of p-methoxyphenol (polymerization inhibitor) were added and the mixture was heated and stirred to 80 ° C.
　次いで、無水コハク酸８６．２部を添加し、窒素－酸素混合気（酸素濃度７％）を導入して、８０℃で８時間保持した。その後、冷却し、固形分５０％、酸価６４ｍｇＫＯＨ／ｇの（ｂ３）（メタ）アクリル酸のエチレンオキサイド付加物の酸無水物変性体の溶液を得た。 Next, 86.2 parts of succinic anhydride was added, a nitrogen-oxygen mixture (oxygen concentration 7%) was introduced, and the mixture was kept at 80 ° C. for 8 hours. Thereafter, the mixture was cooled to obtain an acid anhydride modified product of (b3) (meth) acrylic acid ethylene oxide adduct having a solid content of 50% and an acid value of 64 mgKOH / g.
　　合成例８～９
　表３に示す配合処方に変更した以外は、合成例７と同様にして、（ｂ３）（メタ）アクリル酸のプロピレンオキサイド付加物の酸無水物変性体の溶液（固形分５０％）を得た。 Synthesis Examples 8-9
Except having changed into the compounding prescription shown in Table 3, it carried out similarly to the synthesis example 7, and obtained the solution (solid content 50%) of the acid anhydride modified body of the propylene oxide adduct of (b3) (meth) acrylic acid. .
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　なお、表中の略号の詳細を下記する。 The details of the abbreviations in the table are as follows.
　ブレンマーＡＥ－２００：商品名、日本油脂製、アクリル酸のエチレンオキサイド付加物、アルキレンオキサイド平均付加モル数：４．５モル
　ブレンマーＡＰ－４００：商品名、日本油脂製、アクリル酸のプロピレンオキサイド付加物、アルキレンオキサイド平均付加モル数：６モル
　＜バインダー＞
　合成例１０
　攪拌機、コンデンサー、温度計、窒素導入管および滴下ロートを備えたフラスコに、メチルイソブチルケトン１００部を入れ、窒素雰囲気下で１００℃まで昇温した。 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.
　一方、メチルメタクリレート１０部、ｎ－ブチルアクリレート１０部、ヒドロキシエチルメタクリレート１０部、ベンジルメタクリレート７０部、および、重合開始剤としてのアゾビス－２－メチルブチロニトリル５部を混合し、モノマー混合液を調製した。 On the other hand, 10 parts of methyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of hydroxyethyl methacrylate, 70 parts of benzyl methacrylate, and 5 parts of azobis-2-methylbutyronitrile as a polymerization initiator were mixed to prepare a monomer mixture. Prepared.
　そして、メチルイソブチルケトンが入ったフラスコに、モノマー混合液を３時間かけて滴下し、次いで、３時間熟成反応させた。 Then, the monomer mixture was dropped into the flask containing methyl isobutyl ketone over 3 hours, and then aged for 3 hours.
　これにより、ヒドロキシル基を有する（メタ）アクリル樹脂を得た。 Thereby, a (meth) acrylic resin having a hydroxyl group was obtained.
　その後、反応温度を８０℃に設定し、雰囲気条件を窒素雰囲気から空気雰囲気に切り換え、２－イソシアナトエチルアクリレート（カレンズＡＯＩ、昭和電工製）５部、および、メチルイソブチルケトン５部、重合禁止剤としてのｐ－メトキシフェノールを０．１部加え、４時間反応させた。 Thereafter, the reaction temperature was set to 80 ° C., the 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.
　これにより、固形分５０％の、側鎖に（メタ）アクリロイル基を有する（メタ）アクリル樹脂の溶液を得た。（メタ）アクリル樹脂の（メタ）アクリロイル基当量は約３０００であった。 Thereby, a solution of a (meth) acrylic resin having a (meth) acryloyl group in the side chain and having a solid content of 50% was obtained. The (meth) acryloyl group equivalent of the (meth) acrylic resin was about 3000.
　合成例１１
　表４に示す配合処方に変更した以外は、合成例１０と同様にして、側鎖に（メタ）アクリロイル基を有する（メタ）アクリル樹脂の溶液（固形分５０％）を得た。 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.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　＜金属微粒子分散液および硬化膜＞
　実施例１
　合成例１で得られた（Ａ）多官能（メタ）アクリル化合物の酸無水物変性体の溶液（固形分５０％）が１６．８部となり、（ｂ１）（メタ）アクリル酸のカプロラクトン付加物としてのアロニックスＭ－５３００（東亜合成化学工業製、固形分１００％）が１．４部となり、金属微粒子としてのジルコニア（第一稀元素株式会社製　ＵＥＰ－１００サンカジルコニウム、平均一次粒子径１５ｎｍ）が２８部となり、分散媒としてのメチルイソブチルケトンが５３．８部となり、重合開始剤としてのＩＲＧＡＣＵＲＥ１８４（ＢＡＳＦ製　１－ヒドロキシシクロヘキシルフェニルケトン）が０．４９部となるように、各成分を混合し、金属微粒子分散液を得た。 <Metal fine particle dispersion and cured film>
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) Were 28 parts, methyl isobutyl ketone as a dispersion medium was 53.8 parts, and IRGACURE 184 (BASF 1-hydroxycyclohexyl phenyl ketone) as a polymerization initiator was 0.49 parts. A metal fine particle dispersion was obtained.
　その後、得られた金属微粒子分散液を、基材としてのポリエチレンテレフタレート（ＰＥＴ）フィルム（東レ製　ＵＨ－１３　厚さ１２５μｍ）に対して、バーコーターで乾燥後の膜厚が１μｍとなるように塗布し、８０℃において２分間乾燥させた。 Thereafter, the obtained fine metal particle dispersion was applied to a polyethylene terephthalate (PET) film (UH-13, 125 μm thick, manufactured by Toray) so that the film thickness after drying with a bar coater would be 1 μm. And dried at 80 ° C. for 2 minutes.
　次いで、紫外線照射装置（日本電池社製　装置名ＣＳＯＴ－４０）の高圧水銀灯によって、３００ｍＪ／ｃｍ２および２４０ｍＷ／ｃｍ２の紫外線を照射し、塗膜を硬化させ、基材および硬化膜の積層体を得た。 Subsequently, 300 mJ / cm 2 and 240 mW / cm 2 of ultraviolet rays were irradiated by a high pressure mercury lamp of an ultraviolet irradiation device (product name: CSOT-40, manufactured by Nihon Battery Co., Ltd.), the coating film was cured, and a laminate of the substrate and the cured film Got.
　実施例２～１５および比較例１～５
　表５～８に示す配合処方に変更した以外は、実施例１と同様にして、金属微粒子分散液と、基材および硬化膜の積層体とを得た。 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.
　＜評価＞
　実施例、比較例などにおいて得られる金属微粒子分散液および硬化膜を、以下の方法で評価した。その結果を、表５～８に併せて示す。 <Evaluation>
The metal fine particle dispersions and cured films obtained in Examples and Comparative Examples were evaluated by the following methods. The results are also shown in Tables 5-8.
　（１）金属微粒子分散液の分散性
　金属微粒子分散液を２３℃において静置し、金属微粒子の分散性について目視により確認した。評価の基準を下記する。
Ａ：３ヶ月後にも沈降物が確認されなかった。
Ｂ：３ヶ月後には、少しの沈降物が確認された。
Ｃ：１週間後に、沈降物が確認された。
Ｄ：１日後に、沈降物が確認された。 (1) Dispersibility of metal fine particle dispersion 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.
　（２）硬度
　硬化膜の表面を、スチールウール＃００００にて、幅４０ｍｍ以上となるように、以下に記載の荷重で１０往復磨耗した。その後、基材（ＰＥＴフィルム）の裏面に黒テープを貼り、三波長蛍光灯下にて傷の有無を確認した。評価の基準を下記する。
Ａ＋＋：２００ｇ／ｃｍ２荷重で傷が確認されなかった。
Ａ＋：１００ｇ／ｃｍ２荷重で傷が確認されず２００ｇ／ｃｍ２荷重で傷が確認された。
Ａ　：１００ｇ／ｃｍ２荷重で傷が１～５本確認された。
Ｂ　：１００ｇ／ｃｍ２荷重で傷が６～１０本確認された。
Ｃ　：１００ｇ／ｃｍ２荷重で傷が１１本以上確認された。 (2) Hardness The surface of the cured film was subjected to 10 reciprocating wear with steel wool # 0000 with a load described below so that the width was 40 mm or more. Thereafter, a black tape was attached to the back surface of the substrate (PET film), and the presence or absence of scratches was confirmed under a three-wavelength fluorescent lamp. The criteria for evaluation are as follows.
A ++: No scratch was observed at a load of 200 g / cm 2 .
A +: Scratches were not confirmed at 100 g / cm 2 load, but scratches were confirmed at 200 g / cm 2 load.
A: 1 to 5 scratches were confirmed at 100 g / cm 2 load.
B: 6 to 10 scratches were confirmed at a load of 100 g / cm 2 .
C: 11 or more scratches were confirmed at 100 g / cm 2 load.
　（３）透明性（ＨＡＺＥ）
　基材および硬化膜の積層体を、常態（２３℃、相対湿度５０％）において４０時間放置した後、ヘイズメーター（日本電色工業製、濁度計ＮＤＨ５０００）によりヘイズを測定した。ヘイズの測定はＪＩＳ　Ｋ　７１３６「透明材料のヘイズの求め方」（２０００年版）に準じた。 (3) Transparency (HAZE)
After leaving the laminated body of a base material and a cured film for 40 hours in a normal state (23 degreeC, 50% of relative humidity), haze was measured with the haze meter (Nippon Denshoku Industries make, turbidimeter NDH5000). The haze measurement was in accordance with JIS K 7136 “How to determine the haze of a transparent material” (2000 version).
　なお、測定では、硬化膜側の面から光を照射して測定した。 In the measurement, light was irradiated from the surface on the cured film side.
　また、測定サンプルとして、一辺５０ｍｍの正方形の硬化膜を１０サンプル準備し、それぞれ１回ずつ、合計１０回測定した。そして、各測定における平均値を、ヘイズ値とした。そして、得られたヘイズ値から透明性を評価した。評価の基準を下記する。
Ａ＋：ヘイズ値１．０％未満。
Ａ　：ヘイズ値１．０％以上１．８％未満。
Ｂ　：ヘイズ値１．８％以上２．３％未満。
Ｃ　：ヘイズ値２．３％以上。 Moreover, 10 samples of a square cured film having a side of 50 mm were prepared as measurement samples, and each measurement was performed once, for a total of 10 times. And the average value in each measurement was made into the haze value. And transparency was evaluated from the obtained haze value. The criteria for evaluation are as follows.
A +: Haze value is less than 1.0%.
A: Haze value of 1.0% or more and less than 1.8%.
B: Haze value 1.8% or more and less than 2.3%.
C: Haze value 2.3% or more.
　（４）耐湿熱密着性
　基材および硬化膜の積層体を、湿度８５％、温度８５℃に制御した恒温恒湿機に５００時間保管した後、湿度５０％、温度２３℃の恒温恒湿室に１２時間保管することにより、積層体を湿熱試験した。 (4) Moisture and heat resistant adhesion After storing the laminate of the substrate and the cured film for 500 hours in a constant temperature and humidity controller controlled at 85% humidity and 85 ° C., a constant temperature and humidity chamber at 50% humidity and 23 ° C. The laminate was subjected to a wet heat test by storing for 12 hours.
　そして、湿熱試験後の積層体の硬化膜に対して、ＪＩＳ　Ｋ　５６００－５－６第５部－第６節：付着性（１９９９年）に記載のクロスカット法に準じて、１ｍｍ幅の切り込みを入れ、密着性を評価した。評価基準を下記する。
Ａ＋：カットのふちが完全に滑らかで、どの格子の目にも剥がれが確認されなかった。
Ａ　：カットの交差点において小さな剥がれ（剥がれ率５％未満）が確認された。
Ｂ　：剥がれ（剥がれ率５％以上１５％未満）が確認された。
Ｃ　：大きく剥がれ（剥がれ率１５％以上）が確認された。 Then, a 1 mm wide cut was made on the cured film of the laminate after the wet heat test according to the cross-cut method described in JIS K 5600-5-6 Part 5—Section 6: Adhesion (1999). The adhesion was evaluated. The evaluation criteria are as follows.
A +: The edge of the cut was completely smooth, and no peeling was observed in any lattice eye.
A: Small peeling (peeling rate less than 5%) was confirmed at the intersection of the cuts.
B: Peeling (peeling rate 5% or more and less than 15%) was confirmed.
C: Large peeling (peeling rate of 15% or more) was confirmed.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　なお、表中の略号の詳細を下記する。 The details of the abbreviations in the table are as follows.
　アロニックスＭ４０３：商品名アロニックスＭ４０３、東亞合成社製、ジペンタエリスリトールペンタアクリレートおよびジペンタエリスリトールヘキサアクリレート混合物（ジペンタエリスリトールペンタアクリレート含有率５０～６０％）
　ＤＡ７３０１：商品名ディスパロンＤＡ－７３０１、楠本化成社製、高分子量ポリエステル酸のアマイドアミン塩の７５質量％溶液（溶剤：アルキルシクロヘキサン／プロピレングリコールモノメチルエーテルアセテート）
　アロニックスＭ５３００：商品名アロニックスＭ－５３００、東亜合成製、ω－カルボキシカプロラクトンモノアクリレート
　ジルコニア：第一稀元素株式会社製　ＵＥＰ－１００サンカジルコニウム、平均一次粒子径１５ｎｍ
　アルミナ：大明化学工業株式会社製　ＴＭ－３００、粒子径１０ｎｍ
　二酸化ケイ素：ｅｖｏｎｉｋ社製　ＡＥＲＯＳＩＬＲ８１２、平均一次粒子径７ｎｍ
　ＭＩＢＫ：メチルイソブチルケトン
　ＩＲＧＡＣＵＲＥ１８４：商品名、ＢＡＳＦ製、重合開始剤、１－ヒドロキシシクロヘキシルフェニルケトン
なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示に過ぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記請求の範囲に含まれる。 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., ω-carboxycaprolactone monoacrylate Zirconia: manufactured by Daiichi Rare Element Co., Ltd. UEP-100 Sanka zirconium, average primary particle size 15 nm
Alumina: TM-300, manufactured by Daimei Chemical Co., Ltd., particle size 10nm
Silicon dioxide: AEROSIR 812 manufactured by evonik, average primary particle size 7 nm
MIBK: methyl isobutyl ketone IRGACURE 184: trade name, manufactured by BASF, polymerization initiator, 1-hydroxycyclohexyl phenyl ketone The above invention is provided as an exemplary embodiment of the present invention. Should not be interpreted. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.
　本発明の金属微粒子分散液および硬化膜は、光学部品、ファインセラミック、導電性フィルム、光学フィルムなどの機能性被膜などとして好適に用いられる。 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.

Claims (6)

  1. 　金属微粒子と、
    　分散媒と、
    　金属微粒子分散剤と
    を含有する金属微粒子分散液であって、
    　前記金属微粒子分散剤は、
    　（Ａ）２つ以上の（メタ）アクリロイル基、および、少なくとも１つのヒドロキシル基を有する、多官能（メタ）アクリル化合物の酸無水物変性体と、
    　（Ｂ）１つの（メタ）アクリロイル基を有する単官能（メタ）アクリル化合物とを含有し、
    　　前記単官能（メタ）アクリル化合物は、下記（ｂ１）～（ｂ３）で示される化合物の少なくとも１種を含有することを特徴とする、金属微粒子分散液。
    　　（ｂ１）下記式（１）で示される（メタ）アクリル酸のカプロラクトン付加物。
    　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯ［Ｏ（ＣＨ２）５ＣＯ］ｎＯＨ　　　（１）
    （式（１）中、Ｒ１は、水素原子、メチル基を示し、ｎは、１～１０を示す。）
    　　（ｂ２）下記式（２）で示されるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体。
    　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２Ｏ［ＣＯ（ＣＨ２）５Ｏ］ｎＨ　　　（２）
    （式（２）中、Ｒ１は、水素原子、メチル基を示し、Ｒ２は、エチレン基、プロピレン基およびテトラメチレン基からなる群から選択される少なくとも１種を示し、ｎは、１～１０を示す。）
    　　（ｂ３）下記式（３）で示される（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体。
    　　　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯ（ＣｍＨ２ｍＯ）ｎＨ　　　（３）
    （式（３）中、Ｒ１は、水素原子、メチル基を示し、ｍは、２～４を示し、ｎは、１～１０を示す。）     Metal fine particles,
    A dispersion medium;
    A metal fine particle dispersion containing a metal fine particle dispersant,
    The fine metal particle dispersant is
    (A) an acid anhydride modified product of a polyfunctional (meth) acryl compound having two or more (meth) acryloyl groups and at least one hydroxyl group;
    (B) a monofunctional (meth) acrylic compound having one (meth) acryloyl group,
    The metal fine particle dispersion, wherein the monofunctional (meth) acrylic compound contains 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).
    CH 2 = C (R 1) CO [O (CH 2) 5 CO] n OH (1)
    (In the formula (1), R 1 represents a hydrogen atom or a methyl group, and n represents 1 to 10.)
    (B2) An acid anhydride modified product of a caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the following formula (2).
    CH 2 = C (R 1 ) COOR 2 O [CO (CH 2 ) 5 O] n H (2)
    (In 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, and n represents 1 to 10 is shown.)
    (B3) An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).
    CH 2 = C (R 1) COO (C m H 2m O) n H (3)
    (In the formula (3), R1 represents a hydrogen atom or a methyl group, m represents 2 to 4, and n represents 1 to 10.)
  2. 　（Ｂ）前記単官能（メタ）アクリル化合物が、
    　　上記式（１）で示され、ｎが１～３である（メタ）アクリル酸のカプロラクトン付加物を含有することを特徴とする、請求項１に記載の金属微粒子分散液。     (B) The monofunctional (meth) acrylic compound is
    The metal fine particle dispersion according to claim 1, comprising a caprolactone adduct of (meth) acrylic acid represented by the above formula (1), wherein n is 1 to 3.
  3. 　（Ｂ）前記単官能（メタ）アクリル化合物が、
    　　上記式（２）で示され、ｎが２～５であるヒドロキシアルキル（メタ）アクリレートのカプロラクトン付加物の酸無水物変性体を含有することを特徴とする、請求項１に記載の金属微粒子分散液。     (B) The monofunctional (meth) acrylic compound is
    2. The fine metal particle dispersion according to claim 1, comprising an acid anhydride modified product of a caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the above formula (2), wherein n is 2 to 5. liquid.
  4. 　（Ｂ）前記単官能（メタ）アクリル化合物が、
    　　上記式（３）で示され、ｍが２～３であり、ｎが２～５である（メタ）アクリル酸のアルキレンオキサイド付加物の酸無水物変性体を含有することを特徴とする、請求項１に記載の金属微粒子分散液。     (B) The monofunctional (meth) acrylic compound is
    An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3), wherein m is 2 to 3, and n is 2 to 5, Item 4. The fine metal particle dispersion according to Item 1.
  5. 　さらに、バインダーを含有し、
    　前記バインダーが、（メタ）アクリル樹脂を含有する
    ことを特徴とする、請求項１に記載の金属微粒子分散液。     In addition, it contains a binder,
    The metal fine particle dispersion according to claim 1, wherein the binder contains a (meth) acrylic resin.
  6. 　請求項１に記載の金属微粒子分散液の硬化物であることを特徴とする、硬化膜。 A cured film, which is a cured product of the metal fine particle dispersion according to claim 1.
PCT/JP2017/010491 2016-03-31 2017-03-15 Fine-metal-particle dispersion and cured film WO2017169802A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2017532194A JP6196750B1 (en) 2016-03-31 2017-03-15 Metal fine particle dispersion and cured film
CN201780000674.3A CN107960085B (en) 2016-03-31 2017-03-15 Metal particle dispersion liquid and cured film
KR1020177017648A KR101811187B1 (en) 2016-03-31 2017-03-15 Fine metal particle dispersed liquid and cured film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016071535 2016-03-31
JP2016-071535 2016-03-31

Publications (1)

Publication Number Publication Date
WO2017169802A1 true WO2017169802A1 (en) 2017-10-05

Family

ID=59965421

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/010491 WO2017169802A1 (en) 2016-03-31 2017-03-15 Fine-metal-particle dispersion and cured film

Country Status (4)

Country Link
KR (1) KR101811187B1 (en)
CN (1) CN107960085B (en)
TW (1) TWI615445B (en)
WO (1) WO2017169802A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019112555A (en) * 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 Active energy ray-curable composition and index matching layer and laminate using the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62265249A (en) * 1986-02-20 1987-11-18 ユニオン・カ−バイド・コ−ポレ−シヨン Lactone acrylate having carboxyl as end group
JPH09316369A (en) * 1996-03-28 1997-12-09 Dainippon Printing Co Ltd Antibacterial ionizing-radiation-curable coating material and antibacterial clear film
WO2007138946A1 (en) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. Metal oxide composition, cured film and laminate
WO2014157588A1 (en) * 2013-03-29 2014-10-02 Hoya株式会社 Coating composition
JP2015044905A (en) * 2013-08-27 2015-03-12 昭和電工株式会社 Resin composition, transparent film, and production method and use of the same
WO2016035603A1 (en) * 2014-09-05 2016-03-10 住友化学株式会社 Curable composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4229214B2 (en) * 2006-11-09 2009-02-25 Ｄｉｃ株式会社 Active energy ray-curable aqueous resin composition, active energy ray-curable coating material, method for forming cured coating film, and article

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62265249A (en) * 1986-02-20 1987-11-18 ユニオン・カ−バイド・コ−ポレ−シヨン Lactone acrylate having carboxyl as end group
JPH09316369A (en) * 1996-03-28 1997-12-09 Dainippon Printing Co Ltd Antibacterial ionizing-radiation-curable coating material and antibacterial clear film
WO2007138946A1 (en) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. Metal oxide composition, cured film and laminate
WO2014157588A1 (en) * 2013-03-29 2014-10-02 Hoya株式会社 Coating composition
JP2015044905A (en) * 2013-08-27 2015-03-12 昭和電工株式会社 Resin composition, transparent film, and production method and use of the same
WO2016035603A1 (en) * 2014-09-05 2016-03-10 住友化学株式会社 Curable composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019112555A (en) * 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 Active energy ray-curable composition and index matching layer and laminate using the same
JP7102727B2 (en) 2017-12-25 2022-07-20 東洋インキＳｃホールディングス株式会社 Active energy ray-curable composition and index matching layer and laminate using it
JP2022132323A (en) * 2017-12-25 2022-09-08 東洋インキＳｃホールディングス株式会社 Active energy ray-curable composition and index matching layer and laminate using the same

Also Published As

Publication number Publication date
TWI615445B (en) 2018-02-21
CN107960085B (en) 2019-03-26
TW201807081A (en) 2018-03-01
CN107960085A (en) 2018-04-24
KR101811187B1 (en) 2017-12-20

Similar Documents

Publication Publication Date Title
KR101852314B1 (en) Coating agent and coating film
JP5996086B2 (en) Metal fine particle dispersant, metal fine particle dispersion and cured film
JP5187471B2 (en) Fluorine-containing curable resin, active energy ray-curable composition and cured product thereof
JP5555089B2 (en) Urethane (meth) acrylate and photocurable resin composition containing the same
JP4750473B2 (en) Active energy ray curable resin composition and coating agent using the same
JP2021169613A (en) Curable composition, cured article and laminate
KR20160023555A (en) Epoxy(meth)acrylate compound, resin composition containing the same and cured product thereof, color filter and display device
JP2006213802A (en) Active energy ray-curable resin composition
WO2017169802A1 (en) Fine-metal-particle dispersion and cured film
JP6196750B1 (en) Metal fine particle dispersion and cured film
KR102501500B1 (en) Active energy ray curing type hard coat agent and laminate
JP4974547B2 (en) Active energy ray-curable hard coat resin composition
JP5819481B2 (en) Urethane (meth) acrylate and photocurable resin composition containing the same
KR102181205B1 (en) Fluorinated urethane (meth)acrylate, curable composition, and antireflective film
JP5892799B2 (en) Urethane (meth) acrylate that forms a cured product having elongation and excellent scratch resistance, and a photocurable resin composition containing the same
JP2008297293A (en) Urethane (meth)acrylate compound, active energy radiation-curing composition and its application
JP6465487B2 (en) (Meth) acrylate compound, active energy ray-curable resin composition containing the same, and cured product thereof
JP5605305B2 (en) Polymerizable fluorine surface-modified silica particles and active energy ray-curable composition using the same
JP2022020989A (en) Active energy ray-curable coating agent and coated building material using the same
TWI706807B (en) Metal particle dispersant, metal particle dispersion, coating agent, cured film and binder resin
WO2015025835A1 (en) Multilayer film, optical element, polarizing plate and image display device
KR20240083821A (en) Coating compositions and laminates
JP2023158770A (en) Active energy ray-curable coating agent and method for producing laminate
JP2007270044A (en) Hard coat resin composition for cellulose acetate film

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2017532194

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020177017648

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17774346

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17774346

Country of ref document: EP

Kind code of ref document: A1