WO2017110951A1 - Curable composition, method for curing same, and cured product obtained thereby - Google Patents

Curable composition, method for curing same, and cured product obtained thereby Download PDF

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Publication number
WO2017110951A1
WO2017110951A1 PCT/JP2016/088250 JP2016088250W WO2017110951A1 WO 2017110951 A1 WO2017110951 A1 WO 2017110951A1 JP 2016088250 W JP2016088250 W JP 2016088250W WO 2017110951 A1 WO2017110951 A1 WO 2017110951A1
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Prior art keywords
curable composition
compound
epoxy compound
oxetane
cationic
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PCT/JP2016/088250
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French (fr)
Japanese (ja)
Inventor
一輝 長坂
泰延 大野
和彦 松土
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株式会社Adeka
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Publication of WO2017110951A1 publication Critical patent/WO2017110951A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used

Definitions

  • the present invention relates to a curable composition, a method for curing the same, and a cured product and an adhesive obtained thereby.
  • the curable composition is excellent in adhesion and has a low viscosity, useful for optical films, and the cured product.
  • the present invention relates to a method and a cured product obtained thereby.
  • a curable composition made of epoxy resin has excellent adhesion to various substrates, and a cured product obtained by curing an epoxy resin with a curing agent has heat resistance, chemical resistance, electrical properties, and mechanical properties. Etc. are relatively excellent, and are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.
  • Patent Document 1 proposes a cationic polymerizable adhesive containing an oxetane compound, an aromatic glycidyl ether, and a cationic polymerization initiator.
  • the photocurable composition containing the photocurable component containing the epoxy compound which has an alicyclic epoxy group, a silane coupling agent, and a photocationic polymerization initiator is proposed as an adhesive agent for polarizing plates.
  • Patent Document 3 proposes a cationic adhesive containing an epoxy compound, an oxetane compound and a photocationic polymerization initiator as a cationic adhesive for polarizing plates.
  • Patent Document 4 proposes a cationically polymerizable composition containing an aromatic epoxy compound and an aliphatic epoxy compound or an alicyclic epoxy compound as a cationically polymerizable organic substance.
  • JP 2010-229392 A JP 2013-210445A Special table 2014-505274 gazette International Publication No. 2015/005211
  • an object of the present invention is to provide a curable composition having excellent adhesiveness and low viscosity, useful for optical films, a curing method thereof, and a cured product obtained thereby.
  • the curable composition of the present invention is a curable composition containing 100 parts by weight of the cationic curable component (A) and 0.1 to 15 parts by weight of the cationic polymerization initiator (B),
  • the cationic curable component (A) is characterized by comprising an alicyclic epoxy compound (A1), an aliphatic epoxy compound (A2), and an oxetane compound (A3) as essential components.
  • the curable composition of the present invention preferably further contains an aromatic epoxy compound (A3) as the cationic curable component (A).
  • the curable composition of the present invention further contains 0.1 to 15 parts by mass of a silane coupling agent having an epoxy group (excluding the cationic curable component (A)) (C). Is preferred.
  • the alicyclic epoxy compound (A1) is preferably 1 to 30% by mass in 100% by mass of the cationic curable component (A).
  • the alicyclic epoxy compound (A1) is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 7-oxabicyclo [4.
  • the oxetane compound (A3) is 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, xylylene bisoxetane, It is preferably at least one selected from the group of 3-ethyl-3- (3-ethyl-3-oxetanylmethyloxymethyl) oxetane.
  • the curing method of the curable composition of the present invention is characterized in that the cured product of the present invention is cured by irradiation with active energy rays or heating.
  • the cured product of the present invention is characterized by comprising the curable composition of the present invention.
  • the present invention it is possible to provide a curable composition having excellent adhesiveness and low viscosity, useful for optical films, a curing method thereof, and a cured product obtained thereby.
  • the curable composition of the present invention contains 100 parts by weight of the cationic curable component (A) and 0.1 to 15 parts by weight of the cationic polymerization initiator (B) (hereinafter referred to as “component (A)” and “ (B) component "). Preferably, it further contains 0.1 to 15 parts by mass of a silane coupling agent having an epoxy group (excluding the cationic curable component (A)) (C).
  • the component (A) has the alicyclic epoxy compound (A1), the aliphatic epoxy compound (A2) and the oxetane compound (A3) as essential components, and preferably an aromatic epoxy. Contains compound (A4).
  • components (A) to (C) will be described in detail.
  • the component (A) used in the cured product of the present invention is a compound that is polymerized or cross-linked by a cationic polymerization initiator activated by energy ray irradiation or heating, and an alicyclic epoxy compound (A1),
  • the aliphatic epoxy compound (A2) and the oxetane compound (A3) are essential components, and preferably contains an aromatic epoxy compound (A4).
  • alicyclic epoxy compound (A1) can be obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent.
  • examples include cyclohexene oxide and cyclopentene oxide-containing compounds.
  • hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane Carboxylate is preferable from the viewpoint of improving adhesion.
  • alicyclic epoxy compound (A1) commercially available products can be used.
  • Celoxide 2021P Celoxide 2081, Celoxide 2000, Celoxide 3000, Cyclomer M100 (manufactured by Daicel); CYRACURE UVR-6128 (Dow) ⁇ Chemical Co.).
  • the viscosity of the alicyclic epoxy compound (A1) is 1 to 60% by mass, particularly 5 to 50% by mass with respect to 100% by mass of the component (A). It is preferable because coatability and reactivity are improved.
  • the aliphatic epoxy compound (A2) refers to an epoxy compound that is not classified into the alicyclic epoxy compound (A1) or the aromatic epoxy compound (A4) described later.
  • Specific examples of the aliphatic epoxy compound include aliphatic alcohols.
  • Monofunctional epoxy compounds such as glycidyl etherified products, glycidyl esters of alkylcarboxylic acids, polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyfunctional epoxies such as polyglycidyl esters of aliphatic long-chain polybasic acids Compounds.
  • Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane.
  • Glycidyl ether of alcohol and aliphatic such as propylene glycol, trimethylolpropane, glycerin
  • Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to polyhydric alcohols include diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, epoxidized polybutadiene, and the like.
  • a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because viscosity, coating property, and reactivity are improved, and further ethylene glycol diglycidyl.
  • Ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether is preferred.
  • aliphatic epoxy compound (A2) commercially available products can be used.
  • the aliphatic epoxy compound (A2) is 5 to 40% by mass, particularly 20 to 30% by mass with respect to 100% by mass of the component (A). This is preferable because the property and reactivity are improved.
  • Examples of the oxetane compound (A3) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis.
  • oxetane compound (A3) commercially available products having a cationic polymerizable monomer as a main component can be used.
  • 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether manufactured by Maruzen Petrochemical Co., Ltd.
  • Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 manufactured by Toagosei Co., Ltd.
  • etanacol OXBP manufactured by Ube Industries
  • the oxetane compound (A3) is 10 to 40% by mass, particularly 20 to 30% by mass with respect to 100% by mass of the component (A). This is preferable because the reactivity is improved.
  • the aromatic epoxy compound (A4) refers to an epoxy compound having a plurality of epoxy groups and containing an aromatic ring.
  • the polyfunctional aromatic epoxy compound include at least one aromatic compound such as phenol, cresol, and butylphenol.
  • Glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol; alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol
  • polyglycidyl ethers of phenols polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups
  • polyglycidyl ethers of polyphenols polyglycidyl esters of benzoic acids
  • polybasic acid polys It is preferable to contain at least one selected from the group of glycidyl esters from the viewpoint of reducing the viscosity of the curable composition.
  • aromatic epoxy compound a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound, or a phenol novolac type epoxy compound is preferable because of excellent curability.
  • aromatic epoxy compound (A4) commercially available products can be used.
  • the aromatic epoxy compound (A4) is 20 to 60% by mass, particularly 30 to 50% by mass, with respect to 100% by mass of the component (A), to improve the curability. It is preferable from the viewpoint.
  • a vinyl ether compound (A5) may be further added as the cationic curable component (A).
  • the vinyl ether compound (A5) include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, Examples include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, and the like.
  • the alicyclic epoxy compound (A1), the aliphatic epoxy compound (A2), the oxetane compound (A3), the aromatic epoxy compound (A4), and the vinyl ether compound ( The proportion of A5) used is 1 to 30% by mass of the alicyclic epoxy compound (A1), 5 to 40% by mass of the aliphatic epoxy compound (A2), 100% by mass of the component (A), and the oxetane compound (A3). 10 to 40% by mass, 20 to 60% by mass of the aromatic epoxy compound (A4), and 1 to 15 parts by mass of the vinyl ether compound (A5) improve the viscosity, coating property, reactivity and curability. Therefore, it is preferable.
  • the component (B) used in the curable composition of the present invention may be any compound as long as it can release a substance that initiates cationic polymerization by energy ray irradiation or heating, but preferably , A double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof.
  • a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays or a derivative thereof.
  • Representative examples of such compounds include the following general formula: [A] r + [B] r- And cation and anion salts represented by the formula:
  • the cation [A] r + is preferably onium, and the structure thereof is, for example, the following general formula [(R 2 ) a Q] r + Can be expressed as
  • R 2 is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms.
  • a is an integer of 1 to 5.
  • the a R 2 s are independent and may be the same or different.
  • the anion [B] r- is preferably a halide complex, and the structure thereof is, for example, the following general formula: [LY b ] r- Can be expressed as
  • L is a metal or metalloid which is a central atom of a halide complex
  • B P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc , V, Cr, Mn, Co, and the like.
  • Y is a halogen atom.
  • b is an integer of 3 to 7.
  • anion [LY b ] r- of the general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4 ) ⁇ , hexa Examples thereof include fluorophosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroarsenate (AsF 6 ) ⁇ , hexachloroantimonate (SbCl 6 ) ⁇ and the like.
  • the anion [B] r- is represented by the following general formula: [LY b-1 (OH)] r-
  • the thing of the structure represented by can also be used preferably. L, Y, and b are the same as described above.
  • Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethylsulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , and toluenesulfonate anion.
  • Trinitrobenzenesulfonate anion camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
  • onium salts it is particularly preferable to use the following aromatic onium salts (i) to (iii).
  • aromatic onium salts (i) to (iii) In the curable composition of the present invention, one of these may be used alone, or two or more may be used in combination.
  • aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
  • Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
  • sulfonium salts such as sulfonium cations represented by the following group I or group II and hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, etc.
  • aromatic iodonium salts aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoints of practical use and improvement of photosensitivity.
  • the use ratio of the component (B) relative to the component (A) is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention.
  • the component (B) can be 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass. If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.
  • ⁇ Silane coupling agent having epoxy group (C)> (C) component used for this invention is a silane coupling agent which has an epoxy group, However, What corresponds to (A) component is not contained.
  • an epoxy functional alkoxysilane can be used, for example, ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -glycidyloxypropyltriethoxysilane, ⁇ -glycidyloxypropylmethyldimethoxysilane, ⁇ -glycidyl. Examples thereof include oxypropylmethyldiethoxysilane and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • component (C) commercially available products may be used.
  • D2632, G0261, G0210, T2675 manufactured by Tokyo Chemical Industry Co., Ltd.
  • KBM-303, KBM-402, KBM-403, KBE-402, KBE-403 Shin-Etsu Silicone Co., Ltd.
  • component (C) used is not particularly limited.
  • component (C) is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, relative to 100 parts by weight of component (A). it can.
  • a sensitizer and / or a sensitization aid can be used in the curable composition of the present invention as necessary.
  • the sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength indicated by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B).
  • the sensitization aid is a compound that further promotes the action of the sensitizer.
  • Sensitizers and sensitizers include anthracene compounds and naphthalene compounds.
  • anthracene compound examples include those represented by the following formula (1).
  • R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents an alkyl group.
  • anthracene compound represented by the above formula (1) include the following compounds.
  • naphthalene compound examples include those represented by the following formula (2).
  • R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • naphthalene compound represented by the above formula (2) include the following compounds.
  • 4-methoxy-1-naphthol 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1- Ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene and the like.
  • the use ratio of the sensitizer and the sensitization aid to the component (A) is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention.
  • the curable composition of the present invention can also improve the properties of the cured product by using a thermoplastic organic polymer as necessary.
  • the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methyl.
  • examples thereof include a methacrylate copolymer, a glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.
  • a solvent that can dissolve or disperse the components (A), (B), and (C) that are usually used without any particular limitation can be used.
  • methyl ethyl ketone, methyl Ketones such as amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol Ether solvents such as monomethyl ether and dipropylene glycol dimethyl ether; esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate
  • curable composition of the present invention other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and the like are colored as necessary unless the effects of the present invention are impaired.
  • resin additives such as a flow regulator and an adhesion promoter can be added.
  • the curable composition of the present invention can be applied on a supporting substrate by a known means such as a roll coater, a curtain coater, various types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
  • the material for the support substrate is not particularly limited and those usually used can be used.
  • inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose Polyester; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Poly-1,4-cyclohexanedimethylene terephthalate, Polyethylene-1,2-diphenoxyethane -4,4'-dicarboxylate, polyester such as polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene, etc.
  • Polyolefins Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polyoxy Polymer materials such as ethylene, norbornene resin, and cycloolefin polymer (COP) can be used.
  • the support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • curable composition of the present invention and the cured product include optical materials such as optical films, adhesives, glasses, and imaging lenses, paints, coating agents, lining agents, inks, resists, and liquids. Resist, printing plate, insulating varnish, insulating sheet, laminated board, printed circuit board, semiconductor device, LED package, liquid crystal inlet, organic EL, optical element, electrical insulation, electronic component, separation membrane, etc.
  • Sealant molding material, putty, glass fiber impregnating agent, sealant, passivation film for semiconductors and solar cells, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device
  • Lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets used for screens of projection televisions, etc.
  • Backlights using a sheet can include an optical lens such as a micro lens, an optical element, an optical connector, an optical waveguide, a for optical fabricating casting agent.
  • a metal, wood, rubber, plastic, glass, ceramic product or the like is used as a substrate, and the curable composition of the present invention is applied to the substrate by the above-described means. And curing by light irradiation or heating.
  • a transparent support provided with various layers such as an undercoat layer, an antireflection layer, a hard coat layer, a gas barrier layer, a lubricating layer, and an adhesive layer as necessary may be mentioned. .
  • an inorganic material is used for the substrate, and a film coated by the above method, or vacuum deposition method, ion plating method, plasma CVD method, ion assist method, reactive sputtering method, chemical vapor phase It is also possible to use a laminate of films prepared by various vapor deposition methods such as a growth method.
  • the film thickness is, for example, 5 to 300 nm, although it varies depending on the type of inorganic material used.
  • the vapor deposition film may be formed only on one side of the substrate, or may be formed on both sides of the substrate.
  • the inorganic material examples include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), indium (In), sodium (Na), and boron (B ), Titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), antimony (Sb) and other oxides, indium-tin composite oxide (abbreviated as ITO), antimony-tin composite oxide A composite oxide such as a product (abbreviated as ATO) can be used.
  • examples of energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies and the like, and ultraviolet rays are most preferable economically.
  • examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
  • the conditions for curing the curable composition of the present invention by heating are 70 to 250 ° C. and 1 to 100 minutes.
  • pre-baking PAB
  • PEB pressurization and post-baking
  • baking may be performed at several different temperatures.
  • the heating conditions vary depending on the type and mixing ratio of each component. For example, it is 70 to 180 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Thereafter, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.
  • Examples 1 to 7, Comparative Examples 1 to 4 The components shown in Tables 1 and 2 were thoroughly mixed to obtain compositions of Examples 1 to 7 and Comparative Examples 1 to 4, respectively.
  • As the component (A), the following compounds (A1-1), (A2-1) to (A2-3), (A3-1), (A3-2) and (A4-1) are used, and
  • Compound A1-1 Celoxide 2021P (alicyclic epoxy: manufactured by Daicel)
  • Compound A2-1 1,4-butanediol diglycidyl ether
  • Compound A2-2 Adekaglycilol ED-523T (aliphatic epoxy: manufactured by ADEKA)
  • Compound A2-2 Neopentyl glycol diglycidyl ether compound A3-1: Aron oxetane OXT-221 (Oxetane: manufactured by Toagosei Co., Ltd.)
  • Compound A3-2 Aron oxetane OXT-101 (oxetane: manufactured by Toagosei Co., Ltd.)
  • Compound A4-1 Adeka Resin EP-4100 (Bisphenol A type polyfunctional epoxy: manufactured by ADEKA)
  • Compound C-1 KBM-403 (silane coupling agent: manufactured by Shin-Etsu Silicone)
  • Compound C-2 KBE-403 (Silane coupling agent: Shin-Etsu Silicone)
  • Adhesion 1 Each of the obtained curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was applied to a single glass substrate (5 cm ⁇ 10 cm) with a bar coater # 3, and then COP ( A test piece was obtained by laminating with a cycloolefin polymer) film and using a metal halide lamp to irradiate energy of 1000 mJ / cm 2 at an illuminance of 250 mW / cm 2 and adhere. The obtained test piece was subjected to a 90 degree peel test. The results are shown in Tables 1 and 2.
  • composition 2 Each of the obtained compositions of Examples 6 and 7 and Comparative Example 4 was applied to a single TAC film, and then bonded to a COP (cycloolefin polymer) film subjected to corona discharge treatment using a laminator.
  • a test piece was obtained by applying an energy of 1000 mJ / cm 2 using an electrodeless ultraviolet light lamp and bonding. The obtained test piece was subjected to a 90 degree peel test. The results are shown in Tables 1 and 2.
  • the curable composition of the present invention has excellent adhesion and low viscosity.

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Abstract

Provided is a curable composition that is useful in an optical film, has excellent adhesive properties, and has a low viscosity, as well as a method for curing said composition, and a cured product obtained through said method. The curable composition comprises 100 parts by mass of a cationic curable component (A), and 0.1 to 15 parts by mass of a cationic polymerization initiator (B), wherein the cationic curable component (A) includes, as essential components thereof, an alicyclic epoxy compound (A1), an aliphatic epoxy compound (A2), and an oxetane compound (A3). The cationic curable component (A) preferably further contains an aromatic epoxy compound (A4).

Description

硬化性組成物、その硬化方法、これにより得られる硬化物Curable composition, curing method thereof, and cured product obtained thereby
　本発明は、硬化性組成物、その硬化方法、これにより得られる硬化物および接着剤に関し、詳しくは、光学フィルムに有用な、密着性に優れ、かつ、低粘度の硬化性組成物、その硬化方法、これにより得られる硬化物に関する。 The present invention relates to a curable composition, a method for curing the same, and a cured product and an adhesive obtained thereby. Specifically, the curable composition is excellent in adhesion and has a low viscosity, useful for optical films, and the cured product. The present invention relates to a method and a cured product obtained thereby.
　エポキシ樹脂等からなる硬化性組成物は、各種基材への接着性に優れており、また、エポキシ樹脂を硬化剤で硬化させた硬化物は、耐熱性、耐薬品性、電気特性、機械特性等が比較的優れているため、インキ、塗料、各種コーティング剤、接着剤、光学部材等の分野において用いられている。 A curable composition made of epoxy resin has excellent adhesion to various substrates, and a cured product obtained by curing an epoxy resin with a curing agent has heat resistance, chemical resistance, electrical properties, and mechanical properties. Etc. are relatively excellent, and are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.
　例えば、特許文献１では、オキセタン化合物と芳香族グリシジルエーテルとカチオン重合開始剤とを含有するカチオン重合性接着剤が提案されている。また、特許文献２では、偏光板用接着剤として、脂環式エポキシ基を有するエポキシ化合物を含む光硬化性成分、シランカップリング剤および光カチオン重合開始剤を含有する光硬化性組成物が提案されている。さらに、特許文献３では、偏光板用カチオン性接着剤として、エポキシ化合物、オキセタン化合物および光カチオン性重合開始剤を含有するカチオン性接着剤が提案されている。さらにまた、特許文献４では、カチオン重合性有機物質として、芳香族エポキシ化合物、および脂肪族エポキシ化合物または脂環式エポキシ化合物を含有するカチオン重合性組成物が提案されている。 For example, Patent Document 1 proposes a cationic polymerizable adhesive containing an oxetane compound, an aromatic glycidyl ether, and a cationic polymerization initiator. Moreover, in patent document 2, the photocurable composition containing the photocurable component containing the epoxy compound which has an alicyclic epoxy group, a silane coupling agent, and a photocationic polymerization initiator is proposed as an adhesive agent for polarizing plates. Has been. Further, Patent Document 3 proposes a cationic adhesive containing an epoxy compound, an oxetane compound and a photocationic polymerization initiator as a cationic adhesive for polarizing plates. Furthermore, Patent Document 4 proposes a cationically polymerizable composition containing an aromatic epoxy compound and an aliphatic epoxy compound or an alicyclic epoxy compound as a cationically polymerizable organic substance.
特開２０１０－２２９３９２号公報JP 2010-229392 A 特開２０１３－２１０４４５号公報JP 2013-210445A 特表２０１４－５０５２７４号公報Special table 2014-505274 gazette 国際公開２０１５／００５２１１号公報International Publication No. 2015/005211
　しかしながら、特許文献１～４に記載されている樹脂組成物を光学フィルム用に用いた場合、特許文献１～４に記載されている樹脂組成物では、密着性や塗工性を高度にバランスさせることは難しく、光学フィルムに有用な新たな硬化性組成物が求められているのが現状である。 However, when the resin composition described in Patent Documents 1 to 4 is used for an optical film, the resin composition described in Patent Documents 1 to 4 highly balances adhesion and coating properties. This is difficult, and there is a demand for new curable compositions useful for optical films.
　そこで、本発明の目的は、光学フィルムに有用な、密着性に優れ、かつ、低粘度の硬化性組成物、その硬化方法、これにより得られる硬化物を提供することにある。 Therefore, an object of the present invention is to provide a curable composition having excellent adhesiveness and low viscosity, useful for optical films, a curing method thereof, and a cured product obtained thereby.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、硬化性組成物中におけるカチオン硬化性成分の組成を調整することにより、密着性および塗工性を高度にバランスできることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that adhesion and coating properties can be highly balanced by adjusting the composition of the cationic curable component in the curable composition. The invention has been completed.
　すなわち、本発明の硬化性組成物は、カチオン硬化性成分（Ａ）１００質量部、カチオン重合開始剤（Ｂ）０．１～１５質量部を含有する硬化性組成物であって、
　前記カチオン硬化性成分（Ａ）が、脂環式エポキシ化合物（Ａ１）、脂肪族エポキシ化合物（Ａ２）、およびオキセタン化合物（Ａ３）を必須成分とすることを特徴とするものである。 That is, the curable composition of the present invention is a curable composition containing 100 parts by weight of the cationic curable component (A) and 0.1 to 15 parts by weight of the cationic polymerization initiator (B),
The cationic curable component (A) is characterized by comprising an alicyclic epoxy compound (A1), an aliphatic epoxy compound (A2), and an oxetane compound (A3) as essential components.
　本発明の硬化性組成物においては、前記カチオン硬化性成分（Ａ）として、さらに芳香族エポキシ化合物（Ａ３）を含有することが好ましい。また、本発明の硬化性組成物においては、さらに、エポキシ基を有するシランカップリング剤（ただし、カチオン硬化性成分（Ａ）を除く。）（Ｃ）０．１～１５質量部を含有することが好ましい。さらに、本発明の硬化性組成物においては、前記カチオン硬化性成分（Ａ）１００質量％中、前記脂環式エポキシ化合物（Ａ１）が１～３０質量％であることが好ましい。さらにまた、本発明の硬化性組成物においては、前記脂環式エポキシ化合物（Ａ１）が、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、７－オキサビシクロ［４．１．０］ヘプタン，ポリ［オキシ－（１－オキソ－１，６－ヘキサンジイル）］誘導体、ヘキサン二酸ビス［（７－オキサビシクロ［４．１．０］ヘプタン－３－イル）メチル］、１，２－エポキシ－４－ビニルシクロヘキサン、３，４－エポキシシクロヘキシルメチルメタアクリレートおよびリモネンジオキシドの群より選択される少なくとも一種であることが好ましい。また、本発明の硬化性組成物においては、前記オキセタン化合物（Ａ３）が、３－エチル－３－（ヘキシロキシメチル）オキセタン、３－エチル－３－（ヒドロキシメチル）オキセタン、キシリレンビスオキセタン、３－エチル－３－（３－エチル－３－オキセタニルメチルオキシメチル）オキセタンの群より選択される少なくとも一種であることが好ましい。 The curable composition of the present invention preferably further contains an aromatic epoxy compound (A3) as the cationic curable component (A). The curable composition of the present invention further contains 0.1 to 15 parts by mass of a silane coupling agent having an epoxy group (excluding the cationic curable component (A)) (C). Is preferred. Furthermore, in the curable composition of the present invention, the alicyclic epoxy compound (A1) is preferably 1 to 30% by mass in 100% by mass of the cationic curable component (A). Furthermore, in the curable composition of the present invention, the alicyclic epoxy compound (A1) is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 7-oxabicyclo [4. 1.0] heptane, poly [oxy- (1-oxo-1,6-hexanediyl)] derivative, bis ([7-oxabicyclo [4.1.0] heptan-3-yl) methyl] hexane diacid 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, and limonene dioxide are preferable. Further, in the curable composition of the present invention, the oxetane compound (A3) is 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, xylylene bisoxetane, It is preferably at least one selected from the group of 3-ethyl-3- (3-ethyl-3-oxetanylmethyloxymethyl) oxetane.
　また、本発明の硬化性組成物の硬化方法は、本発明の硬化物を、活性エネルギー線の照射または加熱により硬化させることを特徴とするものである。 The curing method of the curable composition of the present invention is characterized in that the cured product of the present invention is cured by irradiation with active energy rays or heating.
　さらに、本発明の硬化物は、本発明の硬化性組成物からなることを特徴とするものである。 Furthermore, the cured product of the present invention is characterized by comprising the curable composition of the present invention.
　本発明によれば、光学フィルムに有用な、密着性に優れ、かつ、低粘度の硬化性組成物、その硬化方法、これにより得られる硬化物を提供することができる。 According to the present invention, it is possible to provide a curable composition having excellent adhesiveness and low viscosity, useful for optical films, a curing method thereof, and a cured product obtained thereby.
　以下、本発明の硬化性組成物、その硬化方法、これにより得られる硬化物および接着剤について、詳細に説明する。 Hereinafter, the curable composition of the present invention, its curing method, and the cured product and adhesive obtained thereby will be described in detail.
　本発明の硬化性組成物は、カチオン硬化性成分（Ａ）１００質量部、カチオン重合開始剤（Ｂ）０．１～１５質量部を含有する（以下、それぞれ、「（Ａ）成分」および「（Ｂ）成分」とも称す）。好ましくは、さらに、エポキシ基を有するシランカップリング剤（ただし、カチオン硬化性成分（Ａ）を除く。）（Ｃ）０．１～１５質量部を含有する。本発明の硬化性組成物においては、（Ａ）成分は、脂環式エポキシ化合物（Ａ１）、脂肪族エポキシ化合物（Ａ２）およびオキセタン化合物（Ａ３）を必須成分とし、好ましくは、さらに芳香族エポキシ化合物（Ａ４）を含有する。以下、（Ａ）～（Ｃ）成分について、詳細に説明する。 The curable composition of the present invention contains 100 parts by weight of the cationic curable component (A) and 0.1 to 15 parts by weight of the cationic polymerization initiator (B) (hereinafter referred to as “component (A)” and “ (B) component "). Preferably, it further contains 0.1 to 15 parts by mass of a silane coupling agent having an epoxy group (excluding the cationic curable component (A)) (C). In the curable composition of the present invention, the component (A) has the alicyclic epoxy compound (A1), the aliphatic epoxy compound (A2) and the oxetane compound (A3) as essential components, and preferably an aromatic epoxy. Contains compound (A4). Hereinafter, components (A) to (C) will be described in detail.
＜カチオン硬化性成分（Ａ）＞
　本発明の硬化物に使用する（Ａ）成分は、エネルギー線照射または加熱により活性化したカチオン重合開始剤により高分子化または、架橋反応を起こす化合物であり、脂環式エポキシ化合物（Ａ１）、脂肪族エポキシ化合物（Ａ２）およびオキセタン化合物（Ａ３）を必須成分とし、好ましくは、芳香族エポキシ化合物（Ａ４）を含有する。 <Cation curable component (A)>
The component (A) used in the cured product of the present invention is a compound that is polymerized or cross-linked by a cationic polymerization initiator activated by energy ray irradiation or heating, and an alicyclic epoxy compound (A1), The aliphatic epoxy compound (A2) and the oxetane compound (A3) are essential components, and preferably contains an aromatic epoxy compound (A4).
　脂環式エポキシ化合物（Ａ１）の具体例としては、少なくとも１個の脂環式環を有する多価アルコールのポリグリシジルエーテル化物またはシクロヘキセンやシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られるシクロヘキセンオキサイドやシクロペンテンオキサイド含有化合物が挙げられる。例えば、水素添加ビスフェノールＡジグリシジルエーテル、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－１－メチルシクロヘキシル－３，４－エポキシ－１－メチルヘキサンカルボキシレート、６－メチル－３，４－エポキシシクロヘキシルメチル－６－メチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－３－メチルシクロヘキシルメチル－３，４－エポキシ－３－メチルシクロヘキサンカルボキシレート、３，４－エポキシ－５－メチルシクロヘキシルメチル－３，４－エポキシ－５－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、プロパン－２，２－ジイル－ビス（３，４－エポキシシクロヘキサン）、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、ジシクロペンタジエンジエポキサイド、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ－２－エチルヘキシル、１－エポキシエチル－３，４－エポキシシクロヘキサン、１，２－エポキシ－２－エポキシエチルシクロヘキサン、７－オキサビシクロ［４．１．０］ヘプタン，ポリ［オキシ－（１－オキソ－１，６－ヘキサンジイル）］誘導体、ヘキサン二酸ビス［（７－オキサビシクロ［４．１．０］ヘプタン－３－イル）メチル］、α－ピネンオキシド、リモネンジオキシド、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、１，２－エポキシ－４－ビニルシクロヘキサン、３，４－エポキシシクロヘキシルメチルメタアクリレート等が挙げられる。これらの中でも、水素添加ビスフェノールＡジグリシジルエーテル、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレートまたは３，４－エポキシ－１－メチルシクロヘキシル－３，４－エポキシ－１－メチルヘキサンカルボキシレートが、密着性向上の観点から好ましい。 Specific examples of the alicyclic epoxy compound (A1) can be obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples include cyclohexene oxide and cyclopentene oxide-containing compounds. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexane Ruboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide , Ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy 2-epoxyethylcyclohexane, 7-oxabicyclo [4.1.0] heptane, poly [oxy- (1-oxo-1,6-hexanediyl)] derivatives, hexanedioic acid bis [(7-oxabicyclo [4 .1.0] Heptan-3-yl) methyl , Α-pinene oxide, limonene dioxide, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, etc. Is mentioned. Among these, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane Carboxylate is preferable from the viewpoint of improving adhesion.
　脂環式エポキシ化合物（Ａ１）としては、市販品のものを用いることができ、例えば、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０００、セロキサイド３０００、サイクロマーＭ１００（ダイセル社製）；ＣＹＲＡＣＵＲＥ　ＵＶＲ－６１２８（ダウ・ケミカル社製）等が挙げられる。 As the alicyclic epoxy compound (A1), commercially available products can be used. For example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000, Cyclomer M100 (manufactured by Daicel); CYRACURE UVR-6128 (Dow)・ Chemical Co.).
　本発明の硬化性組成物においては、（Ａ）成分１００質量％に対して、脂環式エポキシ化合物（Ａ１）が、１～６０質量％、特に５～５０質量％であることが、粘度、塗工性および反応性が向上するので好ましい。 In the curable composition of the present invention, the viscosity of the alicyclic epoxy compound (A1) is 1 to 60% by mass, particularly 5 to 50% by mass with respect to 100% by mass of the component (A). It is preferable because coatability and reactivity are improved.
　脂肪族エポキシ化合物（Ａ２）とは、脂環式エポキシ化合物（Ａ１）や後述の芳香族エポキシ化合物（Ａ４）に分類されないエポキシ化合物を指し、脂肪族エポキシ化合物の具体例としては、脂肪族アルコールのグリシジルエーテル化物、アルキルカルボン酸のグリシジルエステル等の単官能エポキシ化合物や、脂肪族多価アルコールまたはそのアルキレンオキサイド付加物のポリグリシジルエーテル化物、脂肪族長鎖多塩基酸のポリグリシジルエステル等の多官能エポキシ化合物が挙げられる。代表的な化合物として、アリルグリシジルエーテル、ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、Ｃ１２～１３混合アルキルグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、ポリプロピレングリコールのジグリシジルエーテル等の多価アルコールのグリシジルエーテル、またプロピレングリコール、トリメチロールプロパン、グリセリン等の脂肪族多価アルコールに１種または２種以上のアルキレンオキサイドを付加することによって得られるポリエーテルポリオールのポリグリシジルエーテル化物、脂肪族長鎖二塩基酸のジグリシジルエステルが挙げられる。さらに、脂肪族高級アルコールのモノグリシジルエーテルや高級脂肪酸のグリシジルエステル、エポキシ化大豆油、エポキシステアリン酸オクチル、エポキシステアリン酸ブチル、エポキシ化大豆油、エポキシ化ポリブタジエン等が挙げられる。これらの中でも、脂肪族アルコールのグリシジルエーテル化物あるいは脂肪族多価アルコールまたはそのアルキレンオキサイド付加物のポリグリシジルエーテル化物が、粘度、塗工性および反応性が向上するので好ましく、さらに、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテルまたは１，６－ヘキサンジオールジグリシジルエーテルが好ましい。 The aliphatic epoxy compound (A2) refers to an epoxy compound that is not classified into the alicyclic epoxy compound (A1) or the aromatic epoxy compound (A4) described later. Specific examples of the aliphatic epoxy compound include aliphatic alcohols. Monofunctional epoxy compounds such as glycidyl etherified products, glycidyl esters of alkylcarboxylic acids, polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyfunctional epoxies such as polyglycidyl esters of aliphatic long-chain polybasic acids Compounds. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane. Divalent diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Glycidyl ether of alcohol and aliphatic such as propylene glycol, trimethylolpropane, glycerin Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to polyhydric alcohols include diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, epoxidized polybutadiene, and the like. Among these, a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because viscosity, coating property, and reactivity are improved, and further ethylene glycol diglycidyl. Ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether is preferred.
　脂肪族エポキシ化合物（Ａ２）としては、市販品のものを用いることができ、例えば、デナコールＥＸ－１２１、デナコールＥＸ－１７１、デナコールＥＸ－１９２、デナコールＥＸ－２１１、デナコールＥＸ－２１２、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３２１、デナコールＥＸ－４１１、デナコールＥＸ－４２１、デナコールＥＸ－５１２、デナコールＥＸ－５２１、デナコールＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６２２、デナコールＥＸ－８１０、デナコールＥＸ－８１１、デナコールＥＸ－８５０、デナコールＥＸ－８５１、デナコールＥＸ－８２１、デナコールＥＸ－８３０、デナコールＥＸ－８３２、デナコールＥＸ－８４１、デナコールＥＸ－８６１、デナコールＥＸ－９１１、デナコールＥＸ－９４１、デナコールＥＸ－９２０、デナコールＥＸ－９３１（ナガセケムテックス社製）；エポライトＭ－１２３０、エポライト４０Ｅ、エポライト１００Ｅ、エポライト２００Ｅ、エポライト４００Ｅ、エポライト７０Ｐ、エポライト２００Ｐ、エポライト４００Ｐ、エポライト１５００ＮＰ、エポライト１６００、エポライト８０ＭＦ、エポライト１００ＭＦ（共栄社化学社製）、アデカグリシロールＥＤ－５０３、アデカグリシロールＥＤ－５０３Ｇ、アデカグリシロールＥＤ－５０６、アデカグリシロールＥＤ－５２３Ｐ（ＡＤＥＫＡ社製）等が挙げられる。 As the aliphatic epoxy compound (A2), commercially available products can be used. For example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX- 313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX- 622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol X-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P , Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycilol ED-503, Adeka Glycilol ED-503G, Adeka Glycilol ED-506, Adeka Glycilol ED -523P (made by ADEKA) and the like.
　本発明の硬化性組成物においては、（Ａ）成分１００質量％に対して、脂肪族エポキシ化合物（Ａ２）が５～４０質量％、特に２０～３０質量％であることが、粘度、塗工性および反応性が向上するので好ましい。 In the curable composition of the present invention, the aliphatic epoxy compound (A2) is 5 to 40% by mass, particularly 20 to 30% by mass with respect to 100% by mass of the component (A). This is preferable because the property and reactivity are improved.
　オキセタン化合物（Ａ３）としては、３，７－ビス（３－オキセタニル）－５－オキサ－ノナン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，２－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エタン、１，３－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］プロパン、エチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、トリエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、テトラエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、１，４－ビス（３－エチル－３－オキセタニルメトキシ）ブタン、１，６－ビス（３－エチル－３－オキセタニルメトキシ）ヘキサン、３－エチル－３－（３－エチル－３－オキセタニルメチルオキシメチル）オキセタン、キシリレンビスオキセタン等の二官能オキセタン化合物、３－エチル－３－［（フェノキシ）メチル］オキセタン、３－エチル－３－（ヘキシロキシメチル）オキセタン、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、３－エチル－３－（ヒドロキシメチル）オキセタン、３－エチル―３－（クロロメチル）オキセタン等の一官能オキセタン化合物等が挙げられ、一官能脂肪族オキセタン化合物が、粘度および反応性の点から好ましい。これらは１種単独あるいは２種以上を組み合わせて用いることができる。 Examples of the oxetane compound (A3) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis. [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, , 6-Bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3- (3 Bifunctional oxetane compounds such as ethyl-3-oxetanylmethyloxymethyl) oxetane, xylylenebisoxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3 Monofunctional oxetane compounds such as -ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, etc. Functional aliphatic oxetane compounds are preferred from the standpoints of viscosity and reactivity. These can be used alone or in combination of two or more.
　オキセタン化合物（Ａ３）としては、カチオン重合性モノマーを主成分とする市販品のものを用いることができ、例えば、２－ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、４－ヒドロキシブチルビニルエーテル（丸善石油化学社製）；アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ－１０１、ＯＸＴ－２１１、ＯＸＴ－２１２（東亞合成社製）、エタナコールＯＸＢＰ、ＯＸＴＰ（宇部興産社製）等が挙げられる。 As the oxetane compound (A3), commercially available products having a cationic polymerizable monomer as a main component can be used. For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) ); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), etanacol OXBP, OXTP (manufactured by Ube Industries) .
　本発明の硬化性組成物においては、（Ａ）成分１００質量％に対して、オキセタン化合物（Ａ３）が１０～４０質量％、特に２０～３０質量％であることが、粘度、塗工性および反応性が向上するので好ましい。 In the curable composition of the present invention, the oxetane compound (A3) is 10 to 40% by mass, particularly 20 to 30% by mass with respect to 100% by mass of the component (A). This is preferable because the reactivity is improved.
　芳香族エポキシ化合物（Ａ４）とは、エポキシ基を複数有し芳香環を含むエポキシ化合物を指し、多官能芳香族エポキシ化合物の具体例としては、フェノール、クレゾール、ブチルフェノール等、少なくとも１個の芳香族環を有する１価フェノールまたは、そのアルキレンオキサイド付加物のモノ／ポリグリシジルエーテル化物、例えばビスフェノールＡ、ビスフェノールＦ、または、これらにさらにアルキレンオキサイドを付加した化合物のグリシジルエーテル化物やフェノールノボラック型エポキシ化合物；レゾルシノールやハイドロキノン、カテコール等の２個以上のフェノール性水酸基を有する芳香族化合物のグリシジルエーテル；ベンゼンジメタノールやベンゼンジエタノール、ベンゼンジブタノール等のアルコール性水酸基を２個以上有する芳香族化合物のポリグリシジルエーテル化物；フタル酸、テレフタル酸、トリメリット酸等の２個以上のカルボン酸を有する多塩基酸芳香族化合物のポリグリシジルエステル、安息香酸やトルイル酸、ナフトエ酸等の安息香酸類のポリグリシジルエステル、安息香酸のグリシジルエステル、スチレンオキサイドまたはジビニルベンゼンのエポキシ化物等が挙げられる。これらの中でも、フェノール類のポリグリシジルエーテル、アルコール性水酸基を２個以上有する芳香族化合物のポリグリシジルエーテル化物、多価フェノール類のポリグリシジルエーテル化物、安息香酸類のポリグリシジルエステル、多塩基酸類のポリグリシジルエステルの群から選ばれる少なくとも一種を含有することが、硬化性組成物の低粘度化の観点から好ましい。特に、芳香族エポキシ化合物としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＥ型エポキシ化合物、フェノールノボラック型エポキシ化合物が、硬化性に優れるため好ましい。 The aromatic epoxy compound (A4) refers to an epoxy compound having a plurality of epoxy groups and containing an aromatic ring. Specific examples of the polyfunctional aromatic epoxy compound include at least one aromatic compound such as phenol, cresol, and butylphenol. Monohydric phenol having a ring or mono / polyglycidyl etherified product of an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F, or a compound obtained by further adding an alkylene oxide to the glycidyl etherified product or a phenol novolac type epoxy compound; Glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol; alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol Polyglycidyl etherified products of aromatic compounds having at least one group; polyglycidyl esters of polybasic aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, benzoic acid, toluic acid, naphthoic acid And benzoic acid polyglycidyl ester, benzoic acid glycidyl ester, styrene oxide or epoxidized divinylbenzene, and the like. Among these, polyglycidyl ethers of phenols, polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, polyglycidyl ethers of polyphenols, polyglycidyl esters of benzoic acids, polybasic acid polys. It is preferable to contain at least one selected from the group of glycidyl esters from the viewpoint of reducing the viscosity of the curable composition. In particular, as the aromatic epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound, or a phenol novolac type epoxy compound is preferable because of excellent curability.
　芳香族エポキシ化合物（Ａ４）としては、市販品のものを用いることができ、例えば、デナコールＥＸ－１２１、デナコールＥＸ－１４５、デナコールＥＸ－１４６、デナコールＥＸ－１４７、デナコールＥＸ－２０１、デナコールＥＸ－２０３、デナコールＥＸ－７１１、デナコールＥＸ－７２１、オンコートＥＸ－１０２０、オンコートＥＸ－１０３０、オンコートＥＸ－１０４０、オンコートＥＸ－１０５０、オンコートＥＸ－１０５１、オンコートＥＸ－１０１０、オンコートＥＸ－１０１１、オンコート１０１２（ナガセケムテックス社製）；オグソールＰＧ－１００、オグソールＥＧ－２００、オグソールＥＧ－２１０、オグソールＥＧ－２５０（大阪ガスケミカル社製）；ＨＰ４０３２、ＨＰ４０３２Ｄ、ＨＰ４７００（ＤＩＣ社製）；ＥＳＮ－４７５Ｖ（新日鉄住金化学社製）；エピコートＹＸ８８００（三菱化学社製）；マープルーフＧ－０１０５ＳＡ、マープルーフＧ－０１３０ＳＰ（日油社製）；エピクロンＮ－６６５、エピクロンＨＰ－７２００（ＤＩＣ社製）；ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＸＤ－１０００、ＮＣ－３０００、ＥＰＰＮ－５０１Ｈ、ＥＰＰＮ－５０１ＨＹ、ＥＰＰＮ－５０２Ｈ、ＮＣ－７０００Ｌ（日本化薬社製）；アデカレジンＥＰ－４０００、アデカレジンＥＰ－４００５、アデカレジンＥＰ－４１００、アデカレジンＥＰ－４９０１（ＡＤＥＫＡ社製）；ＴＥＣＨＭＯＲＥ　ＶＧ－３１０１Ｌ（プリンテック社製）等が挙げられる。 As the aromatic epoxy compound (A4), commercially available products can be used. For example, Denacol EX-121, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX- 203, Denacol EX-711, Denacol EX-721, On-coat EX-1020, On-coat EX-1030, On-coat EX-1040, On-coat EX-1050, On-coat EX-1051, On-coat EX-1010, On-coat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical Co.); HP4032, HP4032D, HP4700 (D ESN-475V (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epicote YX8800 (manufactured by Mitsubishi Chemical); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epicron N-665, Epicron HP -7CN (made by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (Nipponization) Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by Printec), and the like.
　本発明の硬化性組成物においては、（Ａ）成分１００質量％に対して、芳香族エポキシ化合物（Ａ４）が２０～６０質量％、特に３０～５０質量％であることが、硬化性向上の観点から好ましい。 In the curable composition of the present invention, the aromatic epoxy compound (A4) is 20 to 60% by mass, particularly 30 to 50% by mass, with respect to 100% by mass of the component (A), to improve the curability. It is preferable from the viewpoint.
　本発明の硬化性組成物には、カチオン硬化性成分（Ａ）として、さらにビニルエーテル化合物（Ａ５）を加えてもよい。ビニルエーテル化合物（Ａ５）としては、例えば、ジエチレングリコールモノビニルエーテル、トリエチレングリコールジビニルエーテル、ｎ－ドデシルビニルエーテル、シクロヘキシルビニルエーテル、２－エチルヘキシルビニルエーテル、２－クロロエチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテル、トリエチレングリコールビニルエーテル、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、１，６－シクロヘキサンジメタノールモノビニルエーテル、エチレングリコールジビニルエーテル、１，４－ブタンジオールジビニルエーテル、１，６－シクロヘキサンジメタノールジビニルエーテル等が挙げられる。 In the curable composition of the present invention, a vinyl ether compound (A5) may be further added as the cationic curable component (A). Examples of the vinyl ether compound (A5) include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, Examples include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, and the like.
　本発明の硬化性組成物においては、（Ａ）成分において、脂環式エポキシ化合物（Ａ１）、脂肪族エポキシ化合物（Ａ２）、オキセタン化合物（Ａ３）、芳香族エポキシ化合物（Ａ４）およびビニルエーテル化合物（Ａ５）の使用割合は、（Ａ）成分１００質量％に対して、脂環式エポキシ化合物（Ａ１）１～３０質量％、脂肪族エポキシ化合物（Ａ２）５～４０質量％、オキセタン化合物（Ａ３）１０～４０質量％、芳香族エポキシ化合物（Ａ４）２０～６０質量％、およびおよびビニルエーテル化合物（Ａ５）１～１５質量部であるのが、粘度、塗工性、反応性および硬化性が向上するので好ましい。 In the curable composition of the present invention, in the component (A), the alicyclic epoxy compound (A1), the aliphatic epoxy compound (A2), the oxetane compound (A3), the aromatic epoxy compound (A4), and the vinyl ether compound ( The proportion of A5) used is 1 to 30% by mass of the alicyclic epoxy compound (A1), 5 to 40% by mass of the aliphatic epoxy compound (A2), 100% by mass of the component (A), and the oxetane compound (A3). 10 to 40% by mass, 20 to 60% by mass of the aromatic epoxy compound (A4), and 1 to 15 parts by mass of the vinyl ether compound (A5) improve the viscosity, coating property, reactivity and curability. Therefore, it is preferable.
＜カチオン重合開始剤（Ｂ）＞
　本発明の硬化性組成物に使用する（Ｂ）成分は、エネルギー線照射または加熱によりカチオン重合を開始させる物質を放出させることが可能な化合物であればどのようなものでも差し支えないが、好ましくは、エネルギー線の照射によってルイス酸を放出するオニウム塩である複塩、またはその誘導体である。かかる化合物の代表的なものとしては、下記一般式、
［Ａ］ｒ＋［Ｂ］ｒ－
で表される陽イオンと陰イオンの塩を挙げることができる。 <Cationic polymerization initiator (B)>
The component (B) used in the curable composition of the present invention may be any compound as long as it can release a substance that initiates cationic polymerization by energy ray irradiation or heating, but preferably , A double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Representative examples of such compounds include the following general formula:
[A] r + [B] r-
And cation and anion salts represented by the formula:
　ここで陽イオン［Ａ］ｒ＋はオニウムであることが好ましく、その構造は、例えば、下記一般式
［（Ｒ２）ａＱ］ｒ＋
で表すことができる。 Here, the cation [A] r + is preferably onium, and the structure thereof is, for example, the following general formula [(R 2 ) a Q] r +
Can be expressed as
　さらに、ここで、Ｒ２は炭素原子数が１～６０であり、炭素原子以外の原子をいくつ含んでいてもよい有機基である。ａは１～５なる整数である。ａ個のＲ２は各々独立で、同一でも異なっていてもよい。また、少なくとも１つは、芳香環を有する上記のような有機基であることが好ましい。ＱはＳ，Ｎ，Ｓｅ，Ｔｅ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｏ，Ｉ，Ｂｒ，Ｃｌ，Ｆ，Ｎ＝Ｎからなる群から選ばれる原子あるいは原子団である。また、陽イオン［Ａ］ｒ＋中のＱの原子価をｑとしたとき、ｒ＝ａ－ｑなる関係が成り立つことが必要である（ただし、Ｎ＝Ｎは原子価０として扱う）。 Further, R 2 is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R 2 s are independent and may be the same or different. Moreover, it is preferable that at least 1 is the above organic groups which have an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] r + is q, it is necessary that the relationship r = a−q holds (where N = N is treated as a valence of 0).
　また、陰イオン［Ｂ］ｒ－は、ハロゲン化物錯体であることが好ましく、その構造は、例えば、下記一般式、
［ＬＹｂ］ｒ－
で表すことができる。 The anion [B] r- is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LY b ] r-
Can be expressed as
　さらに、ここで、Ｌはハロゲン化物錯体の中心原子である金属または半金属（Ｍｅｔａｌｌｏｉｄ）であり、Ｂ，Ｐ，Ａｓ，Ｓｂ，Ｆｅ，Ｓｎ，Ｂｉ，Ａｌ，Ｃａ，Ｉｎ，Ｔｉ，Ｚｎ，Ｓｃ，Ｖ，Ｃｒ，Ｍｎ，Ｃｏ等である。Ｙはハロゲン原子である。ｂは３～７の整数である。また、陰イオン［Ｂ］ｒ－中のＬの原子価をｐとしたとき、ｒ＝ｂ－ｐなる関係が成り立つことが必要である。 Here, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc , V, Cr, Mn, Co, and the like. Y is a halogen atom. b is an integer of 3 to 7. Further, when the valence of L in the anion [B] r− is p, the relationship r = b−p needs to be established.
　一般式の陰イオン［ＬＹｂ］ｒ－の具体例としては、テトラキス（ペンタフルオロフェニル）ボレート、テトラ（３，５－ジフルオロ－４－メトキシフェニル）ボレート、テトラフルオロボレート（ＢＦ４）－、ヘキサフルオロフォスフェート（ＰＦ６）－、ヘキサフルオロアンチモネート（ＳｂＦ６）－、ヘキサフルオロアルセネート（ＡｓＦ６）－、ヘキサクロロアンチモネート（ＳｂＣｌ６）－等を挙げることができる。 Specific examples of the anion [LY b ] r- of the general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4 ) − , hexa Examples thereof include fluorophosphate (PF 6 ) − , hexafluoroantimonate (SbF 6 ) − , hexafluoroarsenate (AsF 6 ) − , hexachloroantimonate (SbCl 6 ) − and the like.
　また、陰イオン［Ｂ］ｒ－は、下記一般式、
［ＬＹｂ－１（ＯＨ）］ｒ－
で表される構造のものも好ましく用いることができる。Ｌ，Ｙ，ｂは上記と同様である。また、その他用いることのできる陰イオンとしては、過塩素酸イオン（ＣｌＯ４）－、トリフルオロメチル亜硫酸イオン（ＣＦ３ＳＯ３）－、フルオロスルホン酸イオン（ＦＳＯ３）－、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート、テトラキス（ペンタフルオロフェニル）ボレート等を挙げることができる。 Further, the anion [B] r- is represented by the following general formula:
[LY b-1 (OH)] r-
The thing of the structure represented by can also be used preferably. L, Y, and b are the same as described above. Other anions that can be used include perchlorate ion (ClO 4 ) − , trifluoromethylsulfite ion (CF 3 SO 3 ) − , fluorosulfonate ion (FSO 3 ) − , and toluenesulfonate anion. , Trinitrobenzenesulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
　本発明では、このようなオニウム塩の中でも、下記の（ｉ）～（ｉｉｉ）の芳香族オニウム塩を使用することが特に好ましい。本発明の硬化性組成物においては、これらのうち１種を単独で用いてもよく、または２種以上を併用してもよい。 In the present invention, among such onium salts, it is particularly preferable to use the following aromatic onium salts (i) to (iii). In the curable composition of the present invention, one of these may be used alone, or two or more may be used in combination.
　（ｉ）フェニルジアゾニウムヘキサフルオロホスフェート、４－メトキシフェニルジアゾニウムヘキサフルオロアンチモネート、４－メチルフェニルジアゾニウムヘキサフルオロホスフェート等のアリールジアゾニウム塩 (I) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
　（ｉｉ）ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ（４－メチルフェニル）ヨードニウムヘキサフルオロホスフェート、ジ（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムヘキサフルオロホスフェート、トリルクミルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等のジアリールヨードニウム塩 (Ii) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
　（ｉｉｉ）下記群Ｉまたは群ＩＩで表されるスルホニウムカチオンとヘキサフルオロアンチモンイオン、ヘキサフルオロフォスフェートイオン、テトラキス（ペンタフルオロフェニル）ボレートイオン等のスルホニウム塩 (Iii) sulfonium salts such as sulfonium cations represented by the following group I or group II and hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, etc.
＜群Ｉ＞
Figure JPOXMLDOC01-appb-I000001
<Group I>
Figure JPOXMLDOC01-appb-I000001
＜群ＩＩ＞
Figure JPOXMLDOC01-appb-I000002
<Group II>
Figure JPOXMLDOC01-appb-I000002
　また、その他好ましいものとしては、（η５－２，４－シクロペンタジエン－１－イル）〔（１，２，３，４，５，６－η）－（１－メチルエチル）ベンゼン〕－アイアン－ヘキサフルオロホスフェート等の鉄－アレーン錯体や、トリス（アセチルアセトナト）アルミニウム、トリス（エチルアセトナトアセタト）アルミニウム、トリス（サリチルアルデヒダト）アルミニウム等のアルミニウム錯体とトリフェニルシラノール等のシラノール類との混合物；チオフェニウム塩、チオラニウム塩、ベンジルアンモニウム、ピリジニウム塩、ヒドラジニウム塩等の塩；ジエチレントリアミン、トリエチレントリアミン、テトラエチレンペンタミン等のポリアルキルポリアミン類；１，２－ジアミノシクロヘキサン、１，４－ジアミノ－３，６－ジエチルシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン類；ｍ－キシリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン類；上記ポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールＡ－ジグリシジルエーテル、ビスフェノールＦ－ジグリシジルエーテル等のグリシジルエーテル類またはカルボン酸のグリシジルエステル類等の各種エポキシ化合物とを常法によって反応させることによって製造されるポリエポキシ付加変性物；上記有機ポリアミン類と、フタル酸、イソフタル酸、ダイマー酸等のカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物；上記ポリアミン類とホルムアルデヒド等のアルデヒド類およびフェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを常法によって反応させることによって製造されるマンニッヒ化変性物；多価カルボン酸（シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、２－メチルコハク酸、２－メチルアジピン酸、３－メチルアジピン酸、３－メチルペンタン二酸、２－メチルオクタン二酸、３，８－ジメチルデカン二酸、３，７－ジメチルデカン二酸、水添ダイマー酸、ダイマー酸等の脂肪族ジカルボン酸類；フタル酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸類；シクロヘキサンジカルボン酸等の脂環式ジカルボン酸類；トリメリト酸、トリメシン酸、ひまし油脂肪酸の三量体等のトリカルボン酸類；ピロメリット酸等のテトラカルボン酸類等）の酸無水物；ジシアンジアミド、イミダゾール類、カルボン酸エステル、スルホン酸エステル、アミンイミド等を挙げることができる。 Other preferable examples include (η 5 -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum, and silanols such as triphenylsilanol A mixture of: thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, hydrazinium salt, etc .; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino -3,6-Di Alicyclic polyamines such as tilcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; the above polyamines, phenylglycidyl ether, butylglycidyl ether, bisphenol A-diglycidyl Polyepoxy addition-modified products produced by reacting ethers, glycidyl ethers such as bisphenol F-diglycidyl ether, or various epoxy compounds such as glycidyl esters of carboxylic acids; and the above-mentioned organic polyamines and phthalates An amidation-modified product produced by reacting a carboxylic acid such as acid, isophthalic acid or dimer acid by a conventional method; aldehydes such as the above polyamines and formaldehyde; Mannich modified product produced by reacting phenols having at least one aldehyde-reactive site with a nucleus such as enol, cresol, xylenol, tert-butylphenol, resorcin, etc .; polyvalent carboxylic acid (shu Acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methyl Aliphatic dicarboxylic acids such as pentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid Aromatic dicarboxylic acids such as acid and naphthalenedicarboxylic acid; cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as acids; tricarboxylic acids such as trimellitic acid, trimesic acid and trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, Examples include sulfonic acid esters and amine imides.
　これらの中でも、実用面と光感度向上の観点から、芳香族ヨードニウム塩、芳香族スルホニウム塩、鉄－アレーン錯体を用いることが好ましい。 Of these, aromatic iodonium salts, aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoints of practical use and improvement of photosensitivity.
　（Ａ）成分に対する（Ｂ）成分の使用割合は特に限定されず、本発明の目的を阻害しない範囲内で概ね通常の使用割合で使用すればよいが、例えば、（Ａ）成分１００質量部に対して、（Ｂ）成分０．１～１５質量部、好ましくは１～１０質量部とすることができる。少なすぎると硬化が不十分となりやすく、多すぎると硬化物の吸水率や硬化物強度等の諸物性に悪影響を与える場合がある。 The use ratio of the component (B) relative to the component (A) is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention. On the other hand, the component (B) can be 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass. If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.
＜エポキシ基を有するシランカップリング剤（Ｃ）＞
　本発明に使用する（Ｃ）成分は、エポキシ基を有するシランカップリング剤であるが、（Ａ）成分に該当するものは含まれない。（Ｃ）成分としては、エポキシ官能性アルコキシシランを用いることができ、例えば、γ－グリシジルオキシプロピルトリメトキシシラン、γ－グリシジルオキシプロピルトリエトキシシラン、γ－グリシジルオキシプロピルメチルジメトキシシラン、γ－グリシジルオキシプロピルメチルジエトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等が挙げられる。 <Silane coupling agent having epoxy group (C)>
(C) component used for this invention is a silane coupling agent which has an epoxy group, However, What corresponds to (A) component is not contained. As the component (C), an epoxy functional alkoxysilane can be used, for example, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyl. Examples thereof include oxypropylmethyldiethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
　（Ｃ）成分としては市販品を用いることもでき、例えば、Ｄ２６３２、Ｇ０２６１、Ｇ０２１０、Ｔ２６７５（東京化成社製）；ＫＢＭ－３０３、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＥ－４０２、ＫＢＥ－４０３（信越シリコーン社製）等が挙げられる。 As the component (C), commercially available products may be used. For example, D2632, G0261, G0210, T2675 (manufactured by Tokyo Chemical Industry Co., Ltd.); KBM-303, KBM-402, KBM-403, KBE-402, KBE-403 ( Shin-Etsu Silicone Co., Ltd.).
　（Ｃ）成分の使用量は、特に限定されないが、例えば、（Ａ）成分１００質量部に対して、（Ｃ）成分０．１～１５質量部、好ましくは１～１０質量部とすることができる。 The amount of component (C) used is not particularly limited. For example, component (C) is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, relative to 100 parts by weight of component (A). it can.
＜その他の成分＞
　本発明の硬化性組成物には、必要に応じて、増感剤および／または増感助剤を用いることができる。増感剤は、カチオン重合開始剤（Ｂ）が示す極大吸収波長よりも長い波長に極大吸収を示し、カチオン重合開始剤（Ｂ）による重合開始反応を促進させる化合物である。また増感助剤は、増感剤の作用を一層促進させる化合物である。 <Other ingredients>
A sensitizer and / or a sensitization aid can be used in the curable composition of the present invention as necessary. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength indicated by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). The sensitization aid is a compound that further promotes the action of the sensitizer.
　増感剤および増感助剤としては、アントラセン系化合物、ナフタレン系化合物等が挙げられる。 Sensitizers and sensitizers include anthracene compounds and naphthalene compounds.
　アントラセン系化合物としては、例えば、下式（１）で表されるものが挙げられる。 Examples of the anthracene compound include those represented by the following formula (1).
Figure JPOXMLDOC01-appb-I000003
（式中、Ｒ１およびＲ２は、各々独立に炭素原子数１～６のアルキル基または炭素原子数２～１２のアルコキシアルキル基を表し、Ｒ３は水素原子または炭素原子数１～６のアルキル基を表す。）
Figure JPOXMLDOC01-appb-I000003
(Wherein R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, and R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents an alkyl group.)
　上記式（１）で表されるアントラセン系化合物の具体例を挙げると、次のような化合物がある。 Specific examples of the anthracene compound represented by the above formula (1) include the following compounds.
　９，１０－ジメトキシアントラセン、９，１０－ジエトキシアントラセン、９，１０－ジプロポキシアントラセン、９，１０－ジイソプロポキシアントラセン、９，１０－ジブトキシアントラセン、９，１０－ジペンチルオキシアントラセン、９，１０－ジヘキシルオキシアントラセン、９，１０－ビス（２－メトキシエトキシ）アントラセン、９，１０－ビス（２－エトキシエトキシ）アントラセン、９，１０－ビス（２－ブトキシエトキシ）アントラセン、９，１０－ビス（３－ブトキシプロポキシ）アントラセン、２－メチル－または２－エチル－９，１０－ジメトキシアントラセン、２－メチル－または２－エチル－９，１０－ジエトキシアントラセン、２－メチル－または２－エチル－９，１０－ジプロポキシアントラセン、２－メチル－または２－エチル－９，１０－ジイソプロポキシアントラセン、２－メチル－または２－エチル－９，１０－ジブトキシアントラセン、２－メチル－または２－エチル－９，１０－ジペンチルオキシアントラセン、２－メチル－または２－エチル－９，１０－ジヘキシルオキシアントラセン等。 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9, 10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl- 9,10-dipropoxyanthracene, 2 Methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene and the like.
　ナフタレン系化合物としては、例えば、下式（２）で表されるものが挙げられる。 Examples of the naphthalene compound include those represented by the following formula (2).
Figure JPOXMLDOC01-appb-I000004
（式中、Ｒ４およびＲ５は各々独立に水素原子または炭素原子数１～６のアルキル基を表す。）
Figure JPOXMLDOC01-appb-I000004
(Wherein R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
　上記式（２）で表されるナフタレン系化合物の具体例を挙げると、次のような化合物がある。 Specific examples of the naphthalene compound represented by the above formula (2) include the following compounds.
　４－メトキシ－１－ナフトール、４－エトキシ－１－ナフトール、４－プロポキシ－１－ナフトール、４－ブトキシ－１－ナフトール、４－ヘキシルオキシ－１－ナフトール、１，４－ジメトキシナフタレン、１－エトキシ－４－メトキシナフタレン、１，４－ジエトキシナフタレン、１，４－ジプロポキシナフタレン、１，４－ジブトキシナフタレン等。 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1- Ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene and the like.
　上記（Ａ）成分に対する増感剤および増感助剤の使用割合は特に限定されず、本発明の目的を阻害しない範囲内で概ね通常の使用割合で使用すればよいが、例えば、（Ａ）成分の１００質量部に対して、増感剤および増感助剤それぞれ０．１～３質量部であるのが、硬化性向上の観点から好ましい。 The use ratio of the sensitizer and the sensitization aid to the component (A) is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention. For example, (A) From the viewpoint of improving curability, 0.1 to 3 parts by mass of each of the sensitizer and the sensitization aid is preferable with respect to 100 parts by mass of the components.
　本発明の硬化性組成物は、必要に応じて熱可塑性有機重合体を用いることによって、硬化物の特性を改善することもできる。熱可塑性有機重合体としては、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート－エチルアクリレート共重合体、ポリ（メタ）アクリル酸、スチレン－（メタ）アクリル酸共重合体、（メタ）アクリル酸－メチルメタクリレート共重合体、グリシジル（メタ）アクリレート－ポリメチル（メタ）アクリレート共重合体、ポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル等が挙げられる。 The curable composition of the present invention can also improve the properties of the cured product by using a thermoplastic organic polymer as necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methyl. Examples thereof include a methacrylate copolymer, a glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.
　本発明の硬化性組成物においては、特に制限されず通常用いられる上記（Ａ）、（Ｂ）および（Ｃ）の各成分を溶解または分散しえる溶媒を用いることができ、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、２－ヘプタノン等のケトン類；エチルエーテル、ジオキサン、テトラヒドロフラン、１，２－ジメトキシエタン、１，２－ジエトキシエタン、プロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル等のエーテル系溶媒；酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸シクロヘキシル、乳酸エチル、コハク酸ジメチル、テキサノール等のエステル系溶媒；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のセロソルブ系溶媒；メタノール、エタノール、イソ－またはｎ－プロパノール、イソ－またはｎ－ブタノール、アミルアルコール等のアルコール系溶媒；エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート（ＰＧＭＥＡ）、ジプロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート、エトキシエチルプロピオネート等のエーテルエステル系溶媒；ベンゼン、トルエン、キシレン等のＢＴＸ系溶媒；ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒；テレピン油、Ｄ－リモネン、ピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール＃３１０（コスモ松山石油（株））、ソルベッソ＃１００（エクソン化学（株））等のパラフィン系溶媒；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、１，２－ジクロロエタン等のハロゲン化脂肪族炭化水素系溶媒；クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒；プロピレンカーボネート、カルビトール系溶媒、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、水等が挙げられ、これらの溶媒は１種または２種以上の混合溶媒として使用することができる。 In the curable composition of the present invention, a solvent that can dissolve or disperse the components (A), (B), and (C) that are usually used without any particular limitation can be used. For example, methyl ethyl ketone, methyl Ketones such as amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol Ether solvents such as monomethyl ether and dipropylene glycol dimethyl ether; esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol Solvent; cellosolve solvent such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; ethylene glycol monomethyl acetate, ethylene Ether ester solvents such as glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; benzene, toluene, xylene BTX solvents such as: Aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; turpentine oil, D-limonene, pinene Terpene hydrocarbon oils; paraffinic solvents such as mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1 Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N , N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like, and these solvents can be used as one or a mixture of two or more.
　また、本発明の硬化性組成物においては、本発明の効果を損なわない限り、必要に応じて他のモノマー、他のエネルギー線感受性重合開始剤、無機フィラー、有機フィラー、顔料、染料等の着色剤、消泡剤、増粘剤、界面活性剤、レべリング剤、難燃剤、チクソ剤、希釈剤、可塑剤、安定剤、重合禁止剤、紫外線吸収剤、酸化防止剤、静電防止剤、流動調整剤、接着促進剤等の各種樹脂添加物等を添加することができる。 In the curable composition of the present invention, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and the like are colored as necessary unless the effects of the present invention are impaired. Agent, antifoaming agent, thickener, surfactant, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, antistatic agent Various resin additives such as a flow regulator and an adhesion promoter can be added.
　本発明の硬化性組成物は、ロールコーター、カーテンコーター、各種の印刷、浸漬等の公知の手段で、支持基体上に塗布することができる。また、一旦フィルム等の支持基体上に施した後、他の支持基体上に転写することもでき、その適用方法に制限はない。 The curable composition of the present invention can be applied on a supporting substrate by a known means such as a roll coater, a curtain coater, various types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
　支持基体の材料としては、特に制限されず通常用いられるものを使用することができ、例えば、ガラス等の無機材料；ジアセチルセルロース、トリアセチルセルロース（ＴＡＣ）、プロピオニルセルロース、ブチリルセルロース、アセチルプロピオニルセルロース、ニトロセルロース等のセルロースエステル；ポリアミド；ポリイミド；ポリウレタン；エポキシ樹脂；ポリカーボネート；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリ－１，４－シクロヘキサンジメチレンテレフタレート、ポリエチレン－１，２－ジフェノキシエタン－４，４’－ジカルボキシレート、ポリブチレンテレフタレート等のポリエステル；ポリスチレン；ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン；ポリ酢酸ビニル、ポリ塩化ビニル、ポリフッ化ビニル等のビニル化合物；ポリメチルメタクリレート、ポリアクリル酸エステル等のアクリル系樹脂；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルケトン；ポリエーテルイミド；ポリオキシエチレン、ノルボルネン樹脂、シクロオレフィンポリマー（ＣＯＰ）等の高分子材料が挙げられる。なお、支持基体に、コロナ放電処理、火炎処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理等の表面活性化処理を行ってもよい。 The material for the support substrate is not particularly limited and those usually used can be used. For example, inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose Polyester; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Poly-1,4-cyclohexanedimethylene terephthalate, Polyethylene-1,2-diphenoxyethane -4,4'-dicarboxylate, polyester such as polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene, etc. Polyolefins; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polyoxy Polymer materials such as ethylene, norbornene resin, and cycloolefin polymer (COP) can be used. The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
　本発明の硬化性組成物およびその硬化物の具体的な用途としては、光学フィルム、接着剤、メガネ、撮像用レンズに代表される光学材料、塗料、コーティング剤、ライニング剤、インキ、レジスト、液状レジスト、印刷版、絶縁ワニス、絶縁シート、積層板、プリント基盤、半導体装置用・ＬＥＤパッケージ用・液晶注入口用・有機ＥＬ用・光素子用・電気絶縁用・電子部品用・分離膜用等の封止剤、成形材料、パテ、ガラス繊維含浸剤、目止め剤、半導体用・太陽電池用等のパッシベーション膜、層間絶縁膜、保護膜、液晶表示装置のバックライトに使用されるプリズムレンズシート、プロジェクションテレビ等のスクリーンに使用されるフレネルレンズシート、レンチキュラーレンズシート等のレンズシートのレンズ部、またはこのようなシートを用いたバックライト等、マイクロレンズ等の光学レンズ、光学素子、光コネクター、光導波路、光学的造形用注型剤等を挙げることができる。 Specific applications of the curable composition of the present invention and the cured product include optical materials such as optical films, adhesives, glasses, and imaging lenses, paints, coating agents, lining agents, inks, resists, and liquids. Resist, printing plate, insulating varnish, insulating sheet, laminated board, printed circuit board, semiconductor device, LED package, liquid crystal inlet, organic EL, optical element, electrical insulation, electronic component, separation membrane, etc. Sealant, molding material, putty, glass fiber impregnating agent, sealant, passivation film for semiconductors and solar cells, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device Lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets used for screens of projection televisions, etc. Backlights using a sheet can include an optical lens such as a micro lens, an optical element, an optical connector, an optical waveguide, a for optical fabricating casting agent.
　例えば、光学フィルムとして適用する場合には、基材として、金属、木材、ゴム、プラスチック、ガラス、セラミック製品等を用い、基材に本発明の硬化性組成物を上述の手段で塗布し、上述の手段で光照射または加熱して硬化させる。光学フィルムの代表的な構成としては、透明支持体に、必要に応じて、下塗り層、反射防止層、ハードコート層、ガスバリア層、潤滑層、粘着剤層等の各層を設けたものが挙げられる。 For example, when applied as an optical film, a metal, wood, rubber, plastic, glass, ceramic product or the like is used as a substrate, and the curable composition of the present invention is applied to the substrate by the above-described means. And curing by light irradiation or heating. As a typical configuration of the optical film, a transparent support provided with various layers such as an undercoat layer, an antireflection layer, a hard coat layer, a gas barrier layer, a lubricating layer, and an adhesive layer as necessary may be mentioned. .
　また、支持基体としては、基材に無機材料を用い、上記の方法により塗布した膜、あるいは真空蒸着法、イオンプレーティング法、プラズマＣＶＤ法、イオンアシスト法、反応性スパッタリング法、化学的気相成長法等の各種蒸着法により作製した膜を積層したものを用いることもできる。 In addition, as a supporting substrate, an inorganic material is used for the substrate, and a film coated by the above method, or vacuum deposition method, ion plating method, plasma CVD method, ion assist method, reactive sputtering method, chemical vapor phase It is also possible to use a laminate of films prepared by various vapor deposition methods such as a growth method.
　蒸着法により膜を積層する場合、基材としては、ガラスを用いるのが好ましく、膜厚は、使用する無機材料の種類等によっても異なるが、例えば、５～３００ｎｍである。蒸着膜は、基板の片面のみに形成させてもよいし、あるいは基板の両面に形成させてもよい。無機材料としては、例えば、ケイ素（Ｓｉ）、アルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、カリウム（Ｋ）、スズ（Ｓｎ）、インジウム（Ｉｎ）、ナトリウム（Ｎａ）、ホウ素（Ｂ）、チタン（Ｔｉ）、鉛（Ｐｂ）、ジルコニウム（Ｚｒ）、イットリウム（Ｙ）、アンチモン（Ｓｂ）等の酸化物や、インジウム・スズ複合酸化物（ＩＴＯと略す。）、アンチモン・スズ複合酸化物（ＡＴＯと略す。）等の複合酸化物を使用することができる。 When laminating films by vapor deposition, it is preferable to use glass as the substrate, and the film thickness is, for example, 5 to 300 nm, although it varies depending on the type of inorganic material used. The vapor deposition film may be formed only on one side of the substrate, or may be formed on both sides of the substrate. Examples of the inorganic material include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), indium (In), sodium (Na), and boron (B ), Titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), antimony (Sb) and other oxides, indium-tin composite oxide (abbreviated as ITO), antimony-tin composite oxide A composite oxide such as a product (abbreviated as ATO) can be used.
　本発明の硬化性組成物をエネルギー線の照射により硬化させる場合、エネルギー線としては、紫外線、電子線、Ｘ線、放射線、高周波などを挙げることができ、紫外線が経済的に最も好ましい。紫外線の光源としては、紫外線レーザー、水銀ランプ、キセノンレーザ、メタルハライドランプなどが挙げられる。 In the case where the curable composition of the present invention is cured by irradiation with energy rays, examples of energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies and the like, and ultraviolet rays are most preferable economically. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
　本発明の硬化性組成物を加熱により硬化させる場合の条件は、７０～２５０℃で１～１００分である。プレベイク（ＰＡＢ；Ｐｒｅ　ａｐｐｌｉｅｄ　ｂａｋｅ）した後、加圧して、ポストベイク（ＰＥＢ；Ｐｏｓｔ　ｅｘｐｏｓｕｒｅ　ｂａｋｅ）してもよいし、異なる数段階の温度でベイクしてもよい。 The conditions for curing the curable composition of the present invention by heating are 70 to 250 ° C. and 1 to 100 minutes. After performing pre-baking (PAB), pressurization and post-baking (PEB) may be performed, or baking may be performed at several different temperatures.
　加熱条件は各成分の種類及び配合割合によって異なるが、例えば、７０～１８０℃で、オーブンなら５～１５分間、ホットプレートなら１～５分間である。その後、塗膜を硬化させるために１８０～２５０℃、好ましくは２００～２５０℃で、オーブンなら３０～９０分間、ホットプレートなら５～３０分間加熱処理することによって硬化膜を得ることができる。 The heating conditions vary depending on the type and mixing ratio of each component. For example, it is 70 to 180 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Thereafter, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.
　以下、本発明の硬化性組成物およびこの硬化性組成物を硬化して得られる硬化物に関し、実施例および比較例を用いてより詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例および比較例では部は質量部を意味する。 Hereinafter, the curable composition of the present invention and a cured product obtained by curing the curable composition will be described in more detail using Examples and Comparative Examples, but the present invention is limited to these Examples. It is not something. In Examples and Comparative Examples, “part” means “part by mass”.
［実施例１～７、比較例１～４］
　下記表１、２に示す配合で各成分を十分に混合して、各々実施例１～７および比較例１～４の組成物を得た。（Ａ）成分としては、下記の化合物（Ａ１－１）、（Ａ２－１）～（Ａ２－３）、（Ａ３－１）、（Ａ３－２）および（Ａ４－１）を用い、（Ｂ）成分および（Ｃ）成分としては、下記の化合物（Ｂ）、および化合物（Ｃ－１）、化合物（Ｃ－２）を用いた。 [Examples 1 to 7, Comparative Examples 1 to 4]
The components shown in Tables 1 and 2 were thoroughly mixed to obtain compositions of Examples 1 to 7 and Comparative Examples 1 to 4, respectively. As the component (A), the following compounds (A1-1), (A2-1) to (A2-3), (A3-1), (A3-2) and (A4-1) are used, and (B) As the component (C) and the component (C), the following compound (B), compound (C-1) and compound (C-2) were used.
化合物Ａ１－１：セロキサイド２０２１Ｐ（脂環式エポキシ：ダイセル社製）
化合物Ａ２－１：１，４－ブタンジオールジグリシジルエーテル
化合物Ａ２－２：アデカグリシロールＥＤ－５２３Ｔ（脂肪族エポキシ：ＡＤＥＫＡ社製）
化合物Ａ２－２：ネオペンチルグリコールジグリシジルエーテル
化合物Ａ３－１：アロンオキセタンＯＸＴ－２２１（オキセタン：東亞合成社製）
化合物Ａ３－２：アロンオキセタンＯＸＴ－１０１（オキセタン：東亞合成社製）
化合物Ａ４－１：アデカレジンＥＰ－４１００（ビスフェノールＡ型多官能エポキシ：ＡＤＥＫＡ社製） Compound A1-1: Celoxide 2021P (alicyclic epoxy: manufactured by Daicel)
Compound A2-1: 1,4-butanediol diglycidyl ether Compound A2-2: Adekaglycilol ED-523T (aliphatic epoxy: manufactured by ADEKA)
Compound A2-2: Neopentyl glycol diglycidyl ether compound A3-1: Aron oxetane OXT-221 (Oxetane: manufactured by Toagosei Co., Ltd.)
Compound A3-2: Aron oxetane OXT-101 (oxetane: manufactured by Toagosei Co., Ltd.)
Compound A4-1: Adeka Resin EP-4100 (Bisphenol A type polyfunctional epoxy: manufactured by ADEKA)
　化合物（Ｂ）：下記式（３）で表される化合物および下記式（４）で表される化合物の混合物のプロピレンカーボネート５０％溶液 Compound (B): 50% propylene carbonate solution of a mixture of a compound represented by the following formula (3) and a compound represented by the following formula (4)
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000006
化合物Ｃ－１：ＫＢＭ－４０３（シランカップリング剤：信越シリコーン社製）
化合物Ｃ－２：ＫＢＥ－４０３（シランカップリング剤：信越シリコーン社製） Compound C-1: KBM-403 (silane coupling agent: manufactured by Shin-Etsu Silicone)
Compound C-2: KBE-403 (Silane coupling agent: Shin-Etsu Silicone)
　得られた実施例１～７および比較例１～４の硬化性組成物について、下記評価を行った。評価結果を表１、２に併記する。 The following evaluations were performed on the curable compositions of Examples 1 to 7 and Comparative Examples 1 to 4 obtained. The evaluation results are also shown in Tables 1 and 2.
（粘度）
　得られた実施例１～７および比較例１～４の硬化性組成物のそれぞれを２５℃においてＥ型粘度計で粘度を測定した。結果を表１、２に併記する。 (viscosity)
The viscosity of each of the obtained curable compositions of Examples 1 to 7 and Comparative Examples 1 to 4 was measured at 25 ° C. with an E-type viscometer. The results are shown in Tables 1 and 2.
（密着性１）
　得られた実施例１～５および比較例１～３の硬化性組成物のそれぞれを、一枚のガラス基板（５ｃｍ×１０ｃｍ）にバーコーター＃３で塗布した後、２ｃｍ幅に切断したＣＯＰ（シクロオレフィンポリマー）フィルムと貼り合わせ、メタルハライドランプを用いて、照度２５０ｍＷ／ｃｍ２で１０００ｍＪ／ｃｍ２のエネルギーを照射して接着して試験片を得た。得られた試験片の９０度ピール試験を行った。結果を表１、２に併記する。 (Adhesion 1)
Each of the obtained curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was applied to a single glass substrate (5 cm × 10 cm) with a bar coater # 3, and then COP ( A test piece was obtained by laminating with a cycloolefin polymer) film and using a metal halide lamp to irradiate energy of 1000 mJ / cm 2 at an illuminance of 250 mW / cm 2 and adhere. The obtained test piece was subjected to a 90 degree peel test. The results are shown in Tables 1 and 2.
（密着性２）
　得られた実施例６、７および比較例４の組成物のそれぞれを、一枚のＴＡＣフィルムに塗布した後、ラミネーターを用いてコロナ放電処理を施したＣＯＰ（シクロオレフィンポリマー）フィルムと貼り合わせ、無電極紫外光ランプを用いて１０００ｍＪ／ｃｍ２のエネルギーを照射して接着して試験片を得た。得られた試験片の９０度ピール試験を行った。結果を表１、２に併記する。 (Adhesion 2)
Each of the obtained compositions of Examples 6 and 7 and Comparative Example 4 was applied to a single TAC film, and then bonded to a COP (cycloolefin polymer) film subjected to corona discharge treatment using a laminator. A test piece was obtained by applying an energy of 1000 mJ / cm 2 using an electrodeless ultraviolet light lamp and bonding. The obtained test piece was subjected to a 90 degree peel test. The results are shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表１、２より、本発明の硬化性組成物は、密着性に優れ、低粘度であることがわかる。
  From Tables 1 and 2, it can be seen that the curable composition of the present invention has excellent adhesion and low viscosity.

Claims (9)

  1. 　カチオン硬化性成分（Ａ）１００質量部、カチオン重合開始剤（Ｂ）０．１～１５質量部を含有する硬化性組成物であって、
    　前記カチオン硬化性成分（Ａ）が、脂環式エポキシ化合物（Ａ１）、脂肪族エポキシ化合物（Ａ２）、およびオキセタン化合物（Ａ３）を必須成分とすることを特徴とする硬化性組成物。     A curable composition containing 100 parts by weight of a cationic curable component (A) and 0.1 to 15 parts by weight of a cationic polymerization initiator (B),
    The curable composition, wherein the cationic curable component (A) comprises an alicyclic epoxy compound (A1), an aliphatic epoxy compound (A2), and an oxetane compound (A3) as essential components.
  2. 　前記カチオン硬化性成分（Ａ）として、さらに芳香族エポキシ化合物（Ａ４）を含有する請求項１記載の硬化性組成物。 The curable composition according to claim 1, further comprising an aromatic epoxy compound (A4) as the cationic curable component (A).
  3. 　さらに、エポキシ基を有するシランカップリング剤（ただし、カチオン硬化性成分（Ａ）を除く。）（Ｃ）０．１～１５質量部を含有する請求項１記載の硬化性組成物。 The curable composition according to claim 1, further comprising 0.1 to 15 parts by mass of a silane coupling agent having an epoxy group (excluding the cationic curable component (A)) (C).
  4. 　前記カチオン硬化性成分（Ａ）１００質量％中、前記脂環式エポキシ化合物（Ａ１）が１～３０質量％である請求項１記載の硬化性組成物。 The curable composition according to claim 1, wherein the alicyclic epoxy compound (A1) is 1 to 30% by mass in 100% by mass of the cationic curable component (A).
  5. 　前記脂環式エポキシ化合物（Ａ１）が、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、７－オキサビシクロ［４．１．０］ヘプタン，ポリ［オキシ－（１－オキソ－１，６－ヘキサンジイル）］誘導体、ヘキサン二酸ビス［（７－オキサビシクロ［４．１．０］ヘプタン－３－イル）メチル］、１，２－エポキシ－４－ビニルシクロヘキサン、３，４－エポキシシクロヘキシルメチルメタアクリレートおよびリモネンジオキシドの群より選択される少なくとも一種である請求項１記載の硬化性組成物。 The alicyclic epoxy compound (A1) is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 7-oxabicyclo [4.1.0] heptane, poly [oxy- (1- Oxo-1,6-hexanediyl)] derivative, bis [hexane oxalate] [(7-oxabicyclo [4.1.0] heptan-3-yl) methyl], 1,2-epoxy-4-vinylcyclohexane, 3 The curable composition according to claim 1, which is at least one selected from the group consisting of 1,4-epoxycyclohexylmethyl methacrylate and limonene dioxide.
  6. 　前記オキセタン化合物（Ａ３）が、３－エチル－３－（ヘキシロキシメチル）オキセタン、３－エチル－３－（ヒドロキシメチル）オキセタン、キシリレンビスオキセタン、３－エチル－３－（３－エチル－３－オキセタニルメチルオキシメチル）オキセタンの群より選択される少なくとも一種である請求項１記載の硬化性組成物。 The oxetane compound (A3) is 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, xylylenebisoxetane, 3-ethyl-3- (3-ethyl-3 The curable composition according to claim 1, which is at least one selected from the group of -oxetanylmethyloxymethyl) oxetane.
  7. 　請求項１～６のうちいずれか一項記載の硬化性組成物を、活性エネルギー線の照射により硬化させることを特徴とする硬化性組成物の硬化方法。 A method for curing a curable composition, comprising curing the curable composition according to any one of claims 1 to 6 by irradiation with active energy rays.
  8. 　請求項１～６のうちいずれか一項記載の硬化性組成物を、加熱により硬化させることを特徴とする硬化性組成物の硬化方法。 A method for curing a curable composition, wherein the curable composition according to any one of claims 1 to 6 is cured by heating.
  9. 　請求項１～６のうちいずれか一項記載の硬化性組成物からなることを特徴とする硬化物。 A cured product comprising the curable composition according to any one of claims 1 to 6.
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