WO2012128325A1 - Polyfunctional epoxy compound - Google Patents

Polyfunctional epoxy compound Download PDF

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Publication number
WO2012128325A1
WO2012128325A1 PCT/JP2012/057371 JP2012057371W WO2012128325A1 WO 2012128325 A1 WO2012128325 A1 WO 2012128325A1 JP 2012057371 W JP2012057371 W JP 2012057371W WO 2012128325 A1 WO2012128325 A1 WO 2012128325A1
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WIPO (PCT)
Prior art keywords
valent
group
epoxy compound
formula
integer
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PCT/JP2012/057371
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French (fr)
Japanese (ja)
Inventor
勇樹 遠藤
武山　敏明
佐代子 柳澤
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to KR1020137026460A priority Critical patent/KR101926076B1/en
Priority to CN201280013358.7A priority patent/CN103429632B/en
Priority to JP2013506004A priority patent/JP5867749B2/en
Publication of WO2012128325A1 publication Critical patent/WO2012128325A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a light or thermosetting epoxy resin composition. More specifically, a light or thermosetting epoxy resin useful for obtaining a cured product having excellent properties such as high adhesion to a substrate, high transparency (transparency to visible light), hard coat properties, and high heat resistance.
  • the present invention relates to a composition (resin composition for electronic materials and optical materials) and a cured product thereof (composite cured product).
  • epoxy resins have been widely used in the field of electronic materials as epoxy resin compositions combined with curing agents.
  • a high refractive index layer of an antireflection film such as an antireflection film for a liquid crystal display
  • an optical thin film such as a reflection plate
  • a sealing material for electronic components a printed wiring board
  • an interlayer In applications such as insulation film materials (such as interlayer insulation film materials for build-up printed circuit boards), molding materials are required to have high adhesion to substrates, hard coat properties, heat resistance, and high transparency to visible light.
  • an epoxy resin composition in which an epoxy compound and a light and thermal acid generator are combined does not use a solvent and can cure the epoxy compound alone.
  • photocationic curing with ultraviolet rays is very excellent in that it does not require a large curing oven and requires less energy.
  • An alicyclic epoxy compound having an epoxy group only in an alicyclic structure is widely used because of its high reactivity to cationic curing using light, but because the structure is rigid, the cured product is hard and brittle. Tend to be.
  • Patent Literature As a polyfunctional epoxy compound having a glycidyl ester group, an epoxy resin composition using cyclobutanetetracarboxylic acid tetraglycidyl ester, cyclopentanetetracarboxylic acid tetraglycidyl ester, or cyclohexanetricarboxylic acid triglycidyl ester has been proposed (Patent Literature). 2 and 3). Further, a carboxyl group-containing resin using an epoxy alkyl ester of cyclohexanedicarboxylic acid having an epoxy group as a crosslinkable compound has been proposed (see Patent Document 4).
  • the present inventors have found that the mother nucleus has various skeletons, the organic group serving as the skeleton has a plurality of side chains, and the side chains have an epoxy group via a hydrocarbon group. It has been found that a polyfunctional epoxy compound having a plurality of epoxy groups and having a plurality of the epoxy groups in one molecule is imparted not only thermosetting properties but also cationic curing properties. Accordingly, the present invention intends to provide a liquid curable composition using the epoxy composition and the epoxy compound and having high cationic curability as well as thermosetting. A cured product obtained from this curable composition has high transparency and high heat resistance.
  • A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an (n4) -valent nitrogen A ring-containing group, a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a (n4) -valent group in combination thereof, wherein R 1 and R 2 are each independently a hydrogen atom Or an alkyl group having 1 to 10 carbon atoms, R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, and n3 represents an integer of 2 to 5 N4 represents an integer of 2 to 8, n5 represents an integer of 0 or 1, and n6 represents an integer of 0 or 1.
  • An epoxy compound represented by As a second aspect, the formula (1) is transformed into the formula (1-1), the formula (1-2), or the formula (1-3): [In the formulas (1-1) and (1-3), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, and (n4) a cyclic group having 4 to 20 carbon atoms. Represents a hydrocarbon group, an (n4) -valent nitrogen-containing cyclic group, an (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a combination of these (n4) -valent groups.
  • a ′ represents a (n4) -valent nitrogen-containing cyclic group
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 3 represents (N3 + 1) represents a valent hydrocarbon group
  • n1 represents an integer of 2
  • n2 represents an integer of 1
  • n3 represents an integer of 2 to 5
  • n4 represents an integer of 2 to 8.
  • the epoxy compound according to the first aspect represented by:
  • A is an (n4) -valent unsaturated hydrocarbon group obtained by removing (n4) hydrogen atoms from ethylene, propylene, or norbornene.
  • (n4) valent cyclic carbonization in which (n4) hydrogen atoms are removed from A is cyclobutane, cyclopentane, cyclohexane, epoxycyclohexane, alkyl-substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane.
  • the epoxy compound according to the first aspect or the second aspect which is a hydrogen group
  • the A is a (n4) -valent nitrogen-containing cyclic group obtained by removing (n4) hydrogen atoms from a trialkyl isocyanurate
  • the A ′ is isocyanuric acid, cyanuric acid, hydantoin, or barbitur
  • the epoxy compound according to the first aspect or the second aspect which is a (n4) -valent nitrogen-containing cyclic group obtained by removing (n4) hydrogen atoms from an acid
  • the A is a (n4) -valent chain hydrocarbon group obtained by removing (n4) hydrogen atoms from propane, butane, pentane, or hexane, according to the first aspect or the second aspect.
  • a curable composition comprising the epoxy compound according to any one of the first aspect to the sixth aspect, and a curing agent
  • the curable composition according to the seventh aspect in which the curing agent is an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, or a polymercaptan
  • the curable composition according to the seventh aspect or the eighth aspect containing the curing agent in a proportion of 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy compound
  • a curable composition comprising the epoxy compound according to any one of the first aspect to the sixth aspect, and an acid generator
  • the curable composition according to the tenth aspect in which the acid generator is a photoacid generator or a thermal acid generator
  • the curable composition according to the eleventh aspect in which the acid generator is an onium salt
  • An epoxy compound having a plurality of epoxy rings bonded to a skeleton organic group via a hydrocarbon group has a greater degree of freedom and reactivity as the hydrocarbon group becomes longer. All the epoxy groups are involved in the reaction, and having a plurality of epoxy rings increases the cationic curability. Further, when the curable composition containing at least the epoxy compound and the photoacid generator is photocured, it is expected that a cured product or a cured coating film capable of achieving both excellent mechanical properties and excellent optical properties can be formed. The In particular, the longer the hydrocarbon group, the higher the toughness of the cured product and cured coating film is expected.
  • the mother nucleus has various skeletons
  • the organic group serving as the skeleton has a plurality of side chains
  • the side chains are connected via a hydrocarbon group.
  • the curable composition of the present invention can further contain an epoxy compound represented by the above formula (1) and a curing agent (for example, an amine or acid anhydride), and optionally a curing aid.
  • the epoxy compound represented by the above formula (1) is intended to be photocured or thermally cured using a photoacid generator or a thermal acid generator. Therefore, by using a photoacid generator or a thermal acid generator, the epoxy curing agents (eg amines and acid anhydrides) usually used are not used, or even if they are used, their content is extremely low. Therefore, the storage stability of the curable composition of the present invention is good. Since the curable composition of the present invention is cured by photocuring by UV irradiation, it can be applied to a heat-sensitive material (base material). Moreover, since the epoxy compound used for this invention is a liquid, the curable composition of this invention using it has favorable filling property. Furthermore, the curable composition containing the epoxy compound of the present invention has characteristics such as low viscosity and quick drying, and can be used for coating and bonding electronic parts, optical parts and precision mechanism parts.
  • the epoxy curing agents eg amines and acid anhydrides
  • the present invention is an epoxy compound represented by the above formula (1).
  • A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an (n4) -valent nitrogen.
  • a ring-containing group, a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a (n4) -valent group in combination thereof wherein R 1 and R 2 are each independently a hydrogen atom Or an alkyl group having 1 to 10 carbon atoms, R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, and n3 represents an integer of 2 to 5 N4 represents an integer of 2 to 8, n5 represents an integer of 0 or 1, and n6 represents an integer of 0 or 1.
  • the above formula (1) includes an epoxy compound represented by the above formula (1-1), formula (1-2), or formula (1-3).
  • A is an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, and (n4) a cyclic hydrocarbon having 4 to 20 carbon atoms.
  • Formula (1) when A is an (n4) -valent unsaturated hydrocarbon group, A is, for example, from ethylene, propylene, or norbornene An (n4) -valent unsaturated hydrocarbon group in which (n4) hydrogen atoms have been removed may be mentioned.
  • A is an (n4) -valent cyclic hydrocarbon group
  • A is, for example, cyclobutane, cyclopentane, cyclohexane, epoxy (N4) -valent cyclic hydrocarbon group in which (n4) hydrogen atoms are removed from cyclohexane, alkyl-substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane.
  • a and A ′ are (n4) -valent nitrogen-containing cyclic groups
  • A is for example, a (n4) -valent nitrogen-containing cyclic group obtained by removing (n4) hydrogen atoms from a trialkyl isocyanurate is, for example, from isocyanuric acid, cyanuric acid, hydantoin, or barbituric acid as A ′ (n4 ) (N4) -valent nitrogen-containing cyclic group in which one hydrogen atom is removed.
  • Formula (1) when A is an (n4) -valent chain hydrocarbon group, A is, for example, propane, butane, pentane, or An (n4) -valent chain hydrocarbon group obtained by removing (n4) hydrogen atoms from hexane is exemplified.
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, and t-butyl.
  • cyclobutyl group 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n- Butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2-methyl-2-ethyl-n-propyl group, 2-methyl-2-methyl-n-propyl group 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl - Chloropropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-methyl-
  • R 3 represents an (n3 + 1) -valent hydrocarbon group, and examples of the hydrocarbon group include an (n3 + 1) -valent hydrocarbon group obtained by removing (n3 + 1) hydrogen atoms from the alkyl group.
  • Examples of B substituted on the mother nucleus include an alkyl ester group, an alkyl group, and an alkyloxy group having an epoxy group exemplified below.
  • A represents a mother nucleus.
  • n5 represents an integer of 0 or 1
  • n6 represents an integer of 0 or 1.
  • a and A ′ as the mother nucleus are exemplified below.
  • B represents the polyfunctional epoxy group described above.
  • A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms
  • A is exemplified below.
  • A represents an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms
  • A is exemplified below.
  • a and A ′ represent a (n4) -valent nitrogen-containing cyclic group
  • a and A ′ are exemplified below.
  • R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • A represents a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms
  • A is exemplified below.
  • the compound represented by the formula (1) of the present invention is composed of a combination of the mother nucleus A and the substituent B.
  • the epoxy compound represented by the above formula (1-1) is obtained by, for example, reacting a carboxylic acid derivative such as a carboxylic acid having the structure of A or a carboxylic acid anhydride with an alkenol, and then obtaining the unsaturated compound obtained. It can be produced by reacting a compound having a bond (intermediate) with a peroxide.
  • the intermediate can be produced by any method regardless of the reaction of carboxylic acid or carboxylic anhydride and alkenol, and the intermediate having an unsaturated bond is reacted with a peroxide to obtain
  • the epoxy compound represented by (1-1) can be produced.
  • alkenol corresponding to B alkyl ester group having a polyfunctional epoxy group substituted on the mother nucleus A is exemplified below.
  • the carboxylic acid or carboxylic anhydride having the structure of the mother nucleus A is exemplified below.
  • Examples of the carboxylic acid or carboxylic anhydride in which A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms are shown below.
  • Examples of the carboxylic acid or carboxylic anhydride in which A represents an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms are illustrated below.
  • Examples of the carboxylic acid in which A represents a (n4) -valent nitrogen-containing cyclic group include triscarboxyalkyl isocyanurate (wherein the alkyl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms). And are exemplified below.
  • R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • Examples of the carboxylic acid or carboxylic anhydride in which A represents a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms are illustrated below.
  • the compound (intermediate) having an unsaturated bond obtained by reacting the carboxylic acid or carboxylic acid anhydride having the above structure A with alkenol can be exemplified by the formula (1-1-1).
  • A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, (n4 ) Represents a valent nitrogen-containing cyclic group, (n4) a valent chain hydrocarbon group having 3 to 10 carbon atoms, or a combination thereof (n4) valent group
  • R 1 and R 2 are each independently Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 3 represents an (n3 + 1) -valent hydrocarbon group
  • n1 represents an integer of 2
  • n2 represents an integer of 1
  • n3 represents 2
  • N4 represents an integer of 2 to 8
  • n4 represents an integer of 2 to 8.
  • the epoxy compound represented by the formula (1-1) used in the present invention is an epoxy compound represented by the formula (1-1) composed of a combination of the formula (4-3) and the formula (2-1). Taking a compound as an example, it can be obtained by the following method.
  • Carboxylic anhydride and alkenol are reacted to synthesize an intermediate (olefin).
  • This reaction is carried out in a solvent such as toluene using a catalyst such as paratoluenesulfonic acid or sulfuric acid at a temperature of room temperature (for example, 20 ° C.) to 110 ° C. for 0 to 100 hours.
  • the unsaturated compound can be oxidized with a peroxide to obtain an epoxy compound.
  • the peroxide for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used.
  • This reaction can be carried out in a solvent such as chloroform at 0 to 60 ° C. for 1 to 200 hours.
  • the above reaction can also be carried out using a dicarboxylic acid compound as a raw material instead of an acid anhydride.
  • a dicarboxylic acid compound as a raw material instead of an acid anhydride.
  • a method of esterifying with an alcohol such as methanol, followed by a transesterification reaction with alkenol, or using a condensing agent such as carbodiimide for the carboxylic acid and alkenol can also be synthesized by a method of reacting them, or a method of converting a carboxylic acid into an acid chloride with thionyl chloride or the like and reacting with an alkenol.
  • the epoxy compound represented by the above formula (1-2) is obtained by reacting a nitrogen-containing ring compound having the structure of A ′ (the compound has an NH group) with an alkenol or allyl halide having a leaving group. And the obtained compound (intermediate) having an unsaturated bond and a peroxide can be reacted.
  • the epoxy compound represented by the above formula (1-2) is obtained by reacting a nitrogen-containing compound having a structure of A ′ (the compound has an NH group) with an epoxy compound having an unsaturated bond, It can also be produced by reacting the obtained alcohol compound with an alkenol or allyl halide having a leaving group, and reacting the obtained compound (intermediate) having an unsaturated bond with a peroxide.
  • the alkenol or allyl halide having a leaving group corresponding to B substituted on the mother nucleus A ′ include, for example, the above formulas (2-1-1), (2-2-1) and (2-3-1).
  • X represents a methanesulfonyloxy group
  • trifluoromethanesulfonyl represents an oxy group, a toluenesulfonyloxy group, a nitrobenzenesulfonyloxy group, an acetyloxy group, a trifluoroacetyloxy group, a chlorine atom, a bromine atom, or an iodine atom.
  • Examples of the nitrogen-containing ring compound having the structure of the mother nucleus A ′ are shown below.
  • a ′ represents a (n4) -valent nitrogen-containing cyclic group
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl having 1 to 10 carbon atoms.
  • R 3 represents an (n3 + 1) -valent hydrocarbon group
  • n1 represents an integer of 2
  • n2 represents an integer of 1
  • n3 represents an integer of 2 to 5
  • n4 represents an integer of 2 to 8 Represents an integer.
  • the epoxy compound represented by the formula (1-2) used in the present invention is an epoxy compound represented by the formula (1-2) composed of a combination of the formula (5-6) and the formula (2-1). Taking a compound as an example, it can be obtained by the following method.
  • An intermediate (olefin) is synthesized by reacting a nitrogen-containing ring compound (the compound has an NH group) with an alkenol having a leaving group.
  • This reaction is carried out in a solvent such as DMF using a base such as sodium hydride, potassium carbonate, t-butoxypotassium, triethylamine and the like at room temperature (for example, 20 ° C.) to the boiling point of the solvent for 0 to 100 hours.
  • the unsaturated compound can be oxidized with a peroxide to obtain an epoxy compound.
  • the peroxide for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used.
  • This reaction can be carried out in a solvent such as chloroform at 0 to 60 ° C. for 1 to 200 hours.
  • the epoxy compound represented by the above formula (1-3) is, for example, a compound having an unsaturated bond obtained by reacting an alcohol having the structure A with an alkenol or allyl halide having a leaving group. It can be produced by reacting (intermediate) with a peroxide.
  • Examples of the alkenol or allyl halide having a leaving group corresponding to B substituted for the mother nucleus A include, for example, the above formula (2-1-1), formula (2-2-1), formula (2-3-1) And methanesulfonyl halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide, acetyl halide, acetic anhydride, trifluoroacetic anhydride, phosphorus oxychloride, oxy
  • the above formula (2-1-2), formula (2-2-2) and formula (2-) obtained by reacting phosphorus bromide, thionyl halide, sulfuryl halide, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like.
  • the compound represented by 3-2) and formula (2-4-2) can be used.
  • the alcohol having the structure of mother nucleus A is exemplified below.
  • Examples of the alcohol in which A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms are shown below.
  • R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the compound (intermediate) having an unsaturated bond obtained by reacting the alcohol having the structure A with an alkenol or allyl halide having a leaving group can be exemplified by the formula (1-3-1). it can.
  • A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms
  • (n4 ) Represents a valent nitrogen-containing cyclic group
  • R 1 and R 2 are each independently Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 3 represents an (n3 + 1) -valent hydrocarbon group
  • n1 represents an integer of 2
  • n2 represents an integer of 1
  • n3 represents 2
  • N4 represents an integer of 2 to 8
  • n4 represents an integer of 2
  • the epoxy compound represented by the formula (1-3) used in the present invention is represented by the formula (1-3) composed of a combination of the formula (4-4) and the formula (2-1). Taking an epoxy compound as an example, it can be obtained by the following method.
  • An alcohol (alkenol) having a leaving group is reacted to synthesize an intermediate (olefin).
  • This reaction is carried out in a solvent such as ether or amide using a base such as sodium hydroxide, potassium carbonate, t-butoxypotassium or triethylamine at room temperature (for example, 20 ° C.) to the boiling point of the solvent for 0 to 100 hours.
  • the unsaturated compound can be oxidized with a peroxide to obtain an epoxy compound.
  • the peroxide for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used.
  • This reaction can be carried out in a solvent such as chloroform at 0 to 60 ° C. for 1 to 200 hours.
  • Examples of the epoxy compound represented by the above formula (1-3) include cyanuric chloride, a formula (2-1-1), a formula (2-2-1), a formula (2-3-1), and a formula. It can also be produced by reacting a compound having an unsaturated bond (intermediate) obtained by reacting with allyl alcohol represented by (2-4-1) or the like and a peroxide as described above.
  • this invention is a curable composition containing the epoxy compound represented by the said Formula (1), and a hardening
  • the curable composition of the present invention can further contain a solvent, another epoxy compound, a curing agent, a surfactant, and an adhesion promoter, if necessary.
  • the ratio of the solid content in the curable composition of the present invention can be 1 to 100% by mass, or 5 to 100% by mass, or 50 to 100% by mass, or 80 to 100% by mass. Solid content is the ratio of the remaining component which removed the solvent from the curable composition.
  • a liquid epoxy compound is used and a curing agent or an acid generator is mixed therewith, it is basically unnecessary to use a solvent, but it is possible to add a solvent if necessary.
  • the acid generator is solid, and the curable compound can be produced by dissolving the acid generator in a solvent such as propylene carbonate and mixing it with a liquid epoxy compound. Even when an acid generator is dissolved in a liquid epoxy compound, a general solvent can be added to adjust the viscosity of the resulting curable composition.
  • the content of the epoxy compound represented by the above formula (1) in the curable composition of the present invention is 8 to 99.9% by mass, preferably 40 based on the solid content of the curable composition. It is -99 mass%, More preferably, it is 70-99 mass%. Further, the content of the acid generator in the curable composition of the present invention is 0.1 to 20% by mass, or 0.1 to 10% by mass based on the solid content of the curable composition. be able to.
  • the curable composition of the present invention contains an acid generator in a proportion of 0.1 to 20% by mass, or 0.1 to 10% by mass with respect to the mass of the epoxy compound represented by the above formula (1). be able to.
  • the epoxy compound represented by the above formula (1) and other epoxy compounds can be used in combination.
  • the epoxy compound represented by the above formula (1) and the other epoxy compounds can be used in a molar ratio of epoxy groups in the range of 1: 0.1 to 1:10.
  • Examples of the epoxy compound other than the epoxy compound represented by the above formula (1) can be exemplified below.
  • Liquid epoxy compound trade name Epicoat 828 (formula (7-2), manufactured by Japan Epoxy Resins Co., Ltd.).
  • Liquid epoxy compound trade name YX8000 (formula (7-3), manufactured by Japan Epoxy Resins Co., Ltd.).
  • Liquid epoxy compound trade name DME100 (formula (7-4), manufactured by Shin Nippon Rika Co., Ltd.).
  • Liquid epoxy compound trade name CE-2021P (formula (7-5), manufactured by Daicel Corporation).
  • the liquid epoxy compound as the liquid epoxy compound, the following tris- (3,4-epoxybutyl) -isocyanurate (formula (7-6)), tris- (4,5-epoxypentyl) -isocyanurate (formula (7-7)), tris- (5,6-epoxyhexyl) -isocyanurate (formula (7-8)), tris (glycidyloxyethyl) isocyanurate (formula (7-9)) can be used. .
  • Liquid epoxy compound modified by adding 0.8 mol of propionic anhydride to 1 mol of tris- (2,3-epoxypropyl) -isocyanurate (formula (7-10), manufactured by Nissan Chemical Industries, Ltd., trade name : Tepic path B22).
  • Formula (7-10) is obtained by converting (7-10-1) :( 7-10-2) :( 7-10-3) :( 7-10-4) in a molar ratio of about 35%: 45%: 17%: contained in a ratio of 3%.
  • Formula (7-11) contains (7-11-1) :( 7-11-2) :( 7-11-3) in a molar ratio of about 60%: 32%: 8%.
  • vinyl ether compounds, oxetane compounds and the like can be used as the cationic curable monomer in addition to the epoxy compound.
  • the vinyl group-containing compound (such as a vinyl ether compound) is not particularly limited as long as it is a compound having a vinyl group.
  • a vinyl group such as a vinyl ether compound
  • HEVE 2-hydroxyethyl vinyl ether
  • DEGV diethylene glycol monovinyl ether
  • HBVE 2-hydroxybutyl vinyl ether
  • Triethylene glycol divinyl ether vinyl compounds having a substituent such as an alkyl group or an allyl group at the ⁇ and / or ⁇ positions can also be used.
  • a vinyl ether compound containing a cyclic ether group such as an epoxy group and / or an oxetane group can be used, and examples thereof include oxynorbornene divinyl ether and 3,3-dimethanol oxetane divinyl ether.
  • a hybrid compound having a vinyl group and a (meth) acryl group can be used, and examples thereof include 2- (2-vinyloxyethoxy) ethyl (VEEA, VEEM) and the like (meth) acrylate. These can be used alone or in combination of two or more.
  • the oxetanyl group-containing compound is not particularly limited as long as it is a compound having an oxetanyl group, and 3-ethyl-3- (phenoxymethyl) oxetane (POX), di [1-ethyl (3-oxetanyl)] Methyl ether (DOX), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (EHOX), 3-ethyl-3- ⁇ [3- (triethoxysilyl) propoxy] methyl ⁇ oxetane (TESOX), oxetanyl Examples thereof include silsesquioxane (OX-SQ), phenol novolac oxetane (PNOX-1009), and the like.
  • POX 3-ethyl-3- (phenoxymethyl) oxetane
  • DOX di [1-ethyl (3-oxetanyl)] Methyl
  • a hybrid compound (1-ethyl-3-oxetanylmethyl (meth) acrylate) having an oxetanyl group and a (meth) acryl group can be used.
  • These oxetane compounds can be used alone or in combination of two or more.
  • curing agent can be obtained.
  • the curing agent acid anhydride, amine, phenol resin, polyamide resin, imidazole, or polymercaptan can be used. Among these, acid anhydrides and amines are particularly preferable. Even if these hardening
  • the curing agent can be contained at a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy compound.
  • the equivalent of the curing agent to the epoxy compound is represented by an equivalent ratio of the curable group of the curing agent to the epoxy group.
  • phenol resin examples include phenol novolac resin and cresol novolac resin.
  • amines examples include piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, diethylenetriamine, and triethylenetetramine.
  • Tetraethylenepentamine diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mensendiamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylene
  • examples include diamine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
  • liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mensendiamine, isophoronediamine, and Diaminodicyclohexylmethane and the like can be preferably used.
  • the polyamide resin is produced by condensation of dimer acid and polyamine, and is a polyamide amine having a primary amine and a secondary amine in the molecule.
  • imidazoles examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy imidazole adduct.
  • Polymercaptan is, for example, one having a mercaptan group at the end of a polypropylene glycol chain or one having a mercaptan group at the end of a polyethylene glycol chain, and is preferably in a liquid form.
  • the acid anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule.
  • These acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trislimitate, maleic anhydride, tetrahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methyl Examples include cyclohexene dicarboxylic acid anhydride and chlorendic acid anhydride.
  • methyltetrahydrophthalic anhydride methyl-5-norbornene-2,3-dicarboxylic acid anhydride (methyl nadic acid anhydride, methyl hymic anhydride), hydrogenated methyl nadic acid which is liquid at normal temperature and normal pressure
  • anhydrides methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.
  • These liquid acid anhydrides have a viscosity of about 10 mPas to 1000 mPas as measured at 25 ° C. In an acid anhydride group, one acid anhydride group is calculated as one equivalent.
  • a hardening adjuvant when obtaining hardened
  • Curing aids include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and diethyl tetrabutylphosphonium dithiophosphate, 1,8-diazabicyclo [5,4,0].
  • Examples thereof include salts of undecan-7-ene, 1,8-diazabicyclo [5,4,0] undecan-7-ene and octyl acid, and quaternary ammonium salts such as zinc octylate and tetrabutylammonium bromide.
  • These curing aids can be used in a proportion of 0.001 to 0.1 parts by mass with respect to 1 part by mass of the curing agent.
  • a curable composition is obtained by mixing the epoxy compound represented by the said Formula (1), the said hardening
  • the mixing is not particularly limited as long as it can be uniformly mixed, but can be performed using, for example, a reaction flask and a stirring blade or a mixer.
  • the mixing is performed under heating as necessary in consideration of the viscosity, and is performed at a temperature of 10 ° C. to 100 ° C. for 0.5 to 1 hour.
  • the obtained curable composition has an appropriate viscosity for use as a liquid sealing material.
  • the curable composition of the present invention can be adjusted to an arbitrary viscosity, and is partially used in a transparent sealing material such as an LED by a casting method, a potting method, a dispenser method, a printing method, etc. Can be sealed.
  • the curable composition is directly mounted in an LED or the like in a liquid state by the above-described method, and then dried and cured to obtain a cured epoxy resin.
  • the cured product obtained from the curable composition is pre-cured at a temperature of 100 to 120 ° C. by applying the curable composition to a substrate or pouring it onto a casting plate coated with a release agent, and 120 to It is obtained by post-curing at a temperature of 200 ° C.
  • the heating time is about 1 to 12 hours, preferably about 2 to 5 hours.
  • the thickness of the coating film obtained from the curable composition of the present invention can be selected from the range of about 0.01 ⁇ m to 10 mm depending on the use of the cured product.
  • the above-mentioned curable composition can contain a solvent if necessary.
  • the solvent include ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.
  • Diethylene glycols such as ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether
  • propylene glycol compounds such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether
  • Propylene glycol alkyl ether acetates such as alkyl ethers, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate
  • Propylene glycol alkyl ether acetates such as propylene glycol propyl ether propionate and propylene glycol butyl ether
  • the curable composition containing the epoxy compound represented by the said Formula (1) and an acid generator can be obtained.
  • a photoacid generator or a thermal acid generator can be used.
  • the photoacid generator or thermal acid generator is not particularly limited as long as it generates an acid directly or indirectly by light irradiation or heating.
  • Specific examples of the photoacid generator include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, iodonium salts, sulfonium salts, onium salts such as phosphonium salts, selenium salts, metallocene complexes, Examples thereof include iron arene complexes.
  • the onium salt used as the photoacid generator is an iodonium salt such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoro.
  • an iodonium salt such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoro.
  • Antimonate diphenyliodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, Bis (p-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, and bis (p-chlorophenyl) iodonium tetrafluoroborate.
  • bis (alkylphenyl) iodonium salts such as bis (4-t-butylphenyl) iodonium hexafluorophosphate, alkoxycarbonylalkoxy-trialkylaryliodonium salts (for example, 4-[(1-ethoxycarbonyl-ethoxy) phenyl]- (2,4,6-trimethylphenyl) -iodonium hexafluorophosphate), bis (alkoxyaryl) iodonium salts (for example, bis (alkoxyphenyl) iodonium salts such as (4-methoxyphenyl) phenyliodonium hexafluoroantimonate) Is mentioned.
  • alkoxycarbonylalkoxy-trialkylaryliodonium salts for example, 4-[(1-ethoxycarbonyl-ethoxy) phenyl]- (2,4,6-trimethylphenyl) -iodonium
  • sulfonium salt examples include triphenylsulfonium chloride, triphenylsulfonium bromide, tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoro.
  • Triphenylsulfonium salts such as borate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, (4-phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) ) Diphenylsulfonium hexafluorophosphate, bis [4- (diphenylsulfonio) fe And sulfonium salts such as bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorophosphate and (4-methoxyphenyl) diphenylsulfonium hexafluoroantimonate). .
  • Examples of the phosphonium salt include triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p-ethoxyphenyl) phosphonium tetrafluoro.
  • Examples thereof include phosphonium salts such as borate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.
  • selenium salts such as triphenyl selenium hexafluorophosphate
  • metallocene complex examples include ( ⁇ 5 or ⁇ 6-isopropylbenzene) ( ⁇ 5-cyclopentadienyl) iron (II) hexafluorophosphate.
  • a metallocene complex is mentioned.
  • the following compounds can also be used as a photoacid generator.
  • a sulfonium salt compound and an iodonium salt compound are preferable.
  • These anionic species include CF 3 SO 3 ⁇ , C 4 F 9 SO 3 ⁇ , C 8 F 17 SO 3 ⁇ , camphorsulfonate anion, tosylate anion, BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ and SbF 6- and the like can be mentioned.
  • Particularly preferred are anionic species such as phosphorous hexafluoride and antimony hexafluoride which exhibit strong acidity.
  • Examples of the photoacid generator include the above formulas (8-1), (8-2), (8-3), (8-8), (8-9), and (8-10). Particularly preferred are formulas (8-1) and (8-2). These photoacid generators can be used alone or in combination of two or more.
  • thermal acid generator examples include sulfonium salts and phosphonium salts, and sulfonium salts are preferably used.
  • R ′ independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms is particularly preferable.
  • the above composition may contain a conventional additive as required.
  • additives include pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistances). Stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, fillers, antistatic agents, curing agents and the like. These additives may be used alone or in combination of two or more.
  • the curable composition containing the epoxy compound represented by the said Formula (1) and a photo-acid generator can be apply
  • Examples of the method for applying the curable composition of the present invention onto a substrate include a flow coating method, a spin coating method, a spray coating method, a screen printing method, a casting method, a bar coating method, a curtain coating method, a roll coating method, and a gravure. Examples thereof include a coating method, a dipping method, and a slit method.
  • the thickness of the coating film formed from the curable composition of the present invention can be selected from the range of about 0.01 ⁇ m to 10 mm depending on the use of the cured product. For example, when used for a photoresist, 0.05 to 10 ⁇ m. (Especially 0.1 to 5 ⁇ m), about 10 ⁇ m to 5 mm (particularly 100 ⁇ m to 1 mm) when used for printed wiring boards, and 0.1 to 100 ⁇ m (particularly when used for optical thin films). In particular, it can be about 0.3 to 50 ⁇ m.
  • Examples of light to be irradiated or exposed in the case of using a photoacid generator include gamma rays, X-rays, ultraviolet rays, visible rays and the like, and usually visible rays or ultraviolet rays, particularly ultraviolet rays are often used.
  • the wavelength of light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, more preferably about 200 to 400 nm, and particularly about 300 to 400 nm.
  • Irradiation dose may vary depending on the thickness of the coating film, for example, 2 ⁇ 20000mJ / cm 2, preferably to the 5 ⁇ 5000mJ / cm 2 approximately.
  • the light source can be selected according to the type of light to be exposed.
  • a low-pressure mercury lamp for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deuterium lamp, a halogen lamp, laser light (helium-cadmium laser, excimer) For example, a laser).
  • laser light helium-cadmium laser, excimer
  • a laser By such light irradiation, the curing reaction of the composition proceeds.
  • the coating film is heated after light irradiation using a photoacid generator, for example, at room temperature to about 250 ° C.
  • the heating time can be selected from a range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, about 5 seconds to 2 hours.
  • the coating film formed on the base material may be subjected to pattern exposure.
  • This pattern exposure may be performed by scanning with a laser beam or by irradiating light through a photomask.
  • a pattern or an image can be formed by developing (or dissolving) a non-irradiated region (unexposed portion) generated by such pattern exposure with a developer.
  • an alkaline aqueous solution or an organic solvent can be used as the developer.
  • alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline,
  • the amine aqueous solution include ethanolamine, propylamine, and ethylenediamine.
  • the alkaline developer is generally an aqueous solution of 10% by mass or less, and preferably an aqueous solution of 0.1 to 3.0% by mass is used. Further, alcohols and surfactants may be added to the developer and used, and the amount of these added is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the developer. Among these, a 0.1 to 2.38 mass% tetramethylammonium hydroxide aqueous solution can be used.
  • the organic solvent as a developing solution can use a general organic solvent, for example, acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether,
  • a general organic solvent for example, acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether
  • Examples include propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, and cyclohexanone.
  • a surfactant may be added to the curable composition of the present invention for the purpose of improving coating properties.
  • surfactants include, but are not limited to, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • the said surfactant can be used individually or in combination of 2 or more types.
  • a fluorosurfactant is preferable because of its high coating property improving effect.
  • Specific examples of the fluorosurfactant include trade names: EFTOP [registered trademark] EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.
  • the addition amount of the surfactant in the curable composition of the present invention is 0.0008 to 4.5% by mass, preferably 0.0008 to 2.7, based on the solid content of the curable composition. % By mass, more preferably 0.0008 to 1.8% by mass.
  • An adhesion promoter can be added to the curable composition of the present invention for the purpose of improving the adhesion to the substrate after development.
  • chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, Alkoxysilanes such as phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, silazanes such as dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -Amin
  • the said adhesion promoter can be used individually or in combination of 2 or more types.
  • the addition amount of the adhesion promoter in the curable composition of the present invention is usually 18% by mass or less, preferably 0.0008 to 9% by mass, more preferably based on the solid content of the curable composition. 0.04 to 9% by mass.
  • the curable composition of the present invention may contain a sensitizer.
  • sensitizers that can be used include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone.
  • sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes. And pyrylium salt dyes.
  • anthracene-based sensitizer when used in combination with a cationic curing catalyst (radiation-sensitive cationic polymerization initiator), the sensitivity is drastically improved and also has a radical polymerization initiation function.
  • the catalyst species can be simplified.
  • specific anthracene compounds dibutoxyanthracene, dipropoxyanthraquinone and the like are effective.
  • the addition amount of the sensitizer in the curable composition of the present invention is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content of the curable composition. .
  • NMR FT-NMR (ECX300) manufactured by JEOL Ltd.
  • LC-MS Liquid chromatograph mass spectrometer manufactured by Waters Co., Ltd.
  • GC-MS Gas chromatograph mass spectrometer manufactured by Shimadzu Corporation (GC-MS QP5050A) TOF-MS (MALDI): MALDI-TOF mass spectrometer (autoflex III) manufactured by Bruker Daltonics Co., Ltd.
  • Viscosity measurement E type viscometer manufactured by Tokimec Co., Ltd.
  • UV / visible / near infrared spectrophotometer UV-3600 manufactured by Shimadzu Corporation Bending test: Precision universal testing machine manufactured by Shimadzu Corporation (AGS-X series) Linear expansion coefficient and glass transition temperature measurement: Thermo Instruments Measuring Machine manufactured by TA Instruments Inc. (TMA Q400) The following epoxy compounds were prepared.
  • the obtained compound is bis (2,2-bis (2,3-epoxypropyloxymethyl) corresponding to the combination of formula (4-3) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. ) Butyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester.
  • the viscosity was 2867 mPa ⁇ s at 25 ° C.
  • This epoxy compound was designated as (i-1).
  • Synthesis example 2 Synthesis of bis (3- (2,3-epoxypropyloxy) -2,2-bis (2,3-epoxypropyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester
  • cis-4-cyclohexene-1,2-dicarboxylic anhydride 8.0 g, paratoluenesulfonic acid monohydrate 2.0 g, toluene 150 mL, pentaerythritol triallyl ether (70%) 39 g was added and reacted at reflux temperature for 35 hours.
  • the obtained compound is bis (3- (2,3-epoxypropyloxy) -2,2 corresponding to the combination of formula (4-3) corresponding to the mother nucleus and formula (2-2) corresponding to the substituent.
  • -B is (2,3-epoxypropyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester.
  • the viscosity was 15808 mPa ⁇ s at 25 ° C.
  • This epoxy compound was designated as (i-2).
  • Synthesis example 3 Synthesis of tris (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1,2,3-propanetricarboxylic acid ester Dean-Stark apparatus, propane-1,2 in a reactor equipped with a condenser , 3-tricarboxylic acid 12 g, p-toluenesulfonic acid monohydrate 2.6 g, toluene 200 mL, and trimethylolpropane diallyl ether (90%) 49 g were added and reacted at reflux temperature for 24 hours.
  • the resulting compound was tris (2,2-bis (2,3-epoxypropyloxymethyl) corresponding to the combination of formula (6-1) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. Butyl) -1,2,3-propanetricarboxylic acid ester. The viscosity was 5421 mPa ⁇ s at 25 ° C. This epoxy compound was designated as (i-3).
  • Synthesis example 4 Synthesis of tetra (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1,2,3,4-butanetetracarboxylic acid ester Dean-Stark apparatus, butane in reactor equipped with cooler Add 7 g of 1,2,3,4-tetracarboxylic dianhydride, 0.7 g of paratoluenesulfonic acid monohydrate, 150 mL of toluene, and 35 g of trimethylolpropane diallyl ether (90%), and at reflux temperature for 51 hours Reacted.
  • Synthesis example 5 Synthesis of 1,3,5-tris [2- [2,2-bis (2,3-epoxypropyloxymethyl) butyloxy] carbonylethyl] isocyanurate 45 g of trimethylolpropane diallyl ether, 360 mL of dichloromethane, 4- 23 g of dimethylaminopyridine, 36 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 18 g of tris (2-carboxyethyl) isocyanurate were added and reacted at room temperature for 3 days. After completion of the reaction, the organic layer was washed with hydrochloric acid and aqueous sodium bicarbonate and concentrated.
  • the reactor was charged with 23 g of 1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) -3- (2,3-propenyloxy) propyloxy] carbonylethyl] isocyanurate, chloroform 1 L and 63 g of metachloroperbenzoic acid were added and reacted at room temperature for 6 days. After completion of the reaction, the reaction was quenched with an aqueous sodium thiosulfate solution and washed with an aqueous sodium bicarbonate solution and water. The organic layer was evaporated to obtain a crude product.
  • Synthesis example 7 Synthesis of 1,3,5-tris [2- [1- (2,3-epoxypropyloxymethyl) -2- (2,3-epoxypropyloxy) ethyloxy] carbonylethyl] isocyanurate After adding 55 g of (2-carboxyethyl) and 170 mL of N, N-dimethylformamide and confirming dissolution, 63 g of thionyl chloride was added dropwise. The mixture was stirred at room temperature for 1 hour, and the precipitated solid was filtered, washed with chloroform, and dried to obtain 54 g of 1,3,5-tris (2-chloroformylethyl) isocyanurate as a white solid.
  • Synthesis example 8 Synthesis of 1,3,5-tris [2,3-bis (2,3-epoxypropyloxy) propyl] isocyanurate 30 g of isocyanuric acid, 5 g of tetramethylammonium chloride, 1,3-dimethyl-2-imidazolidi Non-300 mL and allyl glycidyl ether 95 g were added and reacted at 100 ° C. for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, and the organic layer was washed with sodium bicarbonate water and concentrated.
  • a sulfonium salt propylene carbonate solution (formula (8-2), active ingredient 50%, trade name CPI-101A, manufactured by San Apro Co., Ltd.) was prepared. This was designated as photoacid generator (ii-1).
  • a propylene carbonate solution of a sulfonium salt (formula (8-1), active ingredient 50%, trade name CPI-100P, manufactured by San Apro Co., Ltd.) was prepared. This was designated as photoacid generator (ii-2).
  • Example 1 An epoxy compound and a photoacid generator are blended in the proportions shown in Table 1, mixed with an apparatus (trade name: Awatori Rentaro, manufactured by Shinki Co., Ltd.) for stirring and defoaming, defoamed and curable composition was prepared. All compounding amounts are described in parts by mass, and the epoxy compound and the photoacid generator are described in parts by mass of the active ingredient.
  • the photoacid generators (ii-1) and (ii-2) in the propylene carbonate solution were used as they were.
  • the prepared curable composition was irradiated with UV (ultraviolet rays) from a distance of 9.5 cm, the photocuring behavior was observed with a rheometer, and the storage elastic modulus was 10 4 Pa (1 ⁇ 10 4 Pa). ) (Second) was defined as the curing time (second). UV irradiation was performed for up to 600 seconds.
  • the rheometer was manufactured by Rheologica (trade name VAR-50 type), the lamp was an Hg-Xe lamp, the irradiation UV wavelength was 365 nm, and the irradiation amount was 20 mW / cm 2 .
  • the irradiation window material in UV irradiation used hard glass of 3 mm thickness, and the film thickness of the coating film formed from the curable composition was 50 ⁇ m.
  • the photocuring time of the curable composition was measured and listed in Table 1.
  • Examples 2 to 8 and Comparative Examples 1 to 5 Similarly to Example 1, curable compositions were prepared at the blending ratios shown in Tables 1 to 4, and the photocuring time of the curable composition was measured. The results are shown in Tables 1 to 4.
  • Example 9 The curable composition prepared at the blending ratio shown in Table 5 in the same manner as in Example 1 was applied to a PET film (Toyobo A4100 125 ⁇ m) with a 75 ⁇ m applicator, and UV (ultraviolet) irradiation was performed from the distance of 26.5 cm as shown in the following integration.
  • a tack-free test (a finger touch drying time test) was performed immediately after irradiation.
  • the UV irradiator uses a batch furnace type ultraviolet curing device for 2 kW x 1 lamp (made by Eye Graphics), the lamp uses an Hg lamp (H02-L41 2.0 kW made by Eye Graphics), and the illuminance is 20 mW / cm. 2 (365 nm). Quartz glass was used as the irradiation window material in the UV irradiation.
  • the tack-free time of the curable composition was evaluated and listed in Table 5.
  • Example 10 Comparative Examples 6 to 9
  • the curable composition was prepared at the blending ratio shown in Table 5 in the same manner as in Example 9, and the tack-free time of the curable composition was evaluated and listed in Table 5.
  • the evaluation criteria in Table 5 are 5 for curing ((), sticking a little ( ⁇ ), leaving a mark on the finger ( ⁇ ), surface curing but internal uncured ( ⁇ x), uncured (x). Rated by stage.
  • thermoset Example 11
  • epoxy compound (i-1) and 31.3 g of acid anhydride curing agent Rikacid MH-700 (trade name, manufactured by Shin Nippon Rika Co., Ltd., components are 4-methylhexahydrophthalic anhydride and hexahydro (Mixed phthalic anhydride in a molar ratio of 70:30) was added, and the mixture was degassed by stirring at room temperature for 30 minutes under reduced pressure.
  • Hishicolin PX-4ET (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., the component is tetrabutylphosphonium diethyl phosphorodithioate) was added as a curing accelerator, and the mixture was degassed with stirring for 5 minutes.
  • This mixture was poured between glass plates treated with a release agent sandwiched with 3 mm silicone rubber (treated with release agent SR-2410 (trade name) manufactured by Toray Dow Corning Co., Ltd. for 1 hour at 150 ° C.). Precuring was performed at 100 ° C. for 2 hours, and main curing was performed at 150 ° C. for 5 hours.
  • Example 12 9.4 g of epoxy compound (i-2), 14.3 g of Jamaicacid MH-700, and 0.10 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Example 13 16.5 g of epoxy compound (i-3), 18.7 g of Jamaicacid MH-700, and 0.17 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Example 14 10.2 g of the epoxy compound (i-4), 11.7 g of Spaincid MH-700 and 0.11 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Example 15 5.02 g of the epoxy compound (i-5), 4.66 g of Jamaicacid MH-700 and 0.063 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Example 16 13.5 g of epoxy compound (i-6), 16.6 g of Jamaicacid MH-700 and 0.13 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Example 17 7.66 g of the epoxy compound (i-7), 8.38 g of Jamaicacid MH-700 and 0.078 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Example 18 14.2 g of the epoxy compound (i-8), 20.0 g of Jamaicacid MH-700, and 0.15 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Comparative Example 10 14.7 g of the epoxy compound (i-5), 24.1 g of Jamaicacid MH-700 and 0.15 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • Comparative Example 11 14.6 g of epoxy compound (i-6), 20.9 g of Spaincid MH-700, and 0.15 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
  • the obtained cured product was measured for a three-point bending test (bending strength and bending elastic modulus), transmittance, linear expansion coefficient, and glass transition temperature.
  • the transmittance at 400 nm was measured using a spectrophotometer.
  • the linear expansion coefficient was measured based on JIS K-6911. The thickness of the test piece was accurately measured and measured by a TMA (thermomechanical analysis) expansion / compression method at a load of 0.05 N and a temperature increase rate of 5 ° C./min.
  • Tg glass transition temperature
  • the curable composition containing the epoxy compound of the present invention has light and thermosetting properties, and has excellent adhesion to the substrate, high transparency (transparency to visible light), hard coat properties, high heat resistance, and the like. It has characteristics and can be used for covering and bonding electronic parts, optical parts and precision mechanism parts. For example, cellular phones and camera lenses, optical elements such as light emitting diodes (LEDs) and semiconductor lasers (LD), liquid crystal panels, biochips, camera lenses and prisms, hard disk magnetic parts such as personal computers, CDs and DVDs It can be used for bonding player pickups (parts that capture optical information reflected from the disk), speaker cones and coils, motor magnets, circuit boards, electronic components, automotive internal components, and the like.
  • LEDs light emitting diodes
  • LD semiconductor lasers
  • liquid crystal panels liquid crystal panels
  • biochips biochips
  • camera lenses and prisms hard disk magnetic parts
  • hard disk magnetic parts such as personal computers, CDs and DVDs
  • It can be used for bonding player pickup
  • the curable composition of the present invention is combined with a three-dimensional CAD to cure a resin to form a complex three-dimensional object, applied to optical modeling such as model production of industrial products, optical fiber coating, adhesion, light Application to waveguides, thick film resists (for MEMS) and the like can be mentioned.

Abstract

[Problem] To provide an epoxy resin composition which has low viscosity and which exhibits not only high heat curability but also high cationic curability. [Solution] An epoxy compound represented by formula (1), and a curable composition which comprises the epoxy compound and an acid generator or a curing agent. In formula (1), A is an (n4)-valent C2-10 unsaturated hydrocarbon group, an (n4)-valent C4-20 cyclic hydrocarbon group, an (n4)-valent nitrogen-containing ring group, an (n4)-valent linear c3-10 hydrocarbon group, or an (n4)-valent group consisting of a combination of two or more of such groups, R1 and R2 are each independently a hydrogen atom or C1-10 alkyl, R3 is an (n3+1)-valent hydrocarbon group, n1 is an integer of 2, n2 is an integer of 1, n3 is an integer of 2 to 5, n4 is an integer of 2 to 8, n5 is an integer of 0 or 1, and n6 is an integer of 0 or 1. The acid generator is a photoacid generator or a thermal acid generator, while the curing agent is an acid anhydride or an amine.

Description

多官能エポキシ化合物Multifunctional epoxy compound
　本発明は光又は熱硬化性エポキシ樹脂組成物に関する。より詳しくは、基板に対する高い密着性、高透明性（可視光線に対する透明性）、ハードコート性、高耐熱性などの優れた特性を有する硬化物を得るのに有用な光又は熱硬化性エポキシ樹脂組成物（電子材料用及び光学材料用樹脂組成物）およびその硬化物（コンポジット硬化物）に関する。 The present invention relates to a light or thermosetting epoxy resin composition. More specifically, a light or thermosetting epoxy resin useful for obtaining a cured product having excellent properties such as high adhesion to a substrate, high transparency (transparency to visible light), hard coat properties, and high heat resistance. The present invention relates to a composition (resin composition for electronic materials and optical materials) and a cured product thereof (composite cured product).
　従来、エポキシ樹脂は、硬化剤と組み合わせたエポキシ樹脂組成物として、電子材料分野において幅広く用いられている。このような電子材料分野のうち、例えば、反射防止膜（液晶ディスプレイ用の反射防止膜など）の高屈折率層、光学薄膜（反射板など）、電子部品用封止材、プリント配線基板、層間絶縁膜材料（ビルドアッププリント基板用層間絶縁膜材料など）などの用途では、基材に対する高い密着性、ハードコート性、耐熱性、可視光に対する高透明性などの性能が成形材料に要求される。
　一方で、エポキシ化合物と光および熱酸発生剤とを組み合わせたエポキシ樹脂組成物は溶剤を使用せず、しかもエポキシ化合物を単独で硬化させることができるため、近年多くの検討がされている。特に紫外線による光カチオン硬化は、大型の硬化用オーブンを必要とせず、エネルギー投入量も少ない点で非常に優れている。
　エポキシ基を脂環構造にのみ有する脂環式エポキシ化合物は、光を用いたカチオン硬化には反応性が高いため広く使用されているが、その構造がリジッドであるために硬化物が硬く、もろくなる傾向にある。 Conventionally, epoxy resins have been widely used in the field of electronic materials as epoxy resin compositions combined with curing agents. Among such electronic material fields, for example, a high refractive index layer of an antireflection film (such as an antireflection film for a liquid crystal display), an optical thin film (such as a reflection plate), a sealing material for electronic components, a printed wiring board, an interlayer In applications such as insulation film materials (such as interlayer insulation film materials for build-up printed circuit boards), molding materials are required to have high adhesion to substrates, hard coat properties, heat resistance, and high transparency to visible light. .
On the other hand, an epoxy resin composition in which an epoxy compound and a light and thermal acid generator are combined does not use a solvent and can cure the epoxy compound alone. Therefore, many studies have been made in recent years. In particular, photocationic curing with ultraviolet rays is very excellent in that it does not require a large curing oven and requires less energy.
An alicyclic epoxy compound having an epoxy group only in an alicyclic structure is widely used because of its high reactivity to cationic curing using light, but because the structure is rigid, the cured product is hard and brittle. Tend to be.
　ところで、ラクトン変性された多官能の脂環式エポキシ化合物及びそのエポキシ化合物を用いたエポキシ樹脂組成物およびそれらの製造方法が提案されている（特許文献１参照）。
　一方、グリシジルエステル型のエポキシ化合物は酸発生剤に対する反応性が低く、反応に時間がかかるため、一般的にカチオン硬化には向いていないと考えられてきた。
　グリシジルエステル基を有する多官能エポキシ化合物としては、シクロブタンテトラカルボン酸テトラグリシジルエステルやシクロペンタンテトラカルボン酸テトラグリシジルエステル、シクロヘキサントリカルボン酸トリグリシジルエステルを用いたエポキシ樹脂組成物が提案されている（特許文献２、３参照）。
　また、エポキシ基を有するシクロヘキサンジカルボン酸のエポキシアルキルエステルを架橋性化合物として用いるカルボキシル基含有樹脂が提案されている（特許文献４参照）。　 By the way, a lactone-modified polyfunctional alicyclic epoxy compound, an epoxy resin composition using the epoxy compound, and a production method thereof have been proposed (see Patent Document 1).
On the other hand, glycidyl ester type epoxy compounds have been considered to be generally unsuitable for cationic curing because of their low reactivity to acid generators and the long reaction time.
As a polyfunctional epoxy compound having a glycidyl ester group, an epoxy resin composition using cyclobutanetetracarboxylic acid tetraglycidyl ester, cyclopentanetetracarboxylic acid tetraglycidyl ester, or cyclohexanetricarboxylic acid triglycidyl ester has been proposed (Patent Literature). 2 and 3).
Further, a carboxyl group-containing resin using an epoxy alkyl ester of cyclohexanedicarboxylic acid having an epoxy group as a crosslinkable compound has been proposed (see Patent Document 4).
特開平４－０６９３６０号公報Japanese Patent Laid-Open No. 4-069360 特開昭５０－０１０８９３号公報Japanese Unexamined Patent Publication No. 50-010893 特開２００６－２７４１９０号公報JP 2006-274190 A 米国特許第３５６５９２２号明細書US Pat. No. 3,565,922
　本発明者らは、鋭意検討した結果、母核が種々の骨格を有し、その骨格となる有機基は複数の側鎖を有し、そしてその側鎖は炭化水素基を介してエポキシ基を複数有した構造であって、該エポキシ基を１分子中に複数有する多官能エポキシ化合物は、熱硬化性だけでなくカチオン硬化性が付与されることを見出した。
　これにより、本発明は、前記エポキシ組成物、及び前記エポキシ化合物を用いた液状で、熱硬化性だけでなくカチオン硬化性が高い硬化性組成物を提供しようとするものである。この硬化性組成物から得られる硬化物は、高透明性、高耐熱性を有する。 As a result of intensive studies, the present inventors have found that the mother nucleus has various skeletons, the organic group serving as the skeleton has a plurality of side chains, and the side chains have an epoxy group via a hydrocarbon group. It has been found that a polyfunctional epoxy compound having a plurality of epoxy groups and having a plurality of the epoxy groups in one molecule is imparted not only thermosetting properties but also cationic curing properties.
Accordingly, the present invention intends to provide a liquid curable composition using the epoxy composition and the epoxy compound and having high cationic curability as well as thermosetting. A cured product obtained from this curable composition has high transparency and high heat resistance.
　本発明は、第１観点として、下記式（１）：
Figure JPOXMLDOC01-appb-C000003
 ［式（１）中、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ3は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表し、ｎ５は０又は１の整数を表し、ｎ６は０又は１の整数を表す。］で表されるエポキシ化合物、
　第２観点として、前記式（１）が、式（１－１）、式（１－２）、又は式（１－３）：
Figure JPOXMLDOC01-appb-C000004
 ［式（１－１）及び式（１－３）中において、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、式（１－２）中において、Ａ’は（ｎ４）価の窒素含有環基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ３は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表す。］で表される、第１観点に記載のエポキシ化合物、
　第３観点として、前記Ａがエチレン、プロピレン、又はノルボルネンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の不飽和炭化水素基である、第１観点又は第２観点に記載のエポキシ化合物、
　第４観点として、前記Ａがシクロブタン、シクロペンタン、シクロヘキサン、エポキシシクロヘキサン、アルキル置換されたエポキシシクロヘキサン、ビシクロヘプテン、ビシクロオクテン、又はアダマンタンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の環状炭化水素基である、第１観点又は第２観点に記載のエポキシ化合物、
　第５観点として、前記Ａがトリアルキルイソシアヌレートから（ｎ４）個の水素原子を取り除いた（ｎ４）価の窒素含有環基であり、前記Ａ’がイソシアヌル酸、シアヌル酸、ヒダントイン、又はバルビツール酸から（ｎ４）個の水素原子を取り除いた（ｎ４）価の窒素含有環基である、第１観点又は第２観点に記載のエポキシ化合物、
　第６観点として、前記Ａがプロパン、ブタン、ペンタン、又はヘキサンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の鎖状炭化水素基である、第１観点又は第２観点に記載のエポキシ化合物、
　第７観点として、第１観点乃至第６観点のいずれか一つに記載のエポキシ化合物、及び硬化剤を含む硬化性組成物、
　第８観点として、前記硬化剤が酸無水物、アミン、フェノール樹脂、ポリアミド樹脂、イミダゾール、又はポリメルカプタンである、第７観点に記載の硬化性組成物、
　第９観点として、前記エポキシ化合物のエポキシ基１当量に対して前記硬化剤を０．５～１．５当量の割合で含有する、第７観点又は第８観点に記載の硬化性組成物、
　第１０観点として、第１観点乃至第６観点のいずれか一つに記載のエポキシ化合物、及び酸発生剤を含む硬化性組成物、
　第１１観点として、前記酸発生剤が光酸発生剤又は熱酸発生剤である、第１０観点に記載の硬化性組成物、
　第１２観点として、前記酸発生剤がオニウム塩である、第１１観点に記載の硬化性組成物、
　第１３観点として、前記酸発生剤がスルホニウム塩化合物、又はヨードニウム塩化合物である、第１１観点に記載の硬化性組成物、
　第１４観点として、前記エポキシ化合物の質量に対して前記酸発生剤を０．１～２０質量％の割合で含有する、第１０観点乃至第１３観点のいずれか一つに記載の硬化性組成物
である。 As a first aspect of the present invention, the following formula (1):
Figure JPOXMLDOC01-appb-C000003
 [In the formula (1), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an (n4) -valent nitrogen A ring-containing group, a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a (n4) -valent group in combination thereof, wherein R 1 and R 2 are each independently a hydrogen atom Or an alkyl group having 1 to 10 carbon atoms, R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, and n3 represents an integer of 2 to 5 N4 represents an integer of 2 to 8, n5 represents an integer of 0 or 1, and n6 represents an integer of 0 or 1. An epoxy compound represented by
As a second aspect, the formula (1) is transformed into the formula (1-1), the formula (1-2), or the formula (1-3):
Figure JPOXMLDOC01-appb-C000004
 [In the formulas (1-1) and (1-3), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, and (n4) a cyclic group having 4 to 20 carbon atoms. Represents a hydrocarbon group, an (n4) -valent nitrogen-containing cyclic group, an (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a combination of these (n4) -valent groups. 2), A ′ represents a (n4) -valent nitrogen-containing cyclic group, R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 3 represents (N3 + 1) represents a valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2 to 8. The epoxy compound according to the first aspect, represented by:
As a third aspect, the epoxy compound according to the first aspect or the second aspect, wherein A is an (n4) -valent unsaturated hydrocarbon group obtained by removing (n4) hydrogen atoms from ethylene, propylene, or norbornene. ,
As a fourth aspect, (n4) valent cyclic carbonization in which (n4) hydrogen atoms are removed from A is cyclobutane, cyclopentane, cyclohexane, epoxycyclohexane, alkyl-substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane. The epoxy compound according to the first aspect or the second aspect, which is a hydrogen group,
As a fifth aspect, the A is a (n4) -valent nitrogen-containing cyclic group obtained by removing (n4) hydrogen atoms from a trialkyl isocyanurate, and the A ′ is isocyanuric acid, cyanuric acid, hydantoin, or barbitur The epoxy compound according to the first aspect or the second aspect, which is a (n4) -valent nitrogen-containing cyclic group obtained by removing (n4) hydrogen atoms from an acid,
As a sixth aspect, the A is a (n4) -valent chain hydrocarbon group obtained by removing (n4) hydrogen atoms from propane, butane, pentane, or hexane, according to the first aspect or the second aspect. Epoxy compounds,
As a seventh aspect, a curable composition comprising the epoxy compound according to any one of the first aspect to the sixth aspect, and a curing agent,
As an eighth aspect, the curable composition according to the seventh aspect, in which the curing agent is an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, or a polymercaptan,
As a ninth aspect, the curable composition according to the seventh aspect or the eighth aspect, containing the curing agent in a proportion of 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy compound,
As a tenth aspect, a curable composition comprising the epoxy compound according to any one of the first aspect to the sixth aspect, and an acid generator,
As an eleventh aspect, the curable composition according to the tenth aspect, in which the acid generator is a photoacid generator or a thermal acid generator,
As a twelfth aspect, the curable composition according to the eleventh aspect, in which the acid generator is an onium salt,
As a thirteenth aspect, the curable composition according to the eleventh aspect, in which the acid generator is a sulfonium salt compound or an iodonium salt compound,
As a fourteenth aspect, the curable composition according to any one of the tenth aspect to the thirteenth aspect, containing the acid generator in a proportion of 0.1 to 20% by mass with respect to the mass of the epoxy compound. It is.
　炭化水素基を介して骨格となる有機基に結合した複数のエポキシ環を有するエポキシ化合物は、該炭化水素基を長くすればするほど該エポキシ環の自由度が大きくなり、反応性が高くなるためエポキシ基がすべて反応に関与し、また複数のエポキシ環を有することでカチオン硬化性が高くなる。
　また、上記エポキシ化合物と、光酸発生剤を少なくとも含む硬化性組成物を光硬化させると、優れた機械的特性と優れた光学特性とを両立できる硬化物又は硬化塗膜を形成できることが期待される。特に、炭化水素基を長くするほど、該硬化物及び硬化塗膜の靭性が高くなることが期待される。
　斯かる観点より案出された本発明のエポキシ化合物は、母核が種々の骨格を有し、その骨格となる有機基は複数の側鎖を有し、そしてその側鎖は炭化水素基を介してエポキシ基を複数有した構造であって、該エポキシ基を１分子中に複数有するものとしたことにより、熱硬化性だけでなくカチオン硬化性をも有する特徴的な効果を発揮する。
　本発明の硬化性組成物は、上記式（１）で表されるエポキシ化合物と硬化剤（例えばアミンや酸無水物）、場合によっては、更に硬化助剤を含むことができる。
　また、本発明では、上記式（１）で表されるエポキシ化合物を光酸発生剤又は熱酸発生剤を用いて、光硬化又は熱硬化させようとするものである。したがって、光酸発生剤又は熱酸発生剤を用いることにより、通常用いられるエポキシの硬化剤（例えばアミンや酸無水物）を用いないか又はそれらを用いたとしても極端にそれらの含有量が少ないため、本発明の硬化性組成物の保存安定性が良好である。
　本発明の硬化性組成物は、ＵＶ照射による光硬化により硬化するため、熱に弱い材料（基材）に適用できる。
　また、本発明に用いられるエポキシ化合物は液状であるため、それを用いた本発明の硬化性組成物は充填性が良好である。
　さらに、本発明のエポキシ化合物を含む硬化性組成物は、低粘度、速乾性等の特徴を持ち電子部品、光学部品、精密機構部品の被覆や接着に用いることができる。 An epoxy compound having a plurality of epoxy rings bonded to a skeleton organic group via a hydrocarbon group has a greater degree of freedom and reactivity as the hydrocarbon group becomes longer. All the epoxy groups are involved in the reaction, and having a plurality of epoxy rings increases the cationic curability.
Further, when the curable composition containing at least the epoxy compound and the photoacid generator is photocured, it is expected that a cured product or a cured coating film capable of achieving both excellent mechanical properties and excellent optical properties can be formed. The In particular, the longer the hydrocarbon group, the higher the toughness of the cured product and cured coating film is expected.
In the epoxy compound of the present invention devised from such a viewpoint, the mother nucleus has various skeletons, the organic group serving as the skeleton has a plurality of side chains, and the side chains are connected via a hydrocarbon group. By having a structure having a plurality of epoxy groups and having a plurality of the epoxy groups in one molecule, a characteristic effect having not only thermosetting properties but also cationic curing properties is exhibited.
The curable composition of the present invention can further contain an epoxy compound represented by the above formula (1) and a curing agent (for example, an amine or acid anhydride), and optionally a curing aid.
In the present invention, the epoxy compound represented by the above formula (1) is intended to be photocured or thermally cured using a photoacid generator or a thermal acid generator. Therefore, by using a photoacid generator or a thermal acid generator, the epoxy curing agents (eg amines and acid anhydrides) usually used are not used, or even if they are used, their content is extremely low. Therefore, the storage stability of the curable composition of the present invention is good.
Since the curable composition of the present invention is cured by photocuring by UV irradiation, it can be applied to a heat-sensitive material (base material).
Moreover, since the epoxy compound used for this invention is a liquid, the curable composition of this invention using it has favorable filling property.
Furthermore, the curable composition containing the epoxy compound of the present invention has characteristics such as low viscosity and quick drying, and can be used for coating and bonding electronic parts, optical parts and precision mechanism parts.
　本発明は上記式（１）で表されるエポキシ化合物である。上記式（１）中、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ3は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表し、ｎ５は０又は１の整数を表し、ｎ６は０又は１の整数を表す。 The present invention is an epoxy compound represented by the above formula (1). In the above formula (1), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an (n4) -valent nitrogen. A ring-containing group, a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a (n4) -valent group in combination thereof, wherein R 1 and R 2 are each independently a hydrogen atom Or an alkyl group having 1 to 10 carbon atoms, R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, and n3 represents an integer of 2 to 5 N4 represents an integer of 2 to 8, n5 represents an integer of 0 or 1, and n6 represents an integer of 0 or 1.
　上記式（１）は、上記式（１－１）、式（１－２）、又は式（１－３）で表されるエポキシ化合物を包含する。式（１－１）及び式（１－３）中、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、式（１－２）中、Ａ’は（ｎ４）価の窒素含有環基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ３は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表す。 The above formula (1) includes an epoxy compound represented by the above formula (1-1), formula (1-2), or formula (1-3). In the formulas (1-1) and (1-3), A is an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, and (n4) a cyclic hydrocarbon having 4 to 20 carbon atoms. A (n4) -valent nitrogen-containing cyclic group, an (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a combination thereof (n4) -valent group, represented by the formula (1-2) Wherein A ′ represents a (n4) -valent nitrogen-containing cyclic group, R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 3 represents (n3 + 1) A valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2 to 8.
　式（１）、式（１－１）、及び式（１－３）において、Ａが（ｎ４）価の不飽和炭化水素基である場合、Ａとしては、例えば、エチレン、プロピレン、又はノルボルネンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の不飽和炭化水素基が挙げられる。
　式（１）、式（１－１）、及び式（１－３）において、Ａが（ｎ４）価の環状炭化水素基である場合、Ａとしては、例えば、シクロブタン、シクロペンタン、シクロヘキサン、エポキシシクロヘキサン、アルキル置換されたエポキシシクロヘキサン、ビシクロヘプテン、ビシクロオクテン、又はアダマンタンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の環状炭化水素基が挙げられる。
　式（１）、式（１－１）、式（１－２）、及び式（１－３）において、Ａ及びＡ’が（ｎ４）価の窒素含有環基である場合、Ａとしては、例えば、トリアルキルイソシアヌレートから（ｎ４）個の水素原子を取り除いた（ｎ４）価の窒素含有環基が、Ａ’としては、例えば、イソシアヌル酸、シアヌル酸、ヒダントイン、又はバルビツール酸から（ｎ４）個の水素原子を取り除いた（ｎ４）価の窒素含有環基が挙げられる。
　式（１）、式（１－１）、及び式（１－３）において、Ａが（ｎ４）価の鎖状炭化水素基である場合、Ａとしては、例えば、プロパン、ブタン、ペンタン、又はヘキサンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の鎖状炭化水素基が挙げられる。 In Formula (1), Formula (1-1), and Formula (1-3), when A is an (n4) -valent unsaturated hydrocarbon group, A is, for example, from ethylene, propylene, or norbornene An (n4) -valent unsaturated hydrocarbon group in which (n4) hydrogen atoms have been removed may be mentioned.
In Formula (1), Formula (1-1), and Formula (1-3), when A is an (n4) -valent cyclic hydrocarbon group, A is, for example, cyclobutane, cyclopentane, cyclohexane, epoxy (N4) -valent cyclic hydrocarbon group in which (n4) hydrogen atoms are removed from cyclohexane, alkyl-substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane.
In Formula (1), Formula (1-1), Formula (1-2), and Formula (1-3), when A and A ′ are (n4) -valent nitrogen-containing cyclic groups, A is For example, a (n4) -valent nitrogen-containing cyclic group obtained by removing (n4) hydrogen atoms from a trialkyl isocyanurate is, for example, from isocyanuric acid, cyanuric acid, hydantoin, or barbituric acid as A ′ (n4 ) (N4) -valent nitrogen-containing cyclic group in which one hydrogen atom is removed.
In Formula (1), Formula (1-1), and Formula (1-3), when A is an (n4) -valent chain hydrocarbon group, A is, for example, propane, butane, pentane, or An (n4) -valent chain hydrocarbon group obtained by removing (n4) hydrogen atoms from hexane is exemplified.
　Ｒ1及びＲ2は、それぞれ独立して、水素原子、又は炭素原子数１～１０のアルキル基を表す。
　炭素原子数１～１０のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロプロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基、１－メチル－シクロプロピル基、２－メチル－シクロプロピル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１，１－ジメチル－ｎ－プロピル基、１，２－ジメチル－ｎ－プロピル基、２－メチル－２－エチル－ｎ－プロピル基、２－メチル－２－メチル－ｎ－プロピル基、２，２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、シクロペンチル基、１－メチル－シクロブチル基、２－メチル－シクロブチル基、３－メチル－シクロブチル基、１，２－ジメチル－シクロプロピル基、２，３－ジメチル－シクロプロピル基、１－エチル－シクロプロピル基、２－エチル－シクロプロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１，１－ジメチル－ｎ－ブチル基、１，２－ジメチル－ｎ－ブチル基、１，３－ジメチル－ｎ－ブチル基、２，２－ジメチル－ｎ－ブチル基、２，３－ジメチル－ｎ－ブチル基、３，３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１，１，２－トリメチル－ｎ－プロピル基、１，２，２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基、１－エチル－２－メチル－ｎ－プロピル基、シクロヘキシル基、１－メチル－シクロペンチル基、２－メチル－シクロペンチル基、３－メチル－シクロペンチル基、１－エチル－シクロブチル基、２－エチル－シクロブチル基、３－エチル－シクロブチル基、１，２－ジメチル－シクロブチル基、１，３－ジメチル－シクロブチル基、２，２－ジメチル－シクロブチル基、２，３－ジメチル－シクロブチル基、２，４－ジメチル－シクロブチル基、３，３－ジメチル－シクロブチル基、１－ｎ－プロピル－シクロプロピル基、２－ｎ－プロピル－シクロプロピル基、１－ｉ－プロピル－シクロプロピル基、２－ｉ－プロピル－シクロプロピル基、１，２，２－トリメチル－シクロプロピル基、１，２，３－トリメチル－シクロプロピル基、２，２，３－トリメチル－シクロプロピル基、１－エチル－２－メチル－シクロプロピル基、２－エチル－１－メチル－シクロプロピル基、２－エチル－２－メチル－シクロプロピル基及び２－エチル－３－メチル－シクロプロピル基等が挙げられる。 R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, and t-butyl. Group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n- Butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2-methyl-2-ethyl-n-propyl group, 2-methyl-2-methyl-n-propyl group 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl - Chloropropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n- Pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n -Butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl- n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2- Methyl-n-propyl group, cyclohexyl group, 1 Methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1 , 3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl- Cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2, 3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl -Cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group and the like.
　Ｒ3は（ｎ３＋１）価の炭化水素基を表し、炭化水素基としては、例えば上記アルキル基から（ｎ３＋１）個の水素原子を取り除いた（ｎ３＋１）価の炭化水素基が挙げられる。 R 3 represents an (n3 + 1) -valent hydrocarbon group, and examples of the hydrocarbon group include an (n3 + 1) -valent hydrocarbon group obtained by removing (n3 + 1) hydrogen atoms from the alkyl group.
　上記母核に置換するＢとしては、下記に例示されるエポキシ基を有する、アルキルエステル基、アルキル基、及びアルキルオキシ基が挙げられる。下記においてＡは母核を表す。
Figure JPOXMLDOC01-appb-C000005
 ［式（２－１）乃至式（２－４）中、ｎ５は０又は１の整数を表し、ｎ６は０又は１の整数を表す。］ Examples of B substituted on the mother nucleus include an alkyl ester group, an alkyl group, and an alkyloxy group having an epoxy group exemplified below. In the following, A represents a mother nucleus.
Figure JPOXMLDOC01-appb-C000005
 [In the formulas (2-1) to (2-4), n5 represents an integer of 0 or 1, and n6 represents an integer of 0 or 1. ]
　また、母核となるＡ及びＡ’は、以下に例示される。下記においてＢは上述の多官能エポキシ基を表す。
　Ａが（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基を表す場合、Ａとしては以下に例示される。
Figure JPOXMLDOC01-appb-C000006
 Further, A and A ′ as the mother nucleus are exemplified below. In the following, B represents the polyfunctional epoxy group described above.
When A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, A is exemplified below.
Figure JPOXMLDOC01-appb-C000006
　Ａが（ｎ４）価の炭素原子数４～２０の環状炭化水素基を表す場合、Ａとしては以下に例示される。
Figure JPOXMLDOC01-appb-C000007
 When A represents an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, A is exemplified below.
Figure JPOXMLDOC01-appb-C000007
　Ａ及びＡ’が（ｎ４）価の窒素含有環基を表す場合、Ａ及びＡ’としては以下に例示される。
Figure JPOXMLDOC01-appb-C000008
 ［（式（５－１）中において、Ｒは水素原子又は炭素原子数１～１０のアルキル基を表す。］ When A and A ′ represent a (n4) -valent nitrogen-containing cyclic group, A and A ′ are exemplified below.
Figure JPOXMLDOC01-appb-C000008
 [In the formula (5-1), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.]
　Ａが（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基を表す場合、Ａとしては以下に例示される。
Figure JPOXMLDOC01-appb-C000009
 When A represents a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, A is exemplified below.
Figure JPOXMLDOC01-appb-C000009
　本発明の式（１）で表される化合物は、上記母核Ａと上記置換基Ｂとの組み合わせで構成される。
　上記式（１－１）で表されるエポキシ化合物は、例えば、上記Ａの構造を有するカルボン酸、又はカルボン酸無水物などのカルボン酸誘導体と、アルケノールとを反応させ、そして得られた不飽和結合を有する化合物（中間体）と過酸化物を反応させて製造することができる。また、該中間体はカルボン酸、又はカルボン酸無水物とアルケノールとの反応によらず如何なる方法でも製造することができ、その不飽和結合を有する中間体と過酸化物を反応させて、上記式（１－１）で表されるエポキシ化合物を製造することができる。 The compound represented by the formula (1) of the present invention is composed of a combination of the mother nucleus A and the substituent B.
The epoxy compound represented by the above formula (1-1) is obtained by, for example, reacting a carboxylic acid derivative such as a carboxylic acid having the structure of A or a carboxylic acid anhydride with an alkenol, and then obtaining the unsaturated compound obtained. It can be produced by reacting a compound having a bond (intermediate) with a peroxide. The intermediate can be produced by any method regardless of the reaction of carboxylic acid or carboxylic anhydride and alkenol, and the intermediate having an unsaturated bond is reacted with a peroxide to obtain The epoxy compound represented by (1-1) can be produced.
　上記母核Ａに置換するＢ（多官能エポキシ基を有するアルキルエステル基）に対応するアルケノールは、以下に例示される。
Figure JPOXMLDOC01-appb-C000010
 The alkenol corresponding to B (alkyl ester group having a polyfunctional epoxy group) substituted on the mother nucleus A is exemplified below.
Figure JPOXMLDOC01-appb-C000010
　母核Ａの構造を有するカルボン酸、又はカルボン酸無水物は、以下に例示される。
　Ａが（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基を表すカルボン酸又はカルボン酸無水物としては以下に例示される。
Figure JPOXMLDOC01-appb-C000011
 The carboxylic acid or carboxylic anhydride having the structure of the mother nucleus A is exemplified below.
Examples of the carboxylic acid or carboxylic anhydride in which A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms are shown below.
Figure JPOXMLDOC01-appb-C000011
　Ａが（ｎ４）価の炭素原子数４～２０の環状炭化水素基を表すカルボン酸又はカルボン酸無水物としては以下に例示される。
Figure JPOXMLDOC01-appb-C000012
 Examples of the carboxylic acid or carboxylic anhydride in which A represents an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms are illustrated below.
Figure JPOXMLDOC01-appb-C000012
　Ａが（ｎ４）価の窒素含有環基を表すカルボン酸としては、トリスカルボキシアルキルイソシアヌレート（ただし、アルキル基としては炭素原子数が１～５、好ましくは炭素原子数が１～３である）が挙げられ、以下に例示される。
Figure JPOXMLDOC01-appb-C000013
 ［式（５－１－１）中において、Ｒは水素原子又は炭素原子数１～１０のアルキル基を表す。］ Examples of the carboxylic acid in which A represents a (n4) -valent nitrogen-containing cyclic group include triscarboxyalkyl isocyanurate (wherein the alkyl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms). And are exemplified below.
Figure JPOXMLDOC01-appb-C000013
 [In the formula (5-1-1), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]
　Ａが（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基を表すカルボン酸、又はカルボン酸無水物としては以下に例示される。
Figure JPOXMLDOC01-appb-C000014
 Examples of the carboxylic acid or carboxylic anhydride in which A represents a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms are illustrated below.
Figure JPOXMLDOC01-appb-C000014
　上記Ａの構造を有するカルボン酸、又はカルボン酸無水物と、アルケノールとを反応させて得られる不飽和結合を有する化合物（中間体）は、式（１－１－１）に例示することができる。
Figure JPOXMLDOC01-appb-C000015
 ［式（１－１－１）中、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ３は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表す。］ The compound (intermediate) having an unsaturated bond obtained by reacting the carboxylic acid or carboxylic acid anhydride having the above structure A with alkenol can be exemplified by the formula (1-1-1). .
Figure JPOXMLDOC01-appb-C000015
 [In the formula (1-1-1), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, (n4 ) Represents a valent nitrogen-containing cyclic group, (n4) a valent chain hydrocarbon group having 3 to 10 carbon atoms, or a combination thereof (n4) valent group, R 1 and R 2 are each independently Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, and n3 represents 2 N4 represents an integer of 2 to 8, and n4 represents an integer of 2 to 8. ]
　即ち、本発明に用いられる式（１－１）で表されるエポキシ化合物は、式（４－３）と式（２－１）との組み合わせからなる式（１－１）で表されるエポキシ化合物を例にとれば、以下の方法で得ることができる。
Figure JPOXMLDOC01-appb-C000016
 That is, the epoxy compound represented by the formula (1-1) used in the present invention is an epoxy compound represented by the formula (1-1) composed of a combination of the formula (4-3) and the formula (2-1). Taking a compound as an example, it can be obtained by the following method.
Figure JPOXMLDOC01-appb-C000016
　カルボン酸無水物とアルケノールを反応させて、中間体（オレフィン）を合成する。この反応は、トルエン等の溶媒中で、パラトルエンスルホン酸、硫酸等の触媒を用い、室温（例えば２０℃）～１１０℃の温度、０～１００時間で行われる。そして、この不飽和化合物を過酸化物で酸化してエポキシ化合物を得ることができる。ここで過酸化物としては、例えば、メタクロロ過安息香酸、過酢酸、過酸化水素－タングステン酸等を用いることができる。この反応はクロロホルム等の溶媒中で、０～６０℃、１～２００時間で行うことができる。上記反応は酸無水物の代わりにジカルボン酸化合物を原料に用いても行うことができる。また、トルエン等の溶媒に溶解しづらいカルボン酸の場合は、メタノール等のアルコールでエステル化し、続いてアルケノールとのエステル交換反応を行う方法、またはカルボン酸とアルケノールをカルボジイミド等の縮合剤を使用して反応させる方法、またはカルボン酸を塩化チオニル等で酸クロリドに変換しアルケノールと反応させる方法によっても上記の中間体（オレフィン）を合成できる。 Carboxylic anhydride and alkenol are reacted to synthesize an intermediate (olefin). This reaction is carried out in a solvent such as toluene using a catalyst such as paratoluenesulfonic acid or sulfuric acid at a temperature of room temperature (for example, 20 ° C.) to 110 ° C. for 0 to 100 hours. The unsaturated compound can be oxidized with a peroxide to obtain an epoxy compound. Here, as the peroxide, for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used. This reaction can be carried out in a solvent such as chloroform at 0 to 60 ° C. for 1 to 200 hours. The above reaction can also be carried out using a dicarboxylic acid compound as a raw material instead of an acid anhydride. In the case of a carboxylic acid that is difficult to dissolve in a solvent such as toluene, a method of esterifying with an alcohol such as methanol, followed by a transesterification reaction with alkenol, or using a condensing agent such as carbodiimide for the carboxylic acid and alkenol. The above intermediates (olefins) can also be synthesized by a method of reacting them, or a method of converting a carboxylic acid into an acid chloride with thionyl chloride or the like and reacting with an alkenol.
　上記式（１－２）で表されるエポキシ化合物は、Ａ’の構造を有する窒素含有環化合物（該化合物はＮＨ基を有する。）と、脱離基を有するアルケノールやアリルハライドとを反応させ、そして得られた不飽和結合を有する化合物（中間体）と過酸化物を反応させて製造することができる。
　また、上記式（１－２）で表されるエポキシ化合物は、Ａ’の構造を有する窒素含有化合物（該化合物はＮＨ基を有する。）と、不飽和結合を有するエポキシ化合物とを反応させ、そして得られたアルコール化合物と脱離基を有するアルケノールやアリルハライドとを反応させ、そして得られた不飽和結合を有する化合物（中間体）と過酸化物を反応させて製造することもできる。
　母核Ａ’に置換するＢに対応する脱離基を有するアルケノールやアリルハライドとしては、例えば上記式（２－１－１）、式（２－２－１）、式（２－３－１）、及び（２－４－１）で表される化合物にメタンスルホニルハライド、トリフルオロメタンスルホン酸無水物、トルエンスルホニルハライド、ニトロベンゼンスルホニルハライド、アセチルハライド、無水酢酸、トリフルオロ無水酢酸、オキシ塩化リン、オキシ臭化リン、チオニルハライド、スルフリルハライド、塩化水素、臭化水素、ヨウ化水素等を反応させて得られる下記式（２－１－２）、式（２－２－２）、式（２－３－２）、及び式（２－４－２）で表される化合物を用いることができる。
Figure JPOXMLDOC01-appb-C000017
 ［（式（２－１－２）、式（２－２－２）、式（２－３－２）、及び式（２－４－２）中、Ｘはメタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、トルエンスルホニルオキシ基、ニトロベンゼンスルホニルオキシ基、アセチルオキシ基、トリフルオロアセチルオキシ基、塩素原子、臭素原子、又はヨウ素原子を表す。］ The epoxy compound represented by the above formula (1-2) is obtained by reacting a nitrogen-containing ring compound having the structure of A ′ (the compound has an NH group) with an alkenol or allyl halide having a leaving group. And the obtained compound (intermediate) having an unsaturated bond and a peroxide can be reacted.
　 Further, the epoxy compound represented by the above formula (1-2) is obtained by reacting a nitrogen-containing compound having a structure of A ′ (the compound has an NH group) with an epoxy compound having an unsaturated bond, It can also be produced by reacting the obtained alcohol compound with an alkenol or allyl halide having a leaving group, and reacting the obtained compound (intermediate) having an unsaturated bond with a peroxide.
Examples of the alkenol or allyl halide having a leaving group corresponding to B substituted on the mother nucleus A ′ include, for example, the above formulas (2-1-1), (2-2-1) and (2-3-1). ), And (2-4-1), methanesulfonyl halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide, acetyl halide, acetic anhydride, trifluoroacetic anhydride, phosphorus oxychloride, The following formula (2-1-2), formula (2-2-2), formula (2) obtained by reacting phosphorus oxybromide, thionyl halide, sulfuryl halide, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc. −3-2) and a compound represented by the formula (2-4-2) can be used.
Figure JPOXMLDOC01-appb-C000017
 [In the formula (2-1-2), formula (2-2-2), formula (2-3-2), and formula (2-4-2), X represents a methanesulfonyloxy group, trifluoromethanesulfonyl Represents an oxy group, a toluenesulfonyloxy group, a nitrobenzenesulfonyloxy group, an acetyloxy group, a trifluoroacetyloxy group, a chlorine atom, a bromine atom, or an iodine atom.]
　母核Ａ’の構造を有する窒素含有環化合物（該化合物はＮＨ基を有する。）としては、以下に例示される。
Figure JPOXMLDOC01-appb-C000018
 Examples of the nitrogen-containing ring compound having the structure of the mother nucleus A ′ (the compound has an NH group) are shown below.
Figure JPOXMLDOC01-appb-C000018
　Ａ’の構造を有する窒素含有環化合物（該化合物はＮＨ基を有する。）と、脱離基を有するアルケノールやアリルハライドとを反応させて得られる不飽和結合を有する化合物（中間体）は、式（１－２－１）に例示することができる。
Figure JPOXMLDOC01-appb-C000019
 ［（式（１－２－１）中、Ａ’は（ｎ４）価の窒素含有環基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ３は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表す。］ A compound (intermediate) having an unsaturated bond obtained by reacting a nitrogen-containing ring compound having a structure of A ′ (the compound has an NH group) with an alkenol or allyl halide having a leaving group, This can be illustrated by the formula (1-2-1).
Figure JPOXMLDOC01-appb-C000019
 [In the formula (1-2-1), A ′ represents a (n4) -valent nitrogen-containing cyclic group, and R 1 and R 2 each independently represents a hydrogen atom or an alkyl having 1 to 10 carbon atoms. R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2 to 8 Represents an integer.]
　即ち、本発明に用いられる式（１－２）で表されるエポキシ化合物は、式（５－６）と式（２－１）との組み合わせからなる式（１－２）で表されるエポキシ化合物を例にとれば、以下の方法で得ることができる。
Figure JPOXMLDOC01-appb-C000020
 That is, the epoxy compound represented by the formula (1-2) used in the present invention is an epoxy compound represented by the formula (1-2) composed of a combination of the formula (5-6) and the formula (2-1). Taking a compound as an example, it can be obtained by the following method.
Figure JPOXMLDOC01-appb-C000020
　窒素含有環化合物（該化合物はＮＨ基を有する。）と脱離基を有するアルケノールを反応させて、中間体（オレフィン）を合成する。この反応はＤＭＦ等の溶媒中で、水素化ナトリウム、炭酸カリウム、ｔ－ブトキシカリウム、トリエチルアミン等の塩基を用い、室温（例えば２０℃）～溶媒の沸点温度、０～１００時間で行われる。そして、この不飽和化合物を過酸化物で酸化してエポキシ化合物を得ることができる。ここで過酸化物としては、例えば、メタクロロ過安息香酸、過酢酸、過酸化水素－タングステン酸等を用いることができる。この反応はクロロホルム等の溶媒中で、０～６０℃、１～２００時間で行うことができる。 An intermediate (olefin) is synthesized by reacting a nitrogen-containing ring compound (the compound has an NH group) with an alkenol having a leaving group. This reaction is carried out in a solvent such as DMF using a base such as sodium hydride, potassium carbonate, t-butoxypotassium, triethylamine and the like at room temperature (for example, 20 ° C.) to the boiling point of the solvent for 0 to 100 hours. The unsaturated compound can be oxidized with a peroxide to obtain an epoxy compound. Here, as the peroxide, for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used. This reaction can be carried out in a solvent such as chloroform at 0 to 60 ° C. for 1 to 200 hours.
　さらに、上記式（１－３）で表されるエポキシ化合物は、例えば、上記Ａの構造を有するアルコールと、脱離基を有するアルケノールやアリルハライドとを反応させて得られる不飽和結合を有する化合物（中間体）と過酸化物とを反応させて、製造することができる。
　母核Ａに置換するＢに対応する脱離基を有するアルケノールやアリルハライドとしては、例えば上記式（２－１－１）、式（２－２－１）、式（２－３－１）、及び（２－４－１）で表される化合物にメタンスルホニルハライド、トリフルオロメタンスルホン酸無水物、トルエンスルホニルハライド、ニトロベンゼンスルホニルハライド、アセチルハライド、無水酢酸、トリフルオロ無水酢酸、オキシ塩化リン、オキシ臭化リン、チオニルハライド、スルフリルハライド、塩化水素、臭化水素、ヨウ化水素等を反応させて得られる上記式（２－１－２）、式（２－２－２）、式（２－３－２）、及び式（２－４－２）で表される化合物を用いることができる。 Furthermore, the epoxy compound represented by the above formula (1-3) is, for example, a compound having an unsaturated bond obtained by reacting an alcohol having the structure A with an alkenol or allyl halide having a leaving group. It can be produced by reacting (intermediate) with a peroxide.
Examples of the alkenol or allyl halide having a leaving group corresponding to B substituted for the mother nucleus A include, for example, the above formula (2-1-1), formula (2-2-1), formula (2-3-1) And methanesulfonyl halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide, acetyl halide, acetic anhydride, trifluoroacetic anhydride, phosphorus oxychloride, oxy The above formula (2-1-2), formula (2-2-2) and formula (2-) obtained by reacting phosphorus bromide, thionyl halide, sulfuryl halide, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like. The compound represented by 3-2) and formula (2-4-2) can be used.
　母核Ａの構造を有するアルコールは、以下に例示される。
　Ａが（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基を表すアルコールとしては以下に例示される。
Figure JPOXMLDOC01-appb-C000021
 The alcohol having the structure of mother nucleus A is exemplified below.
Examples of the alcohol in which A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms are shown below.
Figure JPOXMLDOC01-appb-C000021
　Ａが（ｎ４）価の炭素原子数４～２０の環状炭化水素基を表すアルコールとしては以下に例示される。
Figure JPOXMLDOC01-appb-C000022
 Examples of the alcohol in which A represents an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms are shown below.
Figure JPOXMLDOC01-appb-C000022
　Ａが（ｎ４）価の窒素含有環基を表すアルコールとしては以下に例示される。
Figure JPOXMLDOC01-appb-C000023
 ［式（５－１－３）中、Ｒは水素原子又は炭素原子数１～１０のアルキル基を表す。］ Examples of the alcohol in which A represents a (n4) -valent nitrogen-containing cyclic group are shown below.
Figure JPOXMLDOC01-appb-C000023
 [In the formula (5-1-3), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]
　Ａが（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基を表すアルコールとしては以下に例示される。
Figure JPOXMLDOC01-appb-C000024
 Examples of the alcohol in which A represents an (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms are shown below.
Figure JPOXMLDOC01-appb-C000024
　上記Ａの構造を有するアルコールと、脱離基を有するアルケノールやアリルハライドとを反応させて得られる不飽和結合を有する化合物（中間体）は、式（１－３－１）に例示することができる。
Figure JPOXMLDOC01-appb-C000025
 ［式（１－３－１）中、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ３は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表す。］ The compound (intermediate) having an unsaturated bond obtained by reacting the alcohol having the structure A with an alkenol or allyl halide having a leaving group can be exemplified by the formula (1-3-1). it can.
Figure JPOXMLDOC01-appb-C000025
 [In the formula (1-3-1), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, (n4 ) Represents a valent nitrogen-containing cyclic group, (n4) a valent chain hydrocarbon group having 3 to 10 carbon atoms, or a combination thereof (n4) valent group, R 1 and R 2 are each independently Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, and n3 represents 2 N4 represents an integer of 2 to 8, and n4 represents an integer of 2 to 8. ]
　即ち、本発明に用いられる式（１－３）で表されるのエポキシ化合物は、式（４－４）と式（２－１）との組み合わせからなる式（１－３）で表されるエポキシ化合物を例にとれば、以下の方法で得ることができる。
Figure JPOXMLDOC01-appb-C000026
 That is, the epoxy compound represented by the formula (1-3) used in the present invention is represented by the formula (1-3) composed of a combination of the formula (4-4) and the formula (2-1). Taking an epoxy compound as an example, it can be obtained by the following method.
Figure JPOXMLDOC01-appb-C000026
　アルコールと脱離基を有するアルケノールを反応させて、中間体（オレフィン）を合成する。この反応はエーテル、アミド等の溶媒中で、水酸化ナトリウム、炭酸カリウム、ｔ－ブトキシカリウム、トリエチルアミン等の塩基を用い、室温（例えば２０℃）～溶媒の沸点温度、０～１００時間で行われる。そして、この不飽和化合物を過酸化物で酸化してエポキシ化合物を得ることができる。ここで過酸化物としては、例えば、メタクロロ過安息香酸、過酢酸、過酸化水素－タングステン酸等を用いることができる。この反応はクロロホルム等の溶媒中で、０～６０℃、１～２００時間で行うことができる。 An alcohol (alkenol) having a leaving group is reacted to synthesize an intermediate (olefin). This reaction is carried out in a solvent such as ether or amide using a base such as sodium hydroxide, potassium carbonate, t-butoxypotassium or triethylamine at room temperature (for example, 20 ° C.) to the boiling point of the solvent for 0 to 100 hours. . The unsaturated compound can be oxidized with a peroxide to obtain an epoxy compound. Here, as the peroxide, for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used. This reaction can be carried out in a solvent such as chloroform at 0 to 60 ° C. for 1 to 200 hours.
　上記式（１－３）で表されるエポキシ化合物は、例えば、塩化シアヌルと、式（２－１－１）、式（２－２－１）、式（２－３－１）、及び式（２－４－１）等で表されるアリルアルコールとを反応させて得られる不飽和結合を有する化合物（中間体）と過酸化物を上述の様に反応させて製造することもできる。
Figure JPOXMLDOC01-appb-C000027
 Examples of the epoxy compound represented by the above formula (1-3) include cyanuric chloride, a formula (2-1-1), a formula (2-2-1), a formula (2-3-1), and a formula. It can also be produced by reacting a compound having an unsaturated bond (intermediate) obtained by reacting with allyl alcohol represented by (2-4-1) or the like and a peroxide as described above.
Figure JPOXMLDOC01-appb-C000027
　また、本発明は上記式（１）で表されるエポキシ化合物、及び硬化剤を含む硬化性組成物である。
　さらに、本発明は上記式（１）で表されるエポキシ化合物、及び酸発生剤を含む硬化性組成物である。
　本発明の硬化性組成物は、必要により更に溶剤、他のエポキシ化合物、硬化剤、界面活性剤、及び密着促進剤等を含有することができる。 Moreover, this invention is a curable composition containing the epoxy compound represented by the said Formula (1), and a hardening | curing agent.
Furthermore, this invention is a curable composition containing the epoxy compound represented by the said Formula (1), and an acid generator.
The curable composition of the present invention can further contain a solvent, another epoxy compound, a curing agent, a surfactant, and an adhesion promoter, if necessary.
　本発明の硬化性組成物における固形分の割合は、１～１００質量％、又は５～１００質量％、又は５０～１００質量％、又は８０～１００質量％とすることができる。
　固形分とは、硬化性組成物より溶剤を除去した残りの成分の割合である。本発明では液状エポキシ化合物を用い、それに硬化剤又は酸発生剤を混合するため、基本的に溶剤を用いる必要はないが、必要により溶剤を添加することは可能である。例えば、酸発生剤が固体であり、酸発生剤を炭酸プロピレン等の溶剤に溶解し液状エポキシ化合物と混合して硬化性化合物を製造することができる。また、液状エポキシ化合物に酸発生剤を溶解させる場合でも、得られる硬化性組成物の粘度調整のために一般的な溶剤を添加することはできる。 The ratio of the solid content in the curable composition of the present invention can be 1 to 100% by mass, or 5 to 100% by mass, or 50 to 100% by mass, or 80 to 100% by mass.
Solid content is the ratio of the remaining component which removed the solvent from the curable composition. In the present invention, since a liquid epoxy compound is used and a curing agent or an acid generator is mixed therewith, it is basically unnecessary to use a solvent, but it is possible to add a solvent if necessary. For example, the acid generator is solid, and the curable compound can be produced by dissolving the acid generator in a solvent such as propylene carbonate and mixing it with a liquid epoxy compound. Even when an acid generator is dissolved in a liquid epoxy compound, a general solvent can be added to adjust the viscosity of the resulting curable composition.
　本発明の硬化性組成物における上記式（１）で表されるエポキシ化合物の含有量は、該硬化性組成物の固形分の含有量に基づいて、８～９９．９質量％、好ましくは４０～９９質量％、更に好ましくは７０～９９質量％である。
　また本発明の硬化性組成物における酸発生剤の含有量は、該硬化性組成物の固形分の含有量に基づいて、０．１～２０質量％、又は０．１～１０質量％とすることができる。
　本発明の硬化性組成物は、上記式（１）で表されるエポキシ化合物の質量に対して酸発生剤を０．１～２０質量％、又は０．１～１０質量％の割合で含有することができる。 The content of the epoxy compound represented by the above formula (1) in the curable composition of the present invention is 8 to 99.9% by mass, preferably 40 based on the solid content of the curable composition. It is -99 mass%, More preferably, it is 70-99 mass%.
Further, the content of the acid generator in the curable composition of the present invention is 0.1 to 20% by mass, or 0.1 to 10% by mass based on the solid content of the curable composition. be able to.
The curable composition of the present invention contains an acid generator in a proportion of 0.1 to 20% by mass, or 0.1 to 10% by mass with respect to the mass of the epoxy compound represented by the above formula (1). be able to.
　本発明では、上記式（１）で表されるエポキシ化合物と、それ以外のエポキシ化合物を併用することができる。上記式（１）で表されるエポキシ化合物と、それ以外のエポキシ化合物は、エポキシ基のモル比で１：０．１～１：１０の範囲で用いることが可能である。
　上記式（１）で表されるエポキシ化合物以外のエポキシ化合物としては、以下に例示することができる。 In the present invention, the epoxy compound represented by the above formula (1) and other epoxy compounds can be used in combination. The epoxy compound represented by the above formula (1) and the other epoxy compounds can be used in a molar ratio of epoxy groups in the range of 1: 0.1 to 1:10.
Examples of the epoxy compound other than the epoxy compound represented by the above formula (1) can be exemplified below.
　固形エポキシ化合物、トリス－（２，３－エポキシプロピル）－イソシアヌレート（式（７－１）、商品名テピック、日産化学工業（株）製）。
Figure JPOXMLDOC01-appb-C000028
 Solid epoxy compound, tris- (2,3-epoxypropyl) -isocyanurate (formula (7-1), trade name Tepic, manufactured by Nissan Chemical Industries, Ltd.).
Figure JPOXMLDOC01-appb-C000028
　液状エポキシ化合物、商品名エピコート８２８（式（７－２）、ジャパンエポキシレジン（株）製）。
Figure JPOXMLDOC01-appb-C000029
 Liquid epoxy compound, trade name Epicoat 828 (formula (7-2), manufactured by Japan Epoxy Resins Co., Ltd.).
Figure JPOXMLDOC01-appb-C000029
　液状エポキシ化合物、商品名ＹＸ８０００（式（７－３）、ジャパンエポキシレジン（株）製）。
Figure JPOXMLDOC01-appb-C000030
 Liquid epoxy compound, trade name YX8000 (formula (7-3), manufactured by Japan Epoxy Resins Co., Ltd.).
Figure JPOXMLDOC01-appb-C000030
　液状エポキシ化合物、商品名ＤＭＥ１００（式（７－４）、新日本理化（株）製）。
Figure JPOXMLDOC01-appb-C000031
 Liquid epoxy compound, trade name DME100 (formula (7-4), manufactured by Shin Nippon Rika Co., Ltd.).
Figure JPOXMLDOC01-appb-C000031
　液状エポキシ化合物、商品名ＣＥ－２０２１Ｐ（式（７－５）、ダイセル株式会社製）。
Figure JPOXMLDOC01-appb-C000032
 Liquid epoxy compound, trade name CE-2021P (formula (7-5), manufactured by Daicel Corporation).
Figure JPOXMLDOC01-appb-C000032
　また、本発明では、液状エポキシ化合物として、以下のトリス－（３，４－エポキシブチル）－イソシアヌレート（式（７－６））、トリス－（４，５－エポキシペンチル）－イソシアヌレート（式（７－７））、トリス－（５，６－エポキシヘキシル）－イソシアヌレート（式（７－８））、トリス（グリシジルオキシエチル）イソシアヌレート（式（７－９））を用いることができる。
Figure JPOXMLDOC01-appb-C000033
 In the present invention, as the liquid epoxy compound, the following tris- (3,4-epoxybutyl) -isocyanurate (formula (7-6)), tris- (4,5-epoxypentyl) -isocyanurate (formula (7-7)), tris- (5,6-epoxyhexyl) -isocyanurate (formula (7-8)), tris (glycidyloxyethyl) isocyanurate (formula (7-9)) can be used. .
Figure JPOXMLDOC01-appb-C000033
　トリス－（２，３－エポキシプロピル）－イソシアヌレート１モルに無水プロピオン酸０．８モルを加えて変性させた液状エポキシ化合物（式（７－１０）、日産化学工業（株）製、商品名：テピックパスＢ２２）。式（７－１０）は、（７－１０－１）：（７－１０－２）：（７－１０－３）：（７－１０－４）をモル比で約３５％：４５％：１７％：３％の割合で含有する。
Figure JPOXMLDOC01-appb-C000034
 Liquid epoxy compound modified by adding 0.8 mol of propionic anhydride to 1 mol of tris- (2,3-epoxypropyl) -isocyanurate (formula (7-10), manufactured by Nissan Chemical Industries, Ltd., trade name : Tepic path B22). Formula (7-10) is obtained by converting (7-10-1) :( 7-10-2) :( 7-10-3) :( 7-10-4) in a molar ratio of about 35%: 45%: 17%: contained in a ratio of 3%.
Figure JPOXMLDOC01-appb-C000034
　トリス－（２，３－エポキシプロピル）－イソシアヌレート１モルに無水プロピオン酸０．４モルを加えて変性させた液状エポキシ化合物（式（７－１１）、日産化学工業（株）製、商品名テピックパスＢ２６）。式（７－１１）は、（７－１１－１）：（７－１１－２）：（７－１１－３）をモル比で約６０％：３２％：８％の割合で含有する。
Figure JPOXMLDOC01-appb-C000035
 Liquid epoxy compound modified by adding 0.4 mol of propionic anhydride to 1 mol of tris- (2,3-epoxypropyl) -isocyanurate (formula (7-11), manufactured by Nissan Chemical Industries, Ltd., trade name Tepic path B26). Formula (7-11) contains (7-11-1) :( 7-11-2) :( 7-11-3) in a molar ratio of about 60%: 32%: 8%.
Figure JPOXMLDOC01-appb-C000035
　本発明では、カチオン硬化性モノマーとしてエポキシ化合物以外にビニルエーテル化合物、オキセタン化合物等を用いることができる。 In the present invention, vinyl ether compounds, oxetane compounds and the like can be used as the cationic curable monomer in addition to the epoxy compound.
　ビニル基含有化合物（ビニルエーテル化合物等）としては、ビニル基を有する化合物であれば特に限定されず、例えば、２－ヒドロキシエチルビニルエーテル（ＨＥＶＥ）、ジエチレングリコールモノビニルエーテル（ＤＥＧＶ）、２－ヒドロキシブチルビニルエーテル（ＨＢＶＥ）、トリエチレングリコールジビニルエーテルが挙げられる。また、α及び／又はβ位にアルキル基、アリル基等の置換基を有するビニル化合物も使用することができる。また、エポキシ基及び／又はオキセタン基等の環状エーテル基を含むビニルエーテル化合物を使用することができ、例えば、オキシノルボルネンジビニルエーテル、３、３－ジメタノールオキセタンジビニルエーテルが挙げられる。また、ビニル基と（メタ）アクリル基を有するハイブリッド化合物を使用することができ、例えば、（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチル（ＶＥＥＡ，ＶＥＥＭ）等が挙げられる。これらは、単独で又は二種以上を組み合わせて使用することができる。 The vinyl group-containing compound (such as a vinyl ether compound) is not particularly limited as long as it is a compound having a vinyl group. For example, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE) ), Triethylene glycol divinyl ether. In addition, vinyl compounds having a substituent such as an alkyl group or an allyl group at the α and / or β positions can also be used. Further, a vinyl ether compound containing a cyclic ether group such as an epoxy group and / or an oxetane group can be used, and examples thereof include oxynorbornene divinyl ether and 3,3-dimethanol oxetane divinyl ether. In addition, a hybrid compound having a vinyl group and a (meth) acryl group can be used, and examples thereof include 2- (2-vinyloxyethoxy) ethyl (VEEA, VEEM) and the like (meth) acrylate. These can be used alone or in combination of two or more.
　オキセタニル基含有化合物（オキセタン化合物）としては、オキセタニル基を有する化合物であれば特に限定されず、３－エチル－３－（フェノキシメチル）オキセタン（ＰＯＸ）、ジ［１－エチル（３－オキセタニル）］メチルエーテル（ＤＯＸ）、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン（ＥＨＯＸ）、３－エチル－３－｛［３－（トリエトキシシリル）プロポキシ］メチル｝オキセタン（ＴＥＳＯＸ）、オキセタニルシルセスキオキサン（ＯＸ－ＳＱ）、フェノールノボラックオキセタン（ＰＮＯＸ－１００９）等が挙げられる。また、オキセタニル基と（メタ）アクリル基を有するハイブリッド化合物（１－エチル－３－オキセタニルメチル（メタ）アクリレート）を使用することができる。これらのオキセタン系化合物は、単独で又は二種以上を組み合わせて使用することができる。 The oxetanyl group-containing compound (oxetane compound) is not particularly limited as long as it is a compound having an oxetanyl group, and 3-ethyl-3- (phenoxymethyl) oxetane (POX), di [1-ethyl (3-oxetanyl)] Methyl ether (DOX), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (EHOX), 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane (TESOX), oxetanyl Examples thereof include silsesquioxane (OX-SQ), phenol novolac oxetane (PNOX-1009), and the like. In addition, a hybrid compound (1-ethyl-3-oxetanylmethyl (meth) acrylate) having an oxetanyl group and a (meth) acryl group can be used. These oxetane compounds can be used alone or in combination of two or more.
　本発明では、上記式（１）で表されるエポキシ化合物と硬化剤とを含む硬化性組成物を得ることができる。
　硬化剤としては、酸無水物、アミン、フェノール樹脂、ポリアミド樹脂、イミダゾール、又はポリメルカプタンを用いることができる。これらの中でも、特に酸無水物及びアミンが好ましい。これら硬化剤は、固体であっても溶剤に溶解することによって使用することができる。しかし、溶剤の蒸発により硬化物の密度低下や細孔の生成により強度低下、耐水性の低下を生ずるため、硬化剤自体が常温、常圧下で液状のものが好ましい。
　硬化剤は、エポキシ化合物のエポキシ基１当量に対して０．５～１．５当量、好ましくは０．８～１．２当量の割合で含有することができる。エポキシ化合物に対する硬化剤の当量は、エポキシ基に対する硬化剤の硬化性基の当量比で示される。 In this invention, the curable composition containing the epoxy compound represented by the said Formula (1) and a hardening | curing agent can be obtained.
As the curing agent, acid anhydride, amine, phenol resin, polyamide resin, imidazole, or polymercaptan can be used. Among these, acid anhydrides and amines are particularly preferable. Even if these hardening | curing agents are solid, they can be used by melt | dissolving in a solvent. However, since the density of the cured product is reduced due to the evaporation of the solvent and the strength and water resistance are lowered due to the formation of pores, the curing agent itself is preferably liquid at normal temperature and normal pressure.
The curing agent can be contained at a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy compound. The equivalent of the curing agent to the epoxy compound is represented by an equivalent ratio of the curable group of the curing agent to the epoxy group.
　フェノール樹脂としては、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂等が挙げられる。 Examples of the phenol resin include phenol novolac resin and cresol novolac resin.
　アミンとしては、例えば、ピペリジン、Ｎ，Ｎ－ジメチルピペラジン、トリエチレンジアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール、ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジエチルアミノプロピルアミン、Ｎ－アミノエチルピペラジン、ジ（１－メチル－２－アミノシクロヘキシル）メタン、メンセンジアミン、イソフオロンジアミン、ジアミノジシクロヘキシルメタン、１，３－ジアミノメチルシクロヘキサン、キシレンジアミン、メタフェニレンジアミン、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が挙げられる。これらの中でも、液状であるジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジエチルアミノプロピルアミン、Ｎ－アミノエチルピペラジン、ジ（１－メチル－２－アミノシクロヘキシル）メタン、メンセンジアミン、イソフオロンジアミン、及びジアミノジシクロヘキシルメタン等は好ましく用いることができる。 Examples of amines include piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, diethylenetriamine, and triethylenetetramine. , Tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mensendiamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylene Examples include diamine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Among these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mensendiamine, isophoronediamine, and Diaminodicyclohexylmethane and the like can be preferably used.
　ポリアミド樹脂は、ダイマー酸とポリアミンの縮合により生成するもので、分子中に一級アミンと二級アミンを有するポリアミドアミンである。 The polyamide resin is produced by condensation of dimer acid and polyamine, and is a polyamide amine having a primary amine and a secondary amine in the molecule.
　イミダゾール類としては、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾリウムトリメリテート、及びエポキシイミダゾールアダクト等が挙げられる。 Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy imidazole adduct.
　ポリメルカプタンは、例えばポリプロピレングリコール鎖の末端にメルカプタン基が存在するものや、ポリエチレングリコール鎖の末端にメルカプタン基が存在するものであり、液状のものが好ましい。 Polymercaptan is, for example, one having a mercaptan group at the end of a polypropylene glycol chain or one having a mercaptan group at the end of a polyethylene glycol chain, and is preferably in a liquid form.
　酸無水物としては一分子中に複数のカルボキシル基を有する化合物の無水物が好ましい。これらの酸無水物としては、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、エチレングリコールビストリメリテート、グリセロールトリストリメリテート、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、メチルブテニルテトラヒドロ無水フタル酸、ドデセニル無水コハク酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水コハク酸、メチルシクロヘキセンジカルボン酸無水物、クロレンド酸無水物等が挙げられる。
　これらの中でも常温、常圧で液状であるメチルテトラヒドロ無水フタル酸、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物（メチルナジック酸無水物、無水メチルハイミック酸）、水素化メチルナジック酸無水物、メチルブテニルテトラヒドロ無水フタル酸、ドデセニル無水コハク酸、メチルヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸とヘキサヒドロ無水フタル酸との混合物が好ましい。これら液状の酸無水物は粘度が２５℃での測定で１０ｍＰａｓ～１０００ｍＰａｓ程度である。酸無水物基において、１つの酸無水物基は１当量として計算される。 The acid anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule. These acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trislimitate, maleic anhydride, tetrahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methyl Examples include cyclohexene dicarboxylic acid anhydride and chlorendic acid anhydride.
Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride (methyl nadic acid anhydride, methyl hymic anhydride), hydrogenated methyl nadic acid which is liquid at normal temperature and normal pressure Preference is given to anhydrides, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride. These liquid acid anhydrides have a viscosity of about 10 mPas to 1000 mPas as measured at 25 ° C. In an acid anhydride group, one acid anhydride group is calculated as one equivalent.
　また、本発明の硬化性組成物から硬化物を得る際、適宜、硬化助剤が併用されても良い。
　硬化助剤としては、トリフェニルホスフィンやトリブチルホスフィンなどの有機リン化合物、エチルトリフェニルホスホニウムブロマイド、テトラブチルホスホニウムジチオリン酸ジエチル等の第４級ホスホニウム塩、１，８－ジアザビシクロ［５，４，０］ウンデカン－７－エン、１，８－ジアザビシクロ［５，４，０］ウンデカン－７－エンとオクチル酸との塩、オクチル酸亜鉛、テトラブチルアンモニウムブロミド等の第４級アンモニウム塩が挙げられる。これらの硬化助剤は、硬化剤１質量部に対して、０．００１～０．１質量部の割合で用いることができる。 Moreover, when obtaining hardened | cured material from the curable composition of this invention, a hardening adjuvant may be used together suitably.
Curing aids include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and diethyl tetrabutylphosphonium dithiophosphate, 1,8-diazabicyclo [5,4,0]. Examples thereof include salts of undecan-7-ene, 1,8-diazabicyclo [5,4,0] undecan-7-ene and octyl acid, and quaternary ammonium salts such as zinc octylate and tetrabutylammonium bromide. These curing aids can be used in a proportion of 0.001 to 0.1 parts by mass with respect to 1 part by mass of the curing agent.
　本発明では、上記式（１）で表されるエポキシ化合物と上記硬化剤と所望により硬化助剤とを混合することにより、硬化性組成物が得られる。これら混合は均一に混合できれば、特に限定されるものではないが、例えば反応フラスコと撹拌羽根若しくはミキサー等を用いて行うことができる。
　混合は粘度を考慮して必要に応じて加熱下で行われ、１０℃～１００℃の温度で０．５～１時間行われる。
　得られた硬化性組成物は、液状封止材として用いるための適切な粘度を有する。本発明の硬化性組成物は、任意の粘度に調整が可能であり、キャスティング法、ポッティング法、ディスペンサー法、印刷法等によりＬＥＤ等の透明封止材として用いるために、その任意箇所に部分的封止ができる。硬化性組成物を上述の方法で液状のまま直接、ＬＥＤ等に実装した後、乾燥し、硬化することによりエポキシ樹脂硬化物が得られる。
　硬化性組成物から得られる硬化物は、該硬化性組成物を基材に塗布、もしくは離型剤を塗布した注型板に注ぎ込んで、１００～１２０℃の温度で予備硬化し、そして１２０～２００℃の温度で後硬化することにより得られる。
　加熱時間は、１～１２時間、好ましくは２～５時間程度である。
　本発明の硬化性組成物から得られる塗膜の厚みは、硬化物の用途に応じて、０．０１μｍ～１０ｍｍ程度の範囲から選択できる。 In this invention, a curable composition is obtained by mixing the epoxy compound represented by the said Formula (1), the said hardening | curing agent, and a hardening adjuvant as needed. The mixing is not particularly limited as long as it can be uniformly mixed, but can be performed using, for example, a reaction flask and a stirring blade or a mixer.
The mixing is performed under heating as necessary in consideration of the viscosity, and is performed at a temperature of 10 ° C. to 100 ° C. for 0.5 to 1 hour.
The obtained curable composition has an appropriate viscosity for use as a liquid sealing material. The curable composition of the present invention can be adjusted to an arbitrary viscosity, and is partially used in a transparent sealing material such as an LED by a casting method, a potting method, a dispenser method, a printing method, etc. Can be sealed. The curable composition is directly mounted in an LED or the like in a liquid state by the above-described method, and then dried and cured to obtain a cured epoxy resin.
The cured product obtained from the curable composition is pre-cured at a temperature of 100 to 120 ° C. by applying the curable composition to a substrate or pouring it onto a casting plate coated with a release agent, and 120 to It is obtained by post-curing at a temperature of 200 ° C.
The heating time is about 1 to 12 hours, preferably about 2 to 5 hours.
The thickness of the coating film obtained from the curable composition of the present invention can be selected from the range of about 0.01 μm to 10 mm depending on the use of the cured product.
　上記の硬化性組成物は、必要により溶剤を含むことができる。
　溶剤としては、例えば、テトラヒドロフランなどのエーテル類、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などのグリコールエーテル類、メチルセロソルブアセテート、エチルセロソルブアセテートなどのエチレングリコールアルキルエーテルアセテート類、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテルなどのジエチレングリコール類、プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールブチルエーテルなどのプロピレングリコールモノアルキルエーテル類、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのプロピレングリコールアルキルエーテルアセテート類、プロピレングリコールメチルエーテルプロピオネート、プロピレングリコールエチルエーテルプロピオネート、プロピレングリコールプロピルエーテルプロピオネート、プロピレングリコールブチルエーテルプロピオネートなどのプロピレングリコールアルキルエーテルアセテート類、トルエン、キシレンなどの芳香族炭化水素類、メチルエチルケトン、シクロヘキサノン、４－ヒドロキシ－４－メチル－２－ペンタノンなどのケトン類、および酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸メチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、３－ヒドロキシプロピオン酸メチル、３－ヒドロキシプロピオン酸エチル、３－ヒドロキシプロピオン酸プロピル、３－ヒドロキシプロピオン酸ブチル、２－ヒドロキシ－３－メチルブタン酸メチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸プロピル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、エトキシ酢酸プロピル、エトキシ酢酸ブチル、プロポキシ酢酸メチル、プロポキシ酢酸エチル、プロポキシ酢酸プロピル、プロポキシ酢酸ブチル、ブトキシ酢酸メチル、ブトキシ酢酸エチル、ブトキシ酢酸プロピル、ブトキシ酢酸ブチル、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－メトキシプロピオン酸ブチル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル、２－エトキシプロピオン酸プロピル、２－エトキシプロピオン酸ブチル、２－ブトキシプロピオン酸メチル、２－ブトキシプロピオン酸エチル、２－ブトキシプロピオン酸プロピル、２－ブトキシプロピオン酸ブチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸プロピル、３－エトキシプロピオン酸ブチル、３－プロポキシプロピオン酸メチル、３－プロポキシプロピオン酸エチル、３－プロポキシプロピオン酸プロピル、３－プロポキシプロピオン酸ブチル、３－ブトキシプロピオン酸メチル、３－ブトキシプロピオン酸エチル、３－ブトキシプロピオン酸プロピル、３－ブトキシプロピオン酸ブチルなどのエステル類が挙げられる。 The above-mentioned curable composition can contain a solvent if necessary.
Examples of the solvent include ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. Diethylene glycols such as ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether, propylene glycol compounds such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether Propylene glycol alkyl ether acetates such as alkyl ethers, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate , Propylene glycol alkyl ether acetates such as propylene glycol propyl ether propionate and propylene glycol butyl ether propionate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Ketones such as, and acetic acid Chill, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid Butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutanoic acid Methyl, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxyacetic acid Ethyl, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Butyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropion Propyl acid, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropion And esters such as butyl acid, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.
　本発明では、上記式（１）で表されるエポキシ化合物と酸発生剤とを含む硬化性組成物を得ることができる。酸発生剤は、光酸発生剤又は熱酸発生剤を用いることができる。
　光酸発生剤又は熱酸発生剤は、光照射又は加熱により直接又は間接的に酸を発生するものであれば特に限定されない。
　光酸発生剤の具体例としては、トリアジン系化合物、アセトフェノン誘導体化合物、ジスルホン系化合物、ジアゾメタン系化合物、スルホン酸誘導体化合物、ヨードニウム塩、スルホニウム塩、ホスホニウム塩、セレニウム塩等のオニウム塩、メタロセン錯体、鉄アレーン錯体などを挙げることができる。 In this invention, the curable composition containing the epoxy compound represented by the said Formula (1) and an acid generator can be obtained. As the acid generator, a photoacid generator or a thermal acid generator can be used.
The photoacid generator or thermal acid generator is not particularly limited as long as it generates an acid directly or indirectly by light irradiation or heating.
Specific examples of the photoacid generator include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, iodonium salts, sulfonium salts, onium salts such as phosphonium salts, selenium salts, metallocene complexes, Examples thereof include iron arene complexes.
　上記光酸発生剤として用いるオニウム塩は、ヨードニウム塩として、例えばジフェニルヨードニウムクロライド、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムメシレート、ジフェニルヨードニウムトシレート、ジフェニルヨードニウムブロミド、ジフェニルヨードニウムテトラフルオロボレート、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、ジフェニルヨードニウムヘキサフルオロアルセネート、ビス（ｐ－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、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムメシレート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムトシレート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムテトラフルオロボレート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムクロリド、ビス（ｐ－クロロフェニル）ヨードニウムクロライド、ビス（ｐ－クロロフェニル）ヨードニウムテトラフルオロボレートが挙げられる。更にビス（４－ｔ－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などのビス（アルキルフェニル）ヨードニウム塩、アルコキシカルボニルアルコキシ－トリアルキルアリールヨードニウム塩（例えば、４－［（１－エトキシカルボニル－エトキシ）フェニル］－（２，４，６－トリメチルフェニル）－ヨードニウムヘキサフルオロホスフェートなど）、ビス（アルコキシアリール）ヨードニウム塩（例えば、（４－メトキシフェニル）フェニルヨードニウムヘキサフルオロアンチモネートなどのビス（アルコキシフェニル）ヨードニウム塩）が挙げられる。 The onium salt used as the photoacid generator is an iodonium salt such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoro. Antimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, Bis (p-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, and bis (p-chlorophenyl) iodonium tetrafluoroborate. . Furthermore, bis (alkylphenyl) iodonium salts such as bis (4-t-butylphenyl) iodonium hexafluorophosphate, alkoxycarbonylalkoxy-trialkylaryliodonium salts (for example, 4-[(1-ethoxycarbonyl-ethoxy) phenyl]- (2,4,6-trimethylphenyl) -iodonium hexafluorophosphate), bis (alkoxyaryl) iodonium salts (for example, bis (alkoxyphenyl) iodonium salts such as (4-methoxyphenyl) phenyliodonium hexafluoroantimonate) Is mentioned.
　上記スルホニウム塩としては、トリフェニルスルホニウムクロリド、トリフェニルスルホニウムブロミド、トリ（ｐ－メトキシフェニル）スルホニウムテトラフルオロボレート、トリ（ｐ－メトキシフェニル）スルホニウムヘキサフルオロホスホネート、トリ（ｐ－エトキシフェニル）スルホニウムテトラフルオロボレート、トリフェニルスルホニウムトリフレート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムヘキサフルオロホスフェート等のトリフェニルスルホニウム塩や、（４－フェニルチオフェニル）ジフェニルスルホニウムヘキサフルオロアンチモネート、（４－フェニルチオフェニル）ジフェニルスルホニウムヘキサフルオロホスフェート、ビス［４－（ジフェニルスルホニオ）フェニル］スルフィド－ビス－ヘキサフルオロアンチモネート、ビス［４－（ジフェニルスルホニオ）フェニル］スルフィド－ビス－ヘキサフルオロホスフェート、（４－メトキシフェニル）ジフェニルスルホニウムヘキサフルオロアンチモネート）等のスルホニウム塩が挙げられる。 Examples of the sulfonium salt include triphenylsulfonium chloride, triphenylsulfonium bromide, tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoro. Triphenylsulfonium salts such as borate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, (4-phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) ) Diphenylsulfonium hexafluorophosphate, bis [4- (diphenylsulfonio) fe And sulfonium salts such as bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorophosphate and (4-methoxyphenyl) diphenylsulfonium hexafluoroantimonate). .
　上記ホスホニウム塩としては、トリフェニルホスホニウムクロリド、トリフェニルホスホニウムブロミド、トリ（ｐ－メトキシフェニル）ホスホニウムテトラフルオロボレート、トリ（ｐ－メトキシフェニル）ホスホニウムヘキサフルオロホスホネート、トリ（ｐ－エトキシフェニル）ホスホニウムテトラフルオロボレート、４－クロロベンゼンジアゾニウムヘキサフルオロホスフェート、ベンジルトリフェニルホスホニウムヘキサフルオロアンチモネート等のホスホニウム塩が挙げられる。 Examples of the phosphonium salt include triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p-ethoxyphenyl) phosphonium tetrafluoro. Examples thereof include phosphonium salts such as borate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.
　上記セレニウム塩としては、トリフェニルセレニウムヘキサフルオロホスフェートなどのセレニウム塩が、また上記メタロセン錯体としては、（η５又はη６－イソプロピルベンゼン）（η５－シクロペンタジエニル）鉄（ＩＩ）ヘキサフルオロホスフェートなどのメタロセン錯体が挙げられる。
　また、光酸発生剤としては以下の化合物も用いることができる。 Examples of the selenium salt include selenium salts such as triphenyl selenium hexafluorophosphate, and examples of the metallocene complex include (η5 or η6-isopropylbenzene) (η5-cyclopentadienyl) iron (II) hexafluorophosphate. A metallocene complex is mentioned.
Moreover, the following compounds can also be used as a photoacid generator.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　光酸発生剤としては、スルホニウム塩化合物及びヨードニウム塩化合物が好ましい。それらのアニオン種としては、ＣＦ3ＳＯ3 -、Ｃ4Ｆ9ＳＯ3 -、Ｃ8Ｆ17ＳＯ3 -、カンファースルホン酸アニオン、トシル酸アニオン、ＢＦ4 -、ＰＦ6 -、ＡｓＦ6 -及びＳｂＦ6 -などが挙げられる。特に強酸性を示す六フッ化リン及び六フッ化アンチモン等のアニオン種が好ましい。
　そして、光酸発生剤としては、例えば、上記式（８－１）、（８－２）、（８－３）、（８－８）、（８－９）、及び（８－１０）が好ましく、特に式（８－１）及び（８－２）が好ましい。
　これらの光酸発生剤は単独で、又は２種以上を組み合わせて用いることができる。 As the photoacid generator, a sulfonium salt compound and an iodonium salt compound are preferable. These anionic species include CF 3 SO 3 − , C 4 F 9 SO 3 − , C 8 F 17 SO 3 − , camphorsulfonate anion, tosylate anion, BF 4 − , PF 6 − , AsF 6 − and SbF 6- and the like can be mentioned. Particularly preferred are anionic species such as phosphorous hexafluoride and antimony hexafluoride which exhibit strong acidity.
Examples of the photoacid generator include the above formulas (8-1), (8-2), (8-3), (8-8), (8-9), and (8-10). Particularly preferred are formulas (8-1) and (8-2).
These photoacid generators can be used alone or in combination of two or more.
　熱酸発生剤としては、スルホニウム塩及びホスホニウム塩が挙げられ、スルホニウム塩が好ましく用いられる。
　また、熱酸発生剤としては、以下の化合物を例示することができる。
Figure JPOXMLDOC01-appb-C000045
 　Ｒ’は、それぞれ独立して、炭素原子数１～１２のアルキル基、炭素原子数６～２０アリール基を表し、特に炭素原子数１～１２のアルキル基が好ましい。
　これらの熱酸発生剤は単独で、又は２種以上を組み合わせて用いることができる。 Examples of the thermal acid generator include sulfonium salts and phosphonium salts, and sulfonium salts are preferably used.
Moreover, the following compounds can be illustrated as a thermal acid generator.
Figure JPOXMLDOC01-appb-C000045
 R ′ independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms is particularly preferable.
These thermal acid generators can be used alone or in combination of two or more.
　上記の組成物は、必要に応じて慣用の添加剤を含んでいてもよい。このような添加剤としては、例えば、顔料、着色剤、増粘剤、増感剤、消泡剤、レベリング剤、塗布性改良剤、潤滑剤、安定剤（酸化防止剤、熱安定剤、耐光安定剤など）、可塑剤、界面活性剤、溶解促進剤、充填剤、帯電防止剤、硬化剤などが挙げられる。これらの添加剤は単独で又は２種以上組み合わせてもよい。 The above composition may contain a conventional additive as required. Examples of such additives include pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistances). Stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, fillers, antistatic agents, curing agents and the like. These additives may be used alone or in combination of two or more.
　本発明では、上記式（１）で表されるエポキシ化合物及び光酸発生剤を含む硬化性組成物を基板上に塗布し光照射により硬化することができる。また光照射の前後に加熱することもできる。
　また、本発明では、上記式（１）で表されるエポキシ化合物及び熱酸発生剤を含む硬化性組成物を基板上に塗布し加熱により硬化することができる。
　さらに、上記式（１）で表されるエポキシ化合物及び熱酸発生剤と光酸発生剤を含む硬化性組成物を基板上に塗布し加熱後に光照射により硬化することができる。
　上記の硬化性組成物は溶剤を含むことができる。溶剤は上述の溶剤を用いることができる。 In this invention, the curable composition containing the epoxy compound represented by the said Formula (1) and a photo-acid generator can be apply | coated on a board | substrate, and it can harden | cure by light irradiation. Moreover, it can also heat before and after light irradiation.
Moreover, in this invention, the curable composition containing the epoxy compound represented by the said Formula (1) and a thermal acid generator can be apply | coated on a board | substrate, and it can harden | cure by heating.
Furthermore, the epoxy compound represented by the above formula (1), a curable composition containing a thermal acid generator and a photoacid generator can be applied on a substrate and cured by light irradiation after heating.
Said curable composition can contain a solvent. As the solvent, the above-mentioned solvents can be used.
　本発明の硬化性組成物を基板上に塗布方法としては、例えば、フローコーティング法、スピンコーティング法、スプレーコーティング法、スクリーン印刷法、キャスト法、バーコーティング法、カーテンコーティング法、ロールコーティング法、グラビアコーティング法、ディッピング法、スリット法などを挙げることができる。 Examples of the method for applying the curable composition of the present invention onto a substrate include a flow coating method, a spin coating method, a spray coating method, a screen printing method, a casting method, a bar coating method, a curtain coating method, a roll coating method, and a gravure. Examples thereof include a coating method, a dipping method, and a slit method.
　本発明の硬化性組成物から形成される塗膜の厚みは、硬化物の用途に応じて、０．０１μｍ～１０ｍｍ程度の範囲から選択でき、例えば、フォトレジストに用いる場合は０．０５～１０μｍ（特に０．１～５μｍ）程度とすることができ、プリント配線基板に用いる場合は１０μｍ～５ｍｍ（特に１００μｍ～１ｍｍ）程度とすることができ、光学薄膜に用いる場合は０．１～１００μｍ（特に０．３～５０μｍ）程度とすることができる。 The thickness of the coating film formed from the curable composition of the present invention can be selected from the range of about 0.01 μm to 10 mm depending on the use of the cured product. For example, when used for a photoresist, 0.05 to 10 μm. (Especially 0.1 to 5 μm), about 10 μm to 5 mm (particularly 100 μm to 1 mm) when used for printed wiring boards, and 0.1 to 100 μm (particularly when used for optical thin films). In particular, it can be about 0.3 to 50 μm.
　光酸発生剤を用いる場合の照射又は露光する光としては、例えば、ガンマー線、Ｘ線、紫外線、可視光線などが挙げられ、通常、可視光線又は紫外線、特に紫外線が用いられる場合が多い。
　光の波長は、例えば、１５０～８００ｎｍ、好ましくは１５０～６００ｎｍ、さらに好ましくは２００～４００ｎｍ、特に３００～４００ｎｍ程度である。
　照射光量は、塗膜の厚みにより異なるが、例えば、２～２００００ｍＪ／ｃｍ2、好ましくは５～５０００ｍＪ／ｃｍ2程度とすることができる。
　光源としては、露光する光線の種類に応じて選択でき、例えば、紫外線の場合は低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、重水素ランプ、ハロゲンランプ、レーザー光（ヘリウム－カドミウムレーザー、エキシマレーザーなど）などを用いることができる。このような光照射により、前記組成物の硬化反応が進行する。 Examples of light to be irradiated or exposed in the case of using a photoacid generator include gamma rays, X-rays, ultraviolet rays, visible rays and the like, and usually visible rays or ultraviolet rays, particularly ultraviolet rays are often used.
The wavelength of light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, more preferably about 200 to 400 nm, and particularly about 300 to 400 nm.
Irradiation dose may vary depending on the thickness of the coating film, for example, 2 ~ 20000mJ / cm 2, preferably to the 5 ~ 5000mJ / cm 2 approximately.
The light source can be selected according to the type of light to be exposed. For example, in the case of ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deuterium lamp, a halogen lamp, laser light (helium-cadmium laser, excimer) For example, a laser). By such light irradiation, the curing reaction of the composition proceeds.
　熱酸発生剤を用いる場合や、光酸発生剤を用い光照射後に必要により行われる塗膜の加熱は、例えば、室温～２５０℃程度で行われる。加熱時間は、３秒以上（例えば、３秒～５時間程度）の範囲から選択でき、例えば、５秒～２時間程度である。 When a thermal acid generator is used or when necessary, the coating film is heated after light irradiation using a photoacid generator, for example, at room temperature to about 250 ° C. The heating time can be selected from a range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, about 5 seconds to 2 hours.
　さらに、パターンや画像を形成する場合（例えば、プリント配線基板などを製造する場合）、基材上に形成した塗膜をパターン露光してもよい。このパターン露光は、レーザー光の走査により行ってもよく、フォトマスクを介して光照射することにより行ってもよい。このようなパターン露光により生成した非照射領域（未露光部）を現像液で現像（又は溶解）することによりパターン又は画像を形成できる。 Furthermore, when a pattern or an image is formed (for example, when a printed wiring board is manufactured), the coating film formed on the base material may be subjected to pattern exposure. This pattern exposure may be performed by scanning with a laser beam or by irradiating light through a photomask. A pattern or an image can be formed by developing (or dissolving) a non-irradiated region (unexposed portion) generated by such pattern exposure with a developer.
　現像液としては、アルカリ水溶液や有機溶剤を用いることができる。
　アルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウムなどのアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンなどの水酸化四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミンなどのアミン水溶液を挙げることができる。 As the developer, an alkaline aqueous solution or an organic solvent can be used.
Examples of alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, Examples of the amine aqueous solution include ethanolamine, propylamine, and ethylenediamine.
　前記アルカリ現像液は１０質量％以下の水溶液であることが一般的で、好ましくは０．１～３．０質量％の水溶液などが用いられる。さらに上記現像液にアルコール類や界面活性剤を添加して使用することもでき、これらの添加量はそれぞれ、現像液１００質量部に対して、好ましくは０．０５～１０質量部である。この中で、０．１～２．３８質量％の水酸化テトラメチルアンモニウム水溶液を用いることができる。 The alkaline developer is generally an aqueous solution of 10% by mass or less, and preferably an aqueous solution of 0.1 to 3.0% by mass is used. Further, alcohols and surfactants may be added to the developer and used, and the amount of these added is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the developer. Among these, a 0.1 to 2.38 mass% tetramethylammonium hydroxide aqueous solution can be used.
　また、現像液としての有機溶剤は、一般的な有機溶剤を用いることが可能であり、例えば、アセトン、アセトニトリル、トルエン、ジメチルホルムアミド、メタノール、エタノール、イソプロパノール、プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールブチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールブチルエーテルアセテート、乳酸エチル、シクロヘキサノン等が挙げられる。これらは、単独で又は２種以上の混合物として用いることができる。特にプロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルアセテート、乳酸エチル等は好ましく使用することができる。 Moreover, the organic solvent as a developing solution can use a general organic solvent, for example, acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, Examples include propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, and cyclohexanone. These can be used alone or as a mixture of two or more. In particular, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate and the like can be preferably used.
　本発明の硬化性組成物には、塗布性を向上させる目的で界面活性剤を添加しても良い。このような界面活性剤は、フッ素系界面活性剤、シリコーン系界面活性剤、ノニオン系界面活性剤などが挙げられるが、特にこれらに限定されるものではない。前記界面活性剤は、単独で又は２種類以上を組み合わせて用いることができる。
　これらの界面活性剤の中で、塗布性改善効果の高さからフッ素系界面活性剤が好ましい。フッ素系界面活性剤の具体例としては、商品名：エフトップ［登録商標］ＥＦ３０１、ＥＦ３０３、ＥＦ３５２（三菱マテリアル電子化成（株）（（株）トーケムプロダクツ）製）、商品名：メガファック［登録商標］Ｆ１７１、Ｆ１７３、Ｒ－３０、Ｒ－０８、Ｒ－９０、ＢＬ－２０、Ｆ－４８２（ＤＩＣ（株）（大日本インキ化学工業（株））製）、商品名：フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム（株）製）、商品名：アサヒガード［登録商標］ＡＧ７１０、サーフロン［登録商標］Ｓ－３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子（株）製）等が挙げられるが、これらに限定されるものではない。
　本発明の硬化性組成物における界面活性剤の添加量は、該硬化性組成物の固形分の含有量に基づいて、０．０００８～４．５質量％、好ましくは０．０００８～２．７質量％、より好ましくは０．０００８～１．８質量％である。 A surfactant may be added to the curable composition of the present invention for the purpose of improving coating properties. Examples of such surfactants include, but are not limited to, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. The said surfactant can be used individually or in combination of 2 or more types.
Among these surfactants, a fluorosurfactant is preferable because of its high coating property improving effect. Specific examples of the fluorosurfactant include trade names: EFTOP [registered trademark] EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd. (Tochem Products), Inc.), trade name: Megafuck [ Trademarks] F171, F173, R-30, R-08, R-90, BL-20, F-482 (manufactured by DIC Corporation (Dainippon Ink Chemical Co., Ltd.)), trade name: Fluorard FC430, FC431 (manufactured by Sumitomo 3M Limited), trade names: Asahi Guard [registered trademark] AG710, Surflon [registered trademark] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) Although it is mentioned, it is not limited to these.
The addition amount of the surfactant in the curable composition of the present invention is 0.0008 to 4.5% by mass, preferably 0.0008 to 2.7, based on the solid content of the curable composition. % By mass, more preferably 0.0008 to 1.8% by mass.
　本発明の硬化性組成物には、現像後の基板との密着性を向上させる目的で、密着促進剤を添加することができる。これらの密着促進剤としては、トリメチルクロロシラン、ジメチルビニルクロロシラン、メチルジフェニルクロロシラン、クロロメチルジメチルクロロシラン等のクロロシラン類、トリメチルメトキシシラン、ジメチルジエトキシシラン、メチルジメトキシシラン、ジメチルビニルエトキシシラン、ジフェニルジメトキシシラン、フェニルトリエトキシシラン等のアルコキシシラン類、ヘキサメチルジシラザン、Ｎ，Ｎ’－ビス（トリメチルシリル）ウレア、ジメチルトリメチルシリルアミン、トリメチルシリルイミダゾール等のシラザン類、ビニルトリクロロシラン、γ－クロロプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－（Ｎ－ピペリジニル）プロピルトリメトキシシラン等のシラン類、ベンゾトリアゾール、ベンズイミダゾール、インダゾール、イミダゾール、２－メルカプトベンズイミダゾール、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、ウラゾール、チオウラシル、メルカプトイミダゾール、メルカプトピリミジン等の複素環状化合物や、１，１－ジメチルウレア、１，３－ジメチルウレア等の尿素、またはチオ尿素化合物を挙げることができる。前記密着促進剤は、単独で又は２種類以上を組み合わせて用いることができる。
　本発明の硬化性組成物における密着促進剤の添加量は、該硬化性組成物の固形分の含有量に基づいて、通常１８質量％以下、好ましくは０．０００８～９質量％、より好ましくは０．０４～９質量％である。 An adhesion promoter can be added to the curable composition of the present invention for the purpose of improving the adhesion to the substrate after development. As these adhesion promoters, chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, Alkoxysilanes such as phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, silazanes such as dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Lan, silanes such as γ- (N-piperidinyl) propyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, Examples thereof include heterocyclic compounds such as mercaptoimidazole and mercaptopyrimidine, urea such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds. The said adhesion promoter can be used individually or in combination of 2 or more types.
The addition amount of the adhesion promoter in the curable composition of the present invention is usually 18% by mass or less, preferably 0.0008 to 9% by mass, more preferably based on the solid content of the curable composition. 0.04 to 9% by mass.
　本発明の硬化性組成物は、増感剤を含んでいても良い。使用できる増感剤としては、アントラセン、フェノチアゼン、ぺリレン、チオキサントン、ベンゾフェノンチオキサントン等が挙げられる。更に、増感色素としては、チオピリリウム塩系色素、メロシアニン系色素、キノリン系色素、スチリルキノリン系色素、ケトクマリン系色素、チオキサンテン系色素、キサンテン系色素、オキソノール系色素、シアニン系色素、ローダミン系色素、ピリリウム塩系色素等が例示される。特に好ましいのは、アントラセン系の増感剤であり、カチオン硬化触媒（感放射性カチオン重合開始剤）と併用する事により、感度が飛躍的に向上すると共に、ラジカル重合開始機能も有しており、本発明のようにカチオン硬化システムとラジカル硬化システムを併用するハイブリッドタイプでは、触媒種をシンプルにできる。具体的なアントラセンの化合物としては、ジブトキシアントラセン、ジプロポキシアントラキノン等が有効である。
　本発明の硬化性組成物における増感剤の添加量は、該硬化性組成物の固形分の含有量に基づいて、０．０１～２０質量％、好ましくは０．０１～１０質量％である。 The curable composition of the present invention may contain a sensitizer. Examples of sensitizers that can be used include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Further, sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes. And pyrylium salt dyes. Particularly preferred is an anthracene-based sensitizer, and when used in combination with a cationic curing catalyst (radiation-sensitive cationic polymerization initiator), the sensitivity is drastically improved and also has a radical polymerization initiation function. In the hybrid type using both the cationic curing system and the radical curing system as in the present invention, the catalyst species can be simplified. As specific anthracene compounds, dibutoxyanthracene, dipropoxyanthraquinone and the like are effective.
The addition amount of the sensitizer in the curable composition of the present invention is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content of the curable composition. .
　各測定には、それぞれ以下の機器を使用した。
　ＮＭＲ：日本電子株式会社製ＦＴ－ＮＭＲ（ＥＣＸ３００）
　ＬＣ－ＭＳ：株式会社ウォーターズ製液体クロマトグラフ質量分析計（Ａｌｌｉａｎｃｅ－ＺＱ－ＬＣ－ＭＳ）
　ＧＣ－ＭＳ：株式会社島津製作所製ガスクロマトグラフ質量分析計（ＧＣ－ＭＳ ＱＰ５０５０Ａ）
　ＴＯＦ―ＭＳ（ＭＡＬＤＩ）：ブルカーダルトニクス株式会社製ＭＡＬＤＩ－ＴＯＦ質量分析装置（ａｕｔｏｆｌｅｘＩＩＩ）
　粘度測定：株式会社トキメック製Ｅ型粘度計（ＶＩＳＣＯＮＩＣ ＥＤ型）
　透過率測定：株式会社島津製作所製紫外・可視・近赤外分光光度計（ＵＶ－３６００）
　曲げ試験：株式会社島津製作所製精密万能試験機（ＡＧＳ－Ｘ シリーズ）
　線膨張率、ガラス転移温度測定：株式会社ティー・エイ・インスツルメント製熱機械測定装置（ＴＭＡ Ｑ４００）
　以下のエポキシ化合物を準備した。
〔エポキシ化合物の準備〕
　合成例１
　ビス（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステルの合成
　ディーン・スターク装置、冷却器をつけた反応器にシス－４－シクロヘキセン－１，２－ジカルボン酸無水物１０ｇ、パラトルエンスルホン酸・一水和物１．２ｇ、トルエン１００ｍＬ、トリメチロールプロパンジアリルエーテル（９０％）３４ｇを加え、還流温度で１５時間反応させた。反応終了後、重曹水洗浄、水洗浄を行い、濃縮し、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝８０：２０）で精製し、ビス（２，２－ビス（アリルオキシメチル）ブチル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステル３８ｇを淡黄色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝５．９２～５．８０（ｍ、４Ｈ）、５．６６（ｓ、２Ｈ）、５．２７～５．１１（ｍ、８Ｈ）、４．１２～３．９８（ｍ、４Ｈ）、３．９３～３．９１（ｍ、８Ｈ）、３．３０（ｓ、８Ｈ）、３．０３（ｍ、２Ｈ）、２．５６～２．３５（ｍ、４Ｈ）、１．４６～１．３９（ｑ、４Ｈ）、０．８７～０．８２（ｔ、６Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝５６３（Ｍ＋１）。 The following equipment was used for each measurement.
NMR: FT-NMR (ECX300) manufactured by JEOL Ltd.
LC-MS: Liquid chromatograph mass spectrometer manufactured by Waters Co., Ltd. (Alliance-ZQ-LC-MS)
GC-MS: Gas chromatograph mass spectrometer manufactured by Shimadzu Corporation (GC-MS QP5050A)
TOF-MS (MALDI): MALDI-TOF mass spectrometer (autoflex III) manufactured by Bruker Daltonics Co., Ltd.
Viscosity measurement: E type viscometer manufactured by Tokimec Co., Ltd. (VISCONIC ED type)
Transmittance measurement: UV / visible / near infrared spectrophotometer (UV-3600) manufactured by Shimadzu Corporation
Bending test: Precision universal testing machine manufactured by Shimadzu Corporation (AGS-X series)
Linear expansion coefficient and glass transition temperature measurement: Thermo Instruments Measuring Machine manufactured by TA Instruments Inc. (TMA Q400)
The following epoxy compounds were prepared.
[Preparation of epoxy compound]
Synthesis example 1
Synthesis of bis (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester Dean-Stark apparatus, cis in a reactor equipped with a condenser Add 10 g of -4-cyclohexene-1,2-dicarboxylic anhydride, 1.2 g of paratoluenesulfonic acid monohydrate, 100 mL of toluene, 34 g of trimethylolpropane diallyl ether (90%), and react at reflux temperature for 15 hours I let you. After completion of the reaction, washing with aqueous sodium bicarbonate, washing with water, concentration, purification by silica gel chromatography (hexane: ethyl acetate = 80: 20), bis (2,2-bis (allyloxymethyl) butyl) -4, 38 g of 5-epoxycyclohexane-1,2-dicarboxylic acid ester was obtained as a pale yellow liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.92-5.80 (m, 4H), 5.66 (s, 2H), 5.27-5.11 (m, 8H), 4.12 To 3.98 (m, 4H), 3.93 to 3.91 (m, 8H), 3.30 (s, 8H), 3.03 (m, 2H), 2.56 to 2.35 (m 4H), 1.46 to 1.39 (q, 4H), 0.87 to 0.82 (t, 6H)
GC-MS (CI): m / z = 563 (M + 1).
　反応器にビス（２，２－ビス（アリルオキシメチル）ブチル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステル３５ｇ、クロロホルム３００ｍＬ、メタクロロ過安息香酸８６ｇを加え、２日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水を加えて、抽出した。有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝５０：５０→１０：９０）にて精製し、淡黄色液体３２ｇを得た。
　得られた化合物は、母核に対応する式（４－３）と置換基に対応する式（２－１）の組み合わせに相当するビス（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステルであった。
Figure JPOXMLDOC01-appb-C000046
 　粘度は２５℃で２８６７ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－１）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝４．１１～３．９８（ｍ、４Ｈ）、３．７４～３．６８（ｍ、４Ｈ）、３．４２～３．３０（ｍ、１２Ｈ）、３．２３（ｓ、２Ｈ）、３．１３～３．０８（ｍ、４Ｈ）、２．９２～２．８９（ｍ、２Ｈ）、２．７９～２．７６（ｍ、４Ｈ）、２．５９～２．５６（ｍ、４Ｈ）、２．３５～２．２２（ｍ、４Ｈ）、１．４６～１．３９（ｑ、４Ｈ）、０．８８～０．８３（ｔ、６Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝６４３（Ｍ＋１）。 Bis (2,2-bis (allyloxymethyl) butyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester (35 g), chloroform (300 mL), and metachloroperbenzoic acid (86 g) were added to the reactor and reacted for 2 days. . After completion of the reaction, the reaction mixture was quenched with an aqueous sodium thiosulfate solution, and extracted with an aqueous sodium bicarbonate solution. The organic layer was evaporated to obtain a crude product. Purification by silica gel chromatography (hexane: ethyl acetate = 50: 50 → 10: 90) gave 32 g of a pale yellow liquid.
The obtained compound is bis (2,2-bis (2,3-epoxypropyloxymethyl) corresponding to the combination of formula (4-3) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. ) Butyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester.
Figure JPOXMLDOC01-appb-C000046
 The viscosity was 2867 mPa · s at 25 ° C. This epoxy compound was designated as (i-1).
H-NMR (300 MHz, CDCl 3 ): δ = 4.11 to 3.98 (m, 4H), 3.74 to 3.68 (m, 4H), 3.42 to 3.30 (m, 12H) 3.23 (s, 2H), 3.13 to 3.08 (m, 4H), 2.92 to 2.89 (m, 2H), 2.79 to 2.76 (m, 4H), 2 .59 to 2.56 (m, 4H), 2.35 to 2.22 (m, 4H), 1.46 to 1.39 (q, 4H), 0.88 to 0.83 (t, 6H)
GC-MS (CI): m / z = 643 (M + 1).
　合成例２
　ビス（３－（２，３－エポキシプロピルオキシ）－２，２－ビス（２，３－エポキシプロピルオキシメチル）プロピル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステルの合成
　ディーン・スターク装置、冷却器をつけた反応器にシス－４－シクロヘキセン－１，２－ジカルボン酸無水物８．０ｇ、パラトルエンスルホン酸・一水和物２．０ｇ、トルエン１５０ｍＬ、ペンタエリスリトールトリアリルエーテル（７０％）３９ｇを加え、還流温度で３５時間反応させた。反応終了後、重曹水洗浄、水洗浄を行い、濃縮し、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝９０：１０）で精製し、ビス（３－（アリルオキシ）２，２－ビス（アリルオキシメチル）プロピル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステル１７ｇを無色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝５．９２～５．７９（ｍ、６Ｈ）、５．６６（ｓ、２Ｈ）、５．２６～５．１１（ｍ、１２Ｈ）、４．２５～４．１０（ｑ、４Ｈ）、３．９４～３．９１（ｍ、１２Ｈ）、３．４９（ｓ、１２Ｈ）、３．０３（ｍ、２Ｈ）、２．６１～２．５４（ｍ、２Ｈ）、２．３９～２．３１（ｍ、２Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝６４７（Ｍ＋１）。 Synthesis example 2
Synthesis of bis (3- (2,3-epoxypropyloxy) -2,2-bis (2,3-epoxypropyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester In a reactor equipped with a Stark apparatus and a condenser, cis-4-cyclohexene-1,2-dicarboxylic anhydride 8.0 g, paratoluenesulfonic acid monohydrate 2.0 g, toluene 150 mL, pentaerythritol triallyl ether (70%) 39 g was added and reacted at reflux temperature for 35 hours. After completion of the reaction, washing with aqueous sodium hydrogen carbonate, washing with water, concentration, purification by silica gel chromatography (hexane: ethyl acetate = 90: 10), bis (3- (allyloxy) 2,2-bis (allyloxymethyl) 17 g of propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester was obtained as a colorless liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.92-5.79 (m, 6H), 5.66 (s, 2H), 5.26-5.11 (m, 12H), 4.25 To 4.10 (q, 4H), 3.94 to 3.91 (m, 12H), 3.49 (s, 12H), 3.03 (m, 2H), 2.61 to 2.54 (m) 2H), 2.39 to 2.31 (m, 2H)
GC-MS (CI): m / z = 647 (M + 1).
　反応器にビス（３－（アリルオキシ）２，２－ビス（アリルオキシメチル）プロピル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステル１６ｇ、クロロホルム５００ｍＬ、メタクロロ過安息香酸６０ｇを加え、５日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水を加えて、抽出し、有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（酢酸エチル＝１００）にて精製し、無色液体２２ｇを得た。
　得られた化合物は母核に対応する式（４－３）と置換基に対応する式（２－２）の組み合わせに相当するビス（３－（２，３－エポキシプロピルオキシ）－２，２－ビス（２，３－エポキシプロピルオキシメチル）プロピル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステルであった。
Figure JPOXMLDOC01-appb-C000047
 　粘度は２５℃で１５８０８ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－２）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝４．２２～４．１０（ｑ、４Ｈ）、３．７４～３．６９（ｍ、６Ｈ）、３．５３～３．４４（ｍ、１２Ｈ）、３．３６～３．３１（ｍ、６Ｈ）、３．２４（ｓ、２Ｈ）、３．１３～３．０８（ｍ、６Ｈ）、２．９３～２．８９（ｍ、２Ｈ）、２．７８～２．７５（ｔ、６Ｈ）、２．５９～２．５６（ｍ、６Ｈ）、２．３２～２．２４（ｍ、４Ｈ）
　ＬＣ－ＭＳ（ＥＳＩ）：ｍ／ｚ＝７５９（Ｍ＋１）。 To the reactor was added 16 g of bis (3- (allyloxy) 2,2-bis (allyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester, 500 mL of chloroform, and 60 g of metachloroperbenzoic acid. The reaction was performed for 5 days. After completion of the reaction, the reaction mixture was quenched with an aqueous sodium thiosulfate solution, extracted with sodium bicarbonate water, and the organic layer was evaporated to obtain a crude product. Purification by silica gel chromatography (ethyl acetate = 100) gave 22 g of a colorless liquid.
The obtained compound is bis (3- (2,3-epoxypropyloxy) -2,2 corresponding to the combination of formula (4-3) corresponding to the mother nucleus and formula (2-2) corresponding to the substituent. -Bis (2,3-epoxypropyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester.
Figure JPOXMLDOC01-appb-C000047
 The viscosity was 15808 mPa · s at 25 ° C. This epoxy compound was designated as (i-2).
H-NMR (300 MHz, CDCl 3 ): δ = 4.22 to 4.10 (q, 4H), 3.74 to 3.69 (m, 6H), 3.53 to 3.44 (m, 12H) 3.36 to 3.31 (m, 6H), 3.24 (s, 2H), 3.13 to 3.08 (m, 6H), 2.93 to 2.89 (m, 2H), 2 .78 to 2.75 (t, 6H), 2.59 to 2.56 (m, 6H), 2.32 to 2.24 (m, 4H)
LC-MS (ESI): m / z = 759 (M + 1).
　合成例３
　トリス（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－１，２，３－プロパントリカルボン酸エステルの合成
　ディーン・スターク装置、冷却器をつけた反応器にプロパン－１，２，３－トリカルボン酸１２ｇ、パラトルエンスルホン酸・一水和物２．６ｇ、トルエン２００ｍＬ、トリメチロールプロパンジアリルエーテル（９０％）４９ｇを加え、還流温度で２４時間反応させた。反応終了後、重曹水洗浄、水洗浄を行い、濃縮し、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝８０：２０）で精製し、トリス（２，２－ビス（アリルオキシメチル）ブチル）－１，２，３－プロパントリカルボン酸エステル４６ｇを黄色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝５．９２～５．７９（ｍ、６Ｈ）、５．２７～５．１２（ｍ、１２Ｈ）、４．０６～４．０５（ｍ、６Ｈ）、３．９３～３．９１（ｍ、１２Ｈ）、３．３０～３．２３（ｍ、１３Ｈ）、２．８２～２．７４（ｍ、４Ｈ）、１．４７～１．３９（ｑ、６Ｈ）、０．８７～０．８２（ｔ、９Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝７６６（Ｍ＋１）。 Synthesis example 3
Synthesis of tris (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1,2,3-propanetricarboxylic acid ester Dean-Stark apparatus, propane-1,2 in a reactor equipped with a condenser , 3-tricarboxylic acid 12 g, p-toluenesulfonic acid monohydrate 2.6 g, toluene 200 mL, and trimethylolpropane diallyl ether (90%) 49 g were added and reacted at reflux temperature for 24 hours. After completion of the reaction, washing with aqueous sodium bicarbonate, washing with water, concentration, purification by silica gel chromatography (hexane: ethyl acetate = 80: 20), tris (2,2-bis (allyloxymethyl) butyl) -1, 46 g of 2,3-propanetricarboxylic acid ester was obtained as a yellow liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.92-5.79 (m, 6H), 5.27-5.12 (m, 12H), 4.06-4.05 (m, 6H) 3.93 to 3.91 (m, 12H), 3.30 to 3.23 (m, 13H), 2.82 to 2.74 (m, 4H), 1.47 to 1.39 (q, 6H), 0.87 to 0.82 (t, 9H)
GC-MS (CI): m / z = 766 (M + 1).
　反応器にトリス（２，２－ビス（アリルオキシメチル）ブチル）－１，２，３－プロパントリカルボン酸エステル４５ｇ、クロロホルム６００ｍＬ、メタクロロ過安息香酸８７ｇを加え、４日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水を加えて、抽出し、有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝７０：３０）にて精製し、無色液体２２ｇを得た。
　得られた化合物は母核に対応する式（６－１）と置換基に対応する式（２－１）の組み合わせに相当するトリス（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－１，２，３－プロパントリカルボン酸エステルであった。粘度は２５℃で５４２１ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－３）とした。
Figure JPOXMLDOC01-appb-C000048
 　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝４．０５～４．０４（ｍ、６Ｈ）、３．７３～３．６８（ｍ、６Ｈ）、３．４２～３．２４（ｍ、１９Ｈ）、３．１２～３．１０（ｍ、６Ｈ）、２．８３～２．８０（ｄ、２Ｈ）、２．７８～２．７５（ｍ、６Ｈ）、２．６５～２．６３（ｄ、２Ｈ）、２．５９～２．５６（ｍ、６Ｈ）、１．４６～１．３９（ｑ、６Ｈ）、０．８８～０．８３（ｔ、９Ｈ）
　ＬＣ－ＭＳ（ＥＳＩ）：ｍ／ｚ＝８６１（Ｍ＋１）。 To the reactor, 45 g of tris (2,2-bis (allyloxymethyl) butyl) -1,2,3-propanetricarboxylic acid ester, 600 mL of chloroform, and 87 g of metachloroperbenzoic acid were added and reacted for 4 days. After completion of the reaction, the reaction mixture was quenched with an aqueous sodium thiosulfate solution, extracted with sodium bicarbonate water, and the organic layer was evaporated to obtain a crude product. Purification by silica gel chromatography (hexane: ethyl acetate = 70: 30) gave 22 g of a colorless liquid.
The resulting compound was tris (2,2-bis (2,3-epoxypropyloxymethyl) corresponding to the combination of formula (6-1) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. Butyl) -1,2,3-propanetricarboxylic acid ester. The viscosity was 5421 mPa · s at 25 ° C. This epoxy compound was designated as (i-3).
Figure JPOXMLDOC01-appb-C000048
 H-NMR (300 MHz, CDCl 3 ): δ = 4.05 to 4.04 (m, 6H), 3.73 to 3.68 (m, 6H), 3.42 to 3.24 (m, 19H) 3.12 to 3.10 (m, 6H), 2.83 to 2.80 (d, 2H), 2.78 to 2.75 (m, 6H), 2.65 to 2.63 (d, 2H), 2.59 to 2.56 (m, 6H), 1.46 to 1.39 (q, 6H), 0.88 to 0.83 (t, 9H)
LC-MS (ESI): m / z = 861 (M + 1).
　合成例４
　テトラ（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－１，２，３，４－ブタンテトラカルボン酸エステルの合成
　ディーン・スターク装置、冷却器をつけた反応器にブタン－１，２，３，４－テトラカルボン酸二無水物７ｇ、パラトルエンスルホン酸・一水和物０．７ｇ、トルエン１５０ｍＬ、トリメチロールプロパンジアリルエーテル（９０％）３５ｇを加え、還流温度で５１時間反応させた。反応終了後、重曹水洗浄、水洗浄を行い、濃縮し、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝９０：１０）で精製し、テトラ（２，２－ビス（アリルオキシメチル）ブチル）－１，２，３，４－ブタンテトラカルボン酸エステル２０ｇを黄色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝５．９２～５．７９（ｍ、８Ｈ）、５．２７～５．１２（ｍ、１６Ｈ）、４．１３～４．００（ｍ、８Ｈ）、３．９５～３．９１（ｍ、１６Ｈ）、３．３２～３．３０（ｍ、１８Ｈ）、２．８５～２．７６（ｍ、２Ｈ）、２．４０～２．３５（ｍ、２Ｈ）、１．４５～１．４１（ｍ、８Ｈ）、０．８７～０．８１（ｍ、１２Ｈ）
　ＴＯＦ－ＭＳ（ＭＡＬＤＩ）：ｍ／ｚ＝１０４２（Ｍ＋Ｎａ）。 Synthesis example 4
Synthesis of tetra (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1,2,3,4-butanetetracarboxylic acid ester Dean-Stark apparatus, butane in reactor equipped with cooler Add 7 g of 1,2,3,4-tetracarboxylic dianhydride, 0.7 g of paratoluenesulfonic acid monohydrate, 150 mL of toluene, and 35 g of trimethylolpropane diallyl ether (90%), and at reflux temperature for 51 hours Reacted. After completion of the reaction, washing with aqueous sodium bicarbonate, washing with water, concentration, purification by silica gel chromatography (hexane: ethyl acetate = 90: 10), tetra (2,2-bis (allyloxymethyl) butyl) -1, 20 g of 2,3,4-butanetetracarboxylic acid ester was obtained as a yellow liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.92-5.79 (m, 8H), 5.27-5.12 (m, 16H), 4.13-4.00 (m, 8H) 3.95 to 3.91 (m, 16H), 3.32 to 3.30 (m, 18H), 2.85 to 2.76 (m, 2H), 2.40 to 2.35 (m, 2H), 1.45 to 1.41 (m, 8H), 0.87 to 0.81 (m, 12H)
TOF-MS (MALDI): m / z = 1042 (M + Na).
　反応器にテトラ（２，２－ビス（アリルオキシメチル）ブチル）－１，２，３，４－ブタンテトラカルボン酸エステル１９ｇ、クロロホルム５００ｍＬ、メタクロロ過安息香酸４２ｇを加え、９日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水を加えて、抽出した。有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝２０：８０）にて精製し、濃縮した後、トルエン１７０ｇ、活性炭３．４ｇを加え、３時間撹拌した。活性炭をろ過し、溶媒留去して淡黄色液体１６ｇを得た。
　得られた化合物は母核に対応する式（６－２）と置換基に対応する式（２－１）の組み合わせに相当するテトラ（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－１，２，３，４－ブタンテトラカルボン酸エステルであった。
Figure JPOXMLDOC01-appb-C000049
 　粘度は２５℃で１２１８６ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－４）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝４．１５～３．９７（ｍ、８Ｈ）、３．７２～３．６８（ｄ、８Ｈ）、３．４２～３．３２（ｍ、２６Ｈ）、３．１３～３．０９（ｍ、８Ｈ）、２．８５～２．８２（ｍ、２Ｈ）、２．７８～２．７５（ｍ、８Ｈ）、２．５９～２．５６（ｍ、８Ｈ）、２．４５～２．３９（ｍ、２Ｈ）、１．４５～１．４１（ｍ、８Ｈ）、０．８８～０．８２（ｍ、１２Ｈ）
　ＴＯＦ－ＭＳ（ＭＡＬＤＩ）：ｍ／ｚ＝１１７０（Ｍ＋Ｎａ）。 To the reactor, 19 g of tetra (2,2-bis (allyloxymethyl) butyl) -1,2,3,4-butanetetracarboxylic acid ester, 500 mL of chloroform and 42 g of metachloroperbenzoic acid were added and reacted for 9 days. After completion of the reaction, the reaction mixture was quenched with an aqueous sodium thiosulfate solution, and extracted with an aqueous sodium bicarbonate solution. The organic layer was evaporated to obtain a crude product. After purification by silica gel chromatography (hexane: ethyl acetate = 20: 80) and concentration, 170 g of toluene and 3.4 g of activated carbon were added and stirred for 3 hours. The activated carbon was filtered and the solvent was distilled off to obtain 16 g of a pale yellow liquid.
The obtained compound was tetra (2,2-bis (2,3-epoxypropyloxymethyl) corresponding to the combination of formula (6-2) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. Butyl) -1,2,3,4-butanetetracarboxylic acid ester.
Figure JPOXMLDOC01-appb-C000049
 The viscosity was 12186 mPa · s at 25 ° C. This epoxy compound was designated as (i-4).
H-NMR (300 MHz, CDCl 3 ): δ = 4.15-3.97 (m, 8H), 3.72-3.68 (d, 8H), 3.42-3.32 (m, 26H) 3.13 to 3.09 (m, 8H), 2.85 to 2.82 (m, 2H), 2.78 to 2.75 (m, 8H), 2.59 to 2.56 (m, 8H), 2.45 to 2.39 (m, 2H), 1.45 to 1.41 (m, 8H), 0.88 to 0.82 (m, 12H)
TOF-MS (MALDI): m / z = 1170 (M + Na).
　合成例５
　１，３，５－トリス［２―〔２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチルオキシ〕カルボニルエチル］イソシアヌレートの合成
　反応器にトリメチロールプロパンジアリルエーテル４５ｇ、ジクロロメタン３６０ｍＬ、４－ジメチルアミノピリジン２３ｇ、１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩３６ｇ、イソシアヌル酸トリス（２－カルボキシエチル）１８ｇを加え、室温で３日反応させた。反応終了後、有機層を塩酸、重曹水で洗浄し、濃縮した。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝８０：２０→５０：５０）で精製し、１，３，５－トリス［２－〔２，２－ビス（２，３－プロペニルオキシメチル）ブチルオキシ〕カルボニルエチル］イソシアヌレート２７ｇを無色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．９３～５．８０（ｍ、６Ｈ）、５．２８～５．１２（ｍ、１２Ｈ）、４．２１～４．１１（ｍ、６Ｈ）、４．０１（ｓ、６Ｈ）、３．９５～３．９２（ｍ、１２Ｈ）、３．３１（ｓ、１２Ｈ）、２．７０～２．６５（ｍ、６Ｈ）、１．４７～１．４０（ｍ、６Ｈ）、０．８８～０．８３（ｍ、９Ｈ）
　ＬＣ－ＭＳ（ＥＳＩ）：ｍ／ｚ＝９３５（Ｍ＋１）。 Synthesis example 5
Synthesis of 1,3,5-tris [2- [2,2-bis (2,3-epoxypropyloxymethyl) butyloxy] carbonylethyl] isocyanurate 45 g of trimethylolpropane diallyl ether, 360 mL of dichloromethane, 4- 23 g of dimethylaminopyridine, 36 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 18 g of tris (2-carboxyethyl) isocyanurate were added and reacted at room temperature for 3 days. After completion of the reaction, the organic layer was washed with hydrochloric acid and aqueous sodium bicarbonate and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 80: 20 → 50: 50), 1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) butyloxy] carbonylethyl ] 27 g of isocyanurate was obtained as a colorless liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.93 to 5.80 (m, 6H), 5.28 to 5.12 (m, 12H), 4.21 to 4.11 (m, 6H) 4.01 (s, 6H), 3.95 to 3.92 (m, 12H), 3.31 (s, 12H), 2.70 to 2.65 (m, 6H), 1.47 to 1 .40 (m, 6H), 0.88 to 0.83 (m, 9H)
LC-MS (ESI): m / z = 935 (M + 1).
　反応器に１，３，５－トリス［２－〔２，２－ビス（２，３－プロペニルオキシメチル）ブチルオキシ〕カルボニルエチル］イソシアヌレート２７ｇ、クロロホルム５３０ｍＬ、メタクロロ過安息香酸５０ｇを加え、室温で３日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水、水で洗浄した。有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝４０：６０→０：１００）にて精製し、濃縮した後、トルエン２５０ｍＬ、活性炭５ｇを加え、撹拌した。活性炭をろ過し、溶媒留去して無色液体２３ｇを得た。
　得られた化合物は母核に対応する式（５－２）と置換基に対応する式（２－１）の組み合わせに相当する１，３，５－トリス［２－〔２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチルオキシ〕カルボニルエチル］イソシアヌレートであった。
Figure JPOXMLDOC01-appb-C000050
 　粘度は３０℃で１４４６４ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－５）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=４．２０～４．１６（ｍ、６Ｈ）、４．０６（ｓ、６Ｈ）、３．７３～３．６７（ｍ、６Ｈ）、３．４４～３．３１（ｍ、１８Ｈ）、３．１４～３．０８（ｍ、６Ｈ）、２．７９～２．７６（ｍ、６Ｈ）、２．７１～２．６６（ｍ、６Ｈ）、２．５９～２．５７（ｍ、６Ｈ）、１．４７～１．４０（ｍ、６Ｈ）、０．８９～０．８４（ｍ、６Ｈ）
　ＭＡＬＤＩ－ＴＯＦＭＳ：ｍ／ｚ＝１０５２．８２（Ｍ＋Ｎａ） To the reactor was added 27 g of 1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) butyloxy] carbonylethyl] isocyanurate, 530 mL of chloroform and 50 g of metachloroperbenzoic acid at room temperature. The reaction was performed for 3 days. After completion of the reaction, the reaction was quenched with an aqueous sodium thiosulfate solution and washed with an aqueous sodium bicarbonate solution and water. The organic layer was evaporated to obtain a crude product. After purification by silica gel chromatography (hexane: ethyl acetate = 40: 60 → 0: 100) and concentration, 250 mL of toluene and 5 g of activated carbon were added and stirred. The activated carbon was filtered and the solvent was distilled off to obtain 23 g of a colorless liquid.
The obtained compound is 1,3,5-tris [2- [2,2-bis ( 2,3-epoxypropyloxymethyl) butyloxy] carbonylethyl] isocyanurate.
Figure JPOXMLDOC01-appb-C000050
 The viscosity was 14464 mPa · s at 30 ° C. This epoxy compound was designated as (i-5).
H-NMR (300 MHz, CDCl 3 ): δ = 4.20 to 4.16 (m, 6H), 4.06 (s, 6H), 3.73 to 3.67 (m, 6H), 3.44 To 3.31 (m, 18H), 3.14 to 3.08 (m, 6H), 2.79 to 2.76 (m, 6H), 2.71 to 2.66 (m, 6H), 2 .59 to 2.57 (m, 6H), 1.47 to 1.40 (m, 6H), 0.89 to 0.84 (m, 6H)
MALDI-TOFMS: m / z = 1052.82 (M + Na)
　合成例６
　１，３，５－トリス[２―〔２，２－ビス（２，３－エポキシプロピルオキシメチル）－３－（２，３－エポキシプロピルオキシ）プロピルオキシ〕カルボニルエチル]イソシアヌレートの合成
　反応器にペンタエリスリトール５６ｇ、ジクロロメタン４００ｍＬ、４－ジメチルアミノピリジン２９ｇ、１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩４６ｇ、イソシアヌル酸トリス（２－カルボキシエチル）２５ｇを加え、室温で一晩反応させた。反応終了後、有機層を塩酸、重曹水で洗浄し、濃縮した。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝９０：１０→８０：２０→６０：４０）で精製し、１，３，５－トリス[２―〔２，２－ビス（２，３－プロペニルオキシメチル）－３－（２，３－プロペニルオキシ）プロピルオキシ〕カルボニルエチル]イソシアヌレート２４ｇを無色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．９２～５．７９（ｍ、９Ｈ）、５．２７～５．１２（ｍ、１８Ｈ）、４．１８（ｍ、１２Ｈ）、３．９５～３．９２（ｍ、１８Ｈ）、３．４３（ｓ、１８Ｈ）、２．７０～２．６５（ｍ、６Ｈ）
　ＴＯＦ－ＭＳ（ＭＡＬＤＩ）：ｍ／ｚ＝１０８２．４３（Ｍ＋Ｎａ） Synthesis Example 6
Synthesis of 1,3,5-tris [2- [2,2-bis (2,3-epoxypropyloxymethyl) -3- (2,3-epoxypropyloxy) propyloxy] carbonylethyl] isocyanurate Were added 56 g of pentaerythritol, 400 mL of dichloromethane, 29 g of 4-dimethylaminopyridine, 46 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 25 g of tris (2-carboxyethyl) isocyanurate overnight at room temperature. Reacted. After completion of the reaction, the organic layer was washed with hydrochloric acid and aqueous sodium bicarbonate and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 90: 10 → 80: 20 → 60: 40) and 1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) There were obtained 24 g of -3- (2,3-propenyloxy) propyloxy] carbonylethyl] isocyanurate as a colorless liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.92-5.79 (m, 9H), 5.27-5.12 (m, 18H), 4.18 (m, 12H), 3.95 To 3.92 (m, 18H), 3.43 (s, 18H), 2.70 to 2.65 (m, 6H)
TOF-MS (MALDI): m / z = 1082.43 (M + Na)
　反応器に１，３，５－トリス[２―〔２，２－ビス（２，３－プロペニルオキシメチル）－３－（２，３－プロペニルオキシ）プロピルオキシ〕カルボニルエチル]イソシアヌレート２３ｇ、クロロホルム１Ｌ、メタクロロ過安息香酸６３ｇを加え、室温で６日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水、水で洗浄した。有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝２０：８０→０：１００）にて精製し、濃縮した後、トルエン５００ｍＬ、活性炭４ｇを加え、撹拌した。活性炭をろ過し、溶媒留去して無色液体３３ｇを得た。
　得られた化合物は母核に対応する式（５－２）と置換基に対応する式（２－２）の組み合わせに相当する１，３，５－トリス[２―〔２，２－ビス（２，３－エポキシプロピルオキシメチル）－３－（２，３－エポキシプロピルオキシ）プロピルオキシ〕カルボニルエチル]イソシアヌレートであった。
Figure JPOXMLDOC01-appb-C000051
 　粘度は３０℃で１５４６２ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－６）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=４．２０～４．１５（ｍ、１２Ｈ）、３．７４～３．３１（ｍ、３６Ｈ）、３．１２～３．０８（ｍ、９Ｈ）、２．７９～２．５７（ｍ、２４Ｈ）
　ＴＯＦ－ＭＳ（ＭＡＬＤＩ）：ｍ／ｚ＝１２２６．５２（Ｍ＋Ｎａ） The reactor was charged with 23 g of 1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) -3- (2,3-propenyloxy) propyloxy] carbonylethyl] isocyanurate, chloroform 1 L and 63 g of metachloroperbenzoic acid were added and reacted at room temperature for 6 days. After completion of the reaction, the reaction was quenched with an aqueous sodium thiosulfate solution and washed with an aqueous sodium bicarbonate solution and water. The organic layer was evaporated to obtain a crude product. After purification by silica gel chromatography (hexane: ethyl acetate = 20: 80 → 0: 100) and concentration, 500 mL of toluene and 4 g of activated carbon were added and stirred. The activated carbon was filtered and the solvent was distilled off to obtain 33 g of a colorless liquid.
The obtained compound was 1,3,5-tris [2- [2,2-bis () corresponding to the combination of the formula (5-2) corresponding to the mother nucleus and the formula (2-2) corresponding to the substituent. 2,3-epoxypropyloxymethyl) -3- (2,3-epoxypropyloxy) propyloxy] carbonylethyl] isocyanurate.
Figure JPOXMLDOC01-appb-C000051
 The viscosity was 15462 mPa · s at 30 ° C. This epoxy compound was designated as (i-6).
H-NMR (300 MHz, CDCl 3 ): δ = 4.20 to 4.15 (m, 12H), 3.74 to 3.31 (m, 36H), 3.12 to 3.08 (m, 9H) 2.79 to 2.57 (m, 24H)
TOF-MS (MALDI): m / z = 1226.52 (M + Na)
　合成例７
　１，３，５－トリス[２―〔１－（２，３－エポキシプロピルオキシメチル）－２－（２，３－エポキシプロピルオキシ）エチルオキシ〕カルボニルエチル]イソシアヌレートの合成
　反応器にイソシアヌル酸トリス（２－カルボキシエチル）５５ｇ、Ｎ，Ｎ－ジメチルホルムアミド１７０ｍＬを加え、溶解を確認した後、塩化チオニル６３ｇを滴下した。室温で１時間撹拌し、析出した固体をろ過、クロロホルムで洗浄、乾燥し、１，３，５－トリス（２－クロロホルミルエチル）イソシアヌレート５４ｇを白色固体として得た。
　反応器にクロロホルム１００ｍＬ、グリセロールーα、α´―ジアリルエーテル３７ｇ、ピリジン１７ｇを加えた後、撹拌し、１，３，５－トリス（２－クロロホルミルエチル）イソシアヌレート２０ｇを少しずつ加えた。６５℃で３時間反応させた。溶媒留去後、析出した塩をろ過で除き、ろ液にクロロホルムを加え、水で洗浄した。有機層を濃縮後、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝７０：３０→５０：５０）にて精製し、１，３，５－トリス[２―〔１－（２，３－プロペニルオキシメチル）－２－（２，３－プロペニルオキシ）エチルオキシ〕カルボニルエチル]イソシアヌレート２７ｇを無色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．９４～５．８０（ｍ、６Ｈ）、５．２９～５．１２（ｍ、１５Ｈ）、４．２０～４．１６（ｍ、６Ｈ）、４．０４～３．９８（ｍ、１２Ｈ）、３．６０～３．５８（ｄ、１２Ｈ）、２．７４～２．６９（ｔ、６Ｈ） Synthesis example 7
Synthesis of 1,3,5-tris [2- [1- (2,3-epoxypropyloxymethyl) -2- (2,3-epoxypropyloxy) ethyloxy] carbonylethyl] isocyanurate After adding 55 g of (2-carboxyethyl) and 170 mL of N, N-dimethylformamide and confirming dissolution, 63 g of thionyl chloride was added dropwise. The mixture was stirred at room temperature for 1 hour, and the precipitated solid was filtered, washed with chloroform, and dried to obtain 54 g of 1,3,5-tris (2-chloroformylethyl) isocyanurate as a white solid.
To the reactor were added 100 mL of chloroform, 37 g of glycerol-α, α′-diallyl ether, and 17 g of pyridine, followed by stirring, and 20 g of 1,3,5-tris (2-chloroformylethyl) isocyanurate was added little by little. The reaction was carried out at 65 ° C. for 3 hours. After evaporating the solvent, the precipitated salt was removed by filtration, chloroform was added to the filtrate, and the mixture was washed with water. The organic layer was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 70: 30 → 50: 50) to obtain 1,3,5-tris [2- [1- (2,3-propenyloxymethyl) There were obtained 27 g of -2- (2,3-propenyloxy) ethyloxy] carbonylethyl] isocyanurate as a colorless liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.94-5.80 (m, 6H), 5.29-5.12 (m, 15H), 4.20-4.16 (m, 6H) 4.04 to 3.98 (m, 12H), 3.60 to 3.58 (d, 12H), 2.74 to 2.69 (t, 6H)
　反応器に１，３，５－トリス[２―〔１－（２，３－プロペニルオキシメチル）－２－（２，３－プロペニルオキシ）エチルオキシ〕カルボニルエチル]イソシアヌレート２７ｇ、クロロホルム１Ｌ、メタクロロ過安息香酸５９ｇを加え、室温で４日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水、水で洗浄した。有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝７０：３０→５０：５０→３０：７０→１０：９０→０：１００）にて精製し、濃縮した後、トルエン１２０ｍＬ、活性炭２ｇを加え、撹拌した。活性炭をろ過し、溶媒留去して無色液体１２ｇを得た。
　得られた化合物は母核に対応する式（５－２）と置換基に対応する式（２－３）の組み合わせに相当する１，３，５－トリス[２―〔１－（２，３－エポキシプロピルオキシメチル）－２－（２，３－エポキシプロピルオキシ）エチルオキシ〕カルボニルエチル]イソシアヌレートであった。
Figure JPOXMLDOC01-appb-C000052
 　粘度は３０℃で１８０６１ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－７）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．１５～５．１２（ｍ、３Ｈ）、４．２１～４．１６（ｍ、６Ｈ）、３．８３～３．３５（ｍ、２４Ｈ）、３．１４～３．１３（ｍ、６Ｈ）、２．８０～２．５８（ｍ、１８Ｈ）
　ＬＣ－ＭＳ（ＥＳＩ）：ｍ／ｚ＝９０５（Ｍ＋Ｈ） In a reactor, 1,3,5-tris [2- [1- (2,3-propenyloxymethyl) -2- (2,3-propenyloxy) ethyloxy] carbonylethyl] isocyanurate 27 g, chloroform 1 L, metachloroperoxide 59 g of benzoic acid was added and reacted at room temperature for 4 days. After completion of the reaction, the reaction was quenched with an aqueous sodium thiosulfate solution and washed with an aqueous sodium bicarbonate solution and water. The organic layer was evaporated to obtain a crude product. After purification by silica gel chromatography (hexane: ethyl acetate = 70: 30 → 50: 50 → 30: 70 → 10: 90 → 0: 100) and concentration, 120 mL of toluene and 2 g of activated carbon were added and stirred. The activated carbon was filtered and the solvent was distilled off to obtain 12 g of a colorless liquid.
The obtained compound was 1,3,5-tris [2- [1- (2,3, corresponding to a combination of the formula (5-2) corresponding to the mother nucleus and the formula (2-3) corresponding to the substituent. -Epoxypropyloxymethyl) -2- (2,3-epoxypropyloxy) ethyloxy] carbonylethyl] isocyanurate.
Figure JPOXMLDOC01-appb-C000052
 The viscosity was 18061 mPa · s at 30 ° C. This epoxy compound was designated as (i-7).
H-NMR (300 MHz, CDCl 3 ): δ = 5.15 to 5.12 (m, 3H), 4.21 to 4.16 (m, 6H), 3.83 to 3.35 (m, 24H) 3.14 to 3.13 (m, 6H), 2.80 to 2.58 (m, 18H)
LC-MS (ESI): m / z = 905 (M + H)
　合成例８
　１，３，５－トリス〔２，３－ビス（２，３－エポキシプロピルオキシ）プロピル〕イソシアヌレートの合成
　反応器にイソシアヌル酸３０ｇ、テトラメチルアンモニウムクロライド５ｇ、１，３－ジメチルー２－イミダゾリジノン３００mＬ、アリルグリシジルエーテル９５ｇを加え、１００℃で５時間反応させた。反応終了後、酢酸エチルで抽出し、有機層を重曹水で洗浄し、濃縮した。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝３０：７０）で精製し、１，３，５－トリス〔２－ヒドロキシ－３－（２，３－プロペニルオキシ）プロピル〕イソシアヌレート３７ｇを無色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．９４～５．８５（ｍ、３Ｈ）、５．３１～５．１８（ｍ、６Ｈ）、４．２７～３．９３（ｍ、１５Ｈ）、３．５７～３．４５（ｍ、６Ｈ）、２．６７～２．６５（ｍ、３Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝４７１（Ｍ） Synthesis example 8
Synthesis of 1,3,5-tris [2,3-bis (2,3-epoxypropyloxy) propyl] isocyanurate 30 g of isocyanuric acid, 5 g of tetramethylammonium chloride, 1,3-dimethyl-2-imidazolidi Non-300 mL and allyl glycidyl ether 95 g were added and reacted at 100 ° C. for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, and the organic layer was washed with sodium bicarbonate water and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 30: 70) gave 37 g of 1,3,5-tris [2-hydroxy-3- (2,3-propenyloxy) propyl] isocyanurate as a colorless liquid. .
H-NMR (300 MHz, CDCl 3 ): δ = 5.94 to 5.85 (m, 3H), 5.31 to 5.18 (m, 6H), 4.27 to 3.93 (m, 15H) 3.57 to 3.45 (m, 6H), 2.67 to 2.65 (m, 3H)
GC-MS (CI): m / z = 471 (M)
　反応器に水素化ナトリウム１１ｇ、ジメチルホルムアミド７００mＬを加え、０℃で撹拌しながら、１，３，５－トリス〔２－ヒドロキシ－３－（２，３－プロペニルオキシ）プロピル〕イソシアヌレート３５ｇ、アリルブロマイド５４ｇを滴下し、室温で１日間反応させた。反応終了後、水でクエンチ、トルエンで抽出し、有機層をブラインで洗浄し、濃縮した。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝８０：２０→５０：５０）で精製し、１，３，５－トリス〔２，３－ビス（２，３－プロペニルオキシ）プロピル〕イソシアヌレート１３ｇを無色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．９４～５．７９（ｍ、６Ｈ）、５．２７～５．１１（ｍ、１２Ｈ）、４．１９～３．９４（ｍ、１８Ｈ）、３．８６～３．８３（ｍ、３Ｈ）、３．５２～３．５１（ｍ、６Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝５９２（Ｍ＋２） To the reactor, 11 g of sodium hydride and 700 mL of dimethylformamide were added, and while stirring at 0 ° C., 35 g of 1,3,5-tris [2-hydroxy-3- (2,3-propenyloxy) propyl] isocyanurate, allyl 54 g of bromide was added dropwise and reacted at room temperature for 1 day. After completion of the reaction, it was quenched with water and extracted with toluene, and the organic layer was washed with brine and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 80: 20 → 50: 50) and 13 g of 1,3,5-tris [2,3-bis (2,3-propenyloxy) propyl] isocyanurate were colorless liquid Got as.
H-NMR (300 MHz, CDCl 3 ): δ = 5.94-5.79 (m, 6H), 5.27-5.11 (m, 12H), 4.19-3.94 (m, 18H) 3.86 to 3.83 (m, 3H), 3.52 to 3.51 (m, 6H)
GC-MS (CI): m / z = 592 (M + 2)
　反応器に１，３，５－トリス〔２，３－ビス（２，３－プロペニルオキシ）プロピル〕イソシアヌレート２１ｇ、クロロホルム６３０ｍＬ、メタクロロ過安息香酸５９ｇを加え、室温で４日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水、水で洗浄した。有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝２０：８０）にて精製し、濃縮した後、トルエン３２０ｍＬ、活性炭７ｇを加え、撹拌した。活性炭をろ過し、溶媒留去して無色液体３０ｇを得た。
　得られた化合物は母核に対応する式（５－６）と置換基に対応する式（２－４）の組み合わせに相当する１，３，５－トリス〔２，３－ビス（２，３－エポキシプロピルオキシ）プロピル〕イソシアヌレートであった。
Figure JPOXMLDOC01-appb-C000053
 　粘度は２５℃で１７０１１ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－８）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=４．０９～３．７６（ｍ、１５Ｈ）、３．６６～３．３２（ｍ、１２Ｈ）、３．１６～３．０８（ｍ、６Ｈ）、２．７９～２．７１（ｍ、６Ｈ）、２．６２～２．５７（ｍ、６Ｈ）
　ＬＣ－ＭＳ（ＥＳＩ）：ｍ／ｚ＝６８８（Ｍ＋１）。 To the reactor, 21 g of 1,3,5-tris [2,3-bis (2,3-propenyloxy) propyl] isocyanurate, 630 mL of chloroform, and 59 g of metachloroperbenzoic acid were added and reacted at room temperature for 4 days. After completion of the reaction, the reaction was quenched with an aqueous sodium thiosulfate solution and washed with an aqueous sodium bicarbonate solution and water. The organic layer was evaporated to obtain a crude product. After purification by silica gel chromatography (hexane: ethyl acetate = 20: 80) and concentration, 320 mL of toluene and 7 g of activated carbon were added and stirred. The activated carbon was filtered and the solvent was distilled off to obtain 30 g of a colorless liquid.
The obtained compound was 1,3,5-tris [2,3-bis (2,3) corresponding to the combination of the formula (5-6) corresponding to the mother nucleus and the formula (2-4) corresponding to the substituent. -Epoxypropyloxy) propyl] isocyanurate.
Figure JPOXMLDOC01-appb-C000053
 The viscosity was 17011 mPa · s at 25 ° C. This epoxy compound was designated as (i-8).
H-NMR (300 MHz, CDCl 3 ): δ = 4.09 to 3.76 (m, 15H), 3.66 to 3.32 (m, 12H), 3.16 to 3.08 (m, 6H) 2.79 to 2.71 (m, 6H) 2.62 to 2.57 (m, 6H)
LC-MS (ESI): m / z = 688 (M + 1).
　合成例９
　ビス（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－アダマンタン－１，３－ジカルボン酸エステルの合成
　反応器に１，３－アダマンタンジカルボン酸２０ｇ、メタノール２００ｇ、濃硫酸０．８ｇを加え、還流温度で２時間反応させた。反応液を濃縮し、トルエン２００ｍＬを加え、重曹水、続いて水で洗浄した。有機層を濃縮し、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝３：１）で精製し、１，３－アダマンタンジカルボン酸メチルエステル２１ｇを白色固体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=３．６６（ｓ、６Ｈ）、２．１５～１．６８（ｍ、１４Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝２５３（Ｍ＋Ｈ） Synthesis Example 9
Synthesis of bis (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -adamantane-1,3-dicarboxylic acid ester In a reactor, 20 g of 1,3-adamantane dicarboxylic acid, 200 g of methanol, 0. 8 g was added and reacted at reflux temperature for 2 hours. The reaction mixture was concentrated, 200 mL of toluene was added, and the mixture was washed with an aqueous sodium bicarbonate solution and then with water. The organic layer was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 3: 1) to obtain 21 g of 1,3-adamantanedicarboxylic acid methyl ester as a white solid.
H-NMR (300 MHz, CDCl 3 ): δ = 3.66 (s, 6H), 2.15 to 1.68 (m, 14H)
GC-MS (CI): m / z = 253 (M + H)
　反応器に１，３－アダマンタンジカルボン酸メチルエステル２０ｇ、パラトルエンスルホン酸水和物１２ｇ、トルエン２００ｍＬ、トリメチロールプロパンジアリルエーテル（９０％）７０ｇを加え、還流温度で２６日間反応させた。反応液を濃縮し、重曹水、水酸化ナトリウム水溶液で洗浄した。有機層を濃縮し、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝１００：０→９５：５→８０：２０）にて精製し、ビス（２，２－ビス（プロペニルオキシメチル）ブチル）－アダマンタン－１，３－ジカルボン酸エステル１４ｇを褐色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．９１～５．８２（ｍ、４Ｈ）、５．２７～５．１３（ｍ、８Ｈ）、３．９７（ｓ、４Ｈ）、３．９４～３．９２（ｍ、８Ｈ）、３．３２（ｓ、８Ｈ）、２．１６～１．６９（ｍ、１４Ｈ）、１．４６～１．４３（ｑ、４Ｈ）、０．８８～０．８３（ｔ、６Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝６１８（Ｍ＋Ｈ） To the reactor, 20 g of 1,3-adamantanedicarboxylic acid methyl ester, 12 g of paratoluenesulfonic acid hydrate, 200 mL of toluene, and 70 g of trimethylolpropane diallyl ether (90%) were added and reacted at reflux temperature for 26 days. The reaction solution was concentrated and washed with an aqueous sodium bicarbonate solution and an aqueous sodium hydroxide solution. The organic layer was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 100: 0 → 95: 5 → 80: 20), and bis (2,2-bis (propenyloxymethyl) butyl) -adamantane-1 , 3-dicarboxylic acid ester 14 g was obtained as a brown liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.91 to 5.82 (m, 4H), 5.27 to 5.13 (m, 8H), 3.97 (s, 4H), 3.94 To 3.92 (m, 8H), 3.32 (s, 8H), 2.16 to 1.69 (m, 14H), 1.46 to 1.43 (q, 4H), 0.88 to 0 .83 (t, 6H)
GC-MS (CI): m / z = 618 (M + H)
　反応器にビス（２，２－ビス（プロペニルオキシメチル）ブチル）－アダマンタン－１，３－ジカルボン酸エステル１３ｇ、クロロホルム５００ｍＬ、メタクロロ過安息香酸４７ｇを加え、室温で３日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水、水で洗浄した。有機層を溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝７０：３０→５０：５０→３０：７０→１０：９０）にて精製し、濃縮した後、トルエン１３０ｍＬ、活性炭３ｇを加え、撹拌した。活性炭をろ過し、溶媒留去して淡黄色液体９ｇを得た。
　得られた化合物は母核に対応する式（４－１）と置換基に対応する式（２－１）の組み合わせに相当するビス（２，２－ビス（２，３－エポキシプロピルオキシメチル）ブチル）－アダマンタン－１，３－ジカルボン酸エステルであった。
Figure JPOXMLDOC01-appb-C000054
 　粘度は２５℃で２６０９ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－９）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=４．００（ｓ、４Ｈ）、３．７２～３．６７（ｍ、４Ｈ）、３．４４～３．３２（ｍ、１２Ｈ）、３．１０（ｓ、４Ｈ）、２．７９～２．７６（ｍ、４Ｈ）、２．５９～２．５７（ｍ、４Ｈ）、２．０２～１．６９（ｍ、１４Ｈ）、１．４６～１．４３（ｑ、６Ｈ）、０．８９～０．８３（ｔ、４Ｈ）
　ＬＣ－ＭＳ（ＥＳＩ）：ｍ／ｚ＝６８２（Ｍ＋Ｈ） Bis (2,2-bis (propenyloxymethyl) butyl) -adamantane-1,3-dicarboxylic acid ester (13 g), chloroform (500 mL) and metachloroperbenzoic acid (47 g) were added to the reactor and reacted at room temperature for 3 days. After completion of the reaction, the reaction was quenched with an aqueous sodium thiosulfate solution and washed with an aqueous sodium bicarbonate solution and water. The organic layer was evaporated to obtain a crude product. After purification by silica gel chromatography (hexane: ethyl acetate = 70: 30 → 50: 50 → 30: 70 → 10: 90) and concentration, 130 mL of toluene and 3 g of activated carbon were added and stirred. The activated carbon was filtered and the solvent was distilled off to obtain 9 g of a pale yellow liquid.
The obtained compound is bis (2,2-bis (2,3-epoxypropyloxymethyl) corresponding to the combination of the formula (4-1) corresponding to the mother nucleus and the formula (2-1) corresponding to the substituent. Butyl) -adamantane-1,3-dicarboxylic acid ester.
Figure JPOXMLDOC01-appb-C000054
 The viscosity was 2609 mPa · s at 25 ° C. This epoxy compound was designated as (i-9).
H-NMR (300 MHz, CDCl 3 ): δ = 4.00 (s, 4H), 3.72 to 3.67 (m, 4H), 3.44 to 3.32 (m, 12H), 3.10 (S, 4H), 2.79 to 2.76 (m, 4H), 2.59 to 2.57 (m, 4H), 2.02 to 1.69 (m, 14H), 1.46 to 1 .43 (q, 6H), 0.89 to 0.83 (t, 4H)
LC-MS (ESI): m / z = 682 (M + H)
　比較合成例１
　ビス（２，３－エポキシプロピル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステルの合成
　反応器にシス－４－シクロヘキセン－１，２－ジカルボン酸１５ｇ、炭酸カリウム３７ｇ、ジメチルホルムアミド２５５ｍＬ、アリルブロミド３２ｇを加え、室温で１５時間反応させた。反応終了後、ろ過し、トルエンと水を加え、抽出した。水洗浄、濃縮したあと、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝７５：２５）で精製し、ビス（２－プロペニル）－４－シクロヘキセン－１，２－ジカルボン酸エステル２１ｇを淡黄色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝５．９６～５．８２（ｍ、２Ｈ）、５．６８～５．６７（ｍ、２Ｈ）、５．３３～５．１９（ｍ、４Ｈ）、４．６０～４．５８（ｍ、４Ｈ）、３．１１～３．０７（ｍ、２Ｈ）、２．６２～２．５５（ｍ、２Ｈ）、２．４１～２．３３（ｍ、２Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝２５０（Ｍ）。 Comparative Synthesis Example 1
Synthesis of bis (2,3-epoxypropyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester 15 g of cis-4-cyclohexene-1,2-dicarboxylic acid, 37 g of potassium carbonate, 255 mL of dimethylformamide Allyl bromide (32 g) was added and allowed to react at room temperature for 15 hours. After completion of the reaction, the mixture was filtered, and toluene and water were added for extraction. After washing with water and concentrating, the residue was purified by silica gel chromatography (hexane: ethyl acetate = 75: 25) to obtain 21 g of bis (2-propenyl) -4-cyclohexene-1,2-dicarboxylic acid ester as a pale yellow liquid. .
H-NMR (300 MHz, CDCl 3 ): δ = 5.96 to 5.82 (m, 2H), 5.68 to 5.67 (m, 2H), 5.33 to 5.19 (m, 4H) 4.60 to 4.58 (m, 4H), 3.11 to 3.07 (m, 2H), 2.62 to 2.55 (m, 2H), 2.41 to 2.33 (m, 2H)
GC-MS (CI): m / z = 250 (M).
　反応器にビス（２－プロペニル）－４－シクロヘキセン－１，２－ジカルボン酸エステル２１ｇ、クロロホルム３００ｍＬを加え、０－１０℃に冷却後、メタクロロ過安息香酸８７ｇを加え、室温まで昇温し、５日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水を加えて、抽出した。有機層を重曹水洗浄、水洗浄し、乾燥、溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝５０：５０→１０：９０）にて精製して無色液体２０ｇを得た。
　得られた化合物はビス（２，３－エポキシプロピル）－４，５－エポキシシクロヘキサン－１，２－ジカルボン酸エステルであった。
Figure JPOXMLDOC01-appb-C000055
 　粘度は２５℃で１９９２ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－１０）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝４．５１～４．４１（ｍ、２Ｈ）、３．９６～３．８４（ｍ、２Ｈ）、３．２５～３．１９（ｍ、４Ｈ）、３．０１～２．９８（ｍ、２Ｈ）、２．８４～２．８１（ｍ、２Ｈ）、２．６６～２．６１（ｍ、２Ｈ）、２．２７～２．２０（ｍ、４Ｈ）、
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝２９８（Ｍ）。 To the reactor, 21 g of bis (2-propenyl) -4-cyclohexene-1,2-dicarboxylic acid ester and 300 mL of chloroform were added. After cooling to 0-10 ° C., 87 g of metachloroperbenzoic acid was added, and the temperature was raised to room temperature. The reaction was performed for 5 days. After completion of the reaction, the reaction mixture was quenched with an aqueous sodium thiosulfate solution, and extracted with an aqueous sodium bicarbonate solution. The organic layer was washed with aqueous sodium bicarbonate, washed with water, dried and evaporated to give a crude product. Purification by silica gel chromatography (hexane: ethyl acetate = 50: 50 → 10: 90) gave 20 g of a colorless liquid.
The resulting compound was bis (2,3-epoxypropyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester.
Figure JPOXMLDOC01-appb-C000055
 The viscosity was 1992 mPa · s at 25 ° C. This epoxy compound was designated as (i-10).
H-NMR (300 MHz, CDCl 3 ): δ = 4.51 to 4.41 (m, 2H), 3.96 to 3.84 (m, 2H), 3.25 to 3.19 (m, 4H) 3.01 to 2.98 (m, 2H), 2.84 to 2.81 (m, 2H), 2.66 to 2.61 (m, 2H), 2.27 to 2.20 (m, 4H),
GC-MS (CI): m / z = 298 (M).
　比較合成例２
　テトラ（２，３－エポキシプロピル）－１，２，３，４－ブタンテトラカルボン酸エステルの合成
　反応器に１，２，３，４－ブタンテトラカルボン酸５３ｇ、炭酸カリウム１５５ｇ、Ｎ，Ｎ－ジメチルホルムアミド８９２ｍＬ、アリルブロミド１７７ｇを加え、６８度で１１時間反応させた。反応終了後、トルエンと共に水洗浄を行い、濃縮し、シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝８０：２０）で精製し、テトラ（２－プロペニル）－１，２，３，４－ブタンテトラカルボン酸エステル７１ｇを淡黄色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝５．９４～５．８２（ｍ、４Ｈ）、５．３５～５．２２（ｍ、８Ｈ）、４．６１～４．５８（ｍ、８Ｈ）、３．４１～３．３７（ｍ、２Ｈ）、２．９０～２．８１（ｍ、２Ｈ）、２．５０～２．４３（ｍ、２Ｈ）、
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝３９５（Ｍ＋Ｈ）、 Comparative Synthesis Example 2
Synthesis of tetra (2,3-epoxypropyl) -1,2,3,4-butanetetracarboxylic acid ester In a reactor, 53 g of 1,2,3,4-butanetetracarboxylic acid, 155 g of potassium carbonate, N, N— 892 mL of dimethylformamide and 177 g of allyl bromide were added and reacted at 68 degrees for 11 hours. After completion of the reaction, the mixture is washed with toluene, concentrated, purified by silica gel chromatography (hexane: ethyl acetate = 80: 20), and tetra (2-propenyl) -1,2,3,4-butanetetracarboxylic acid. 71 g of ester was obtained as a pale yellow liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.94 to 5.82 (m, 4H), 5.35 to 5.22 (m, 8H), 4.61 to 4.58 (m, 8H) 3.41 to 3.37 (m, 2H), 2.90 to 2.81 (m, 2H), 2.50 to 2.43 (m, 2H),
GC-MS (CI): m / z = 395 (M + H),
　反応器にテトラ（２－プロペニル）－１，２，３，４－ブタンテトラカルボン酸エステル４０ｇ、クロロホルム８００ｍＬを加え、０－１０℃に冷却後、メタクロロ過安息香酸１１２ｇを加え、室温まで昇温し、９６時間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水を加えて、抽出した。有機層を水洗浄し、溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝２０：８０）にて精製して無色液体２２ｇを得た。室温で放置したところ結晶が析出したため、エノタールで洗浄し、白色固体を得た。結晶の融点をＤＳＣで測定したところ、４９．６℃であった。　得られた化合物はテトラ（３，４－エポキシプロピル）－１，２，３，４－ブタンテトラカルボン酸エステルであった。
Figure JPOXMLDOC01-appb-C000056
 　このエポキシ化合物を（ｉ－１１）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ3）：δ＝４．５２～４．４２（ｍ、４Ｈ）、４．００～３．９０（ｍ、４Ｈ）、３．４４～３．４１（ｍ、２Ｈ）、３．２５～３．１８（ｍ、４Ｈ）、２．９３～２．８３（ｍ、６Ｈ）、２．６７～２．６３（ｍ、４Ｈ）、２．５５～２．４９（ｍ、２Ｈ）、
　ＬＣ－ＭＳ（ＥＳＩ）：ｍ／ｚ＝４８１．２（Ｍ＋Ｎａ）。 Add 40 g of tetra (2-propenyl) -1,2,3,4-butanetetracarboxylic acid ester and 800 mL of chloroform to the reactor, cool to 0-10 ° C, add 112 g of metachloroperbenzoic acid, and warm to room temperature. And allowed to react for 96 hours. After completion of the reaction, the reaction mixture was quenched with an aqueous sodium thiosulfate solution, and extracted with an aqueous sodium bicarbonate solution. The organic layer was washed with water and the solvent was distilled off to obtain a crude product. Purification by silica gel chromatography (hexane: ethyl acetate = 20: 80) gave 22 g of a colorless liquid. Crystals precipitated when allowed to stand at room temperature and washed with enothal to give a white solid. It was 49.6 degreeC when melting | fusing point of the crystal was measured by DSC. The resulting compound was tetra (3,4-epoxypropyl) -1,2,3,4-butanetetracarboxylic acid ester.
Figure JPOXMLDOC01-appb-C000056
 This epoxy compound was designated as (i-11).
H-NMR (300 MHz, CDCl 3 ): δ = 4.52 to 4.42 (m, 4H), 4.00 to 3.90 (m, 4H), 3.44 to 3.41 (m, 2H) 3.25 to 3.18 (m, 4H), 2.93 to 2.83 (m, 6H), 2.67 to 2.63 (m, 4H), 2.55 to 2.49 (m, 2H),
LC-MS (ESI): m / z = 481.2 (M + Na).
　比較合成例３
　ビス（２，３－エポキシプロピル）－アダマンタン－１，３－ジカルボン酸エステルの合成
　反応器に１，３－アダマンタンジカルボン酸２０ｇ、炭酸カリウム３２ｇ、Ｎ，Ｎ－ジメチルホルムアミド５００ｍＬ、アリルブロミド３２ｇを加え、６５℃で４時間反応させた。反応液をろ過し、ろ液にトルエンを加え、水で洗浄した。得られた有機層を濃縮し、ビス（２，３－プロペニル）－アダマンタン－１，３－ジカルボン酸エステル２８ｇを黄色液体として得た。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=５．９７～５．８４（ｍ、２Ｈ）、５．３３～５．２０（ｍ、４Ｈ）、４．５８～４．５５（ｍ、４Ｈ）、２．１７～１．６９（ｍ、１４Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝３０４（Ｍ）。 Comparative Synthesis Example 3
Synthesis of bis (2,3-epoxypropyl) -adamantane-1,3-dicarboxylic acid ester 20 g of 1,3-adamantane dicarboxylic acid, 32 g of potassium carbonate, 500 mL of N, N-dimethylformamide and 32 g of allyl bromide were added to the reactor. , Reacted at 65 ° C. for 4 hours. The reaction solution was filtered, toluene was added to the filtrate, and the mixture was washed with water. The obtained organic layer was concentrated to obtain 28 g of bis (2,3-propenyl) -adamantane-1,3-dicarboxylic acid ester as a yellow liquid.
H-NMR (300 MHz, CDCl 3 ): δ = 5.97 to 5.84 (m, 2H), 5.33 to 5.20 (m, 4H), 4.58 to 4.55 (m, 4H) 2.17 to 1.69 (m, 14H)
GC-MS (CI): m / z = 304 (M).
　反応器にビス（２，３－プロペニル）－アダマンタン－１，３－ジカルボン酸エステル２７ｇ、メタクロロ過安息香酸６２ｇ、クロロホルム５００ｍＬを加え、室温で５日間反応させた。反応終了後、チオ硫酸ナトリウム水溶液でクエンチし、重曹水を加えて、抽出した。有機層を水洗浄し、溶媒留去して粗物を得た。シリカゲルクロマトグラフィー（ヘキサン：酢酸エチル＝７０：３０→５０：５０）にて精製し、濃縮した後、トルエン２５０ｍＬ、活性炭５ｇを加え、撹拌した。活性炭をろ過し、溶媒留去して無色液体２０ｇを得た。
　得られた化合物はビス（２，３－エポキシプロピル）－アダマンタン－１，３－ジカルボン酸エステルであった。
Figure JPOXMLDOC01-appb-C000057
 　粘度は２５℃で２０７ｍＰａ・ｓであった。このエポキシ化合物を（ｉ－１２）とした。
　Ｈ－ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ３）：δ=４．４３～４．３８（ｍ、２Ｈ）、３．９６～３．９０（ｍ、２Ｈ）、３．２３～３．１７（ｍ、２Ｈ）、２．８６～２．８３（ｍ、２Ｈ）、２．６６～２．６３（ｍ、２Ｈ）、２．１８～１．７０（ｍ、１４Ｈ）
　ＧＣ－ＭＳ（ＣＩ）：ｍ／ｚ＝３３６（Ｍ） To the reactor, 27 g of bis (2,3-propenyl) -adamantane-1,3-dicarboxylic acid ester, 62 g of metachloroperbenzoic acid and 500 mL of chloroform were added and reacted at room temperature for 5 days. After completion of the reaction, the reaction mixture was quenched with an aqueous sodium thiosulfate solution, and extracted with an aqueous sodium bicarbonate solution. The organic layer was washed with water and the solvent was distilled off to obtain a crude product. After purification by silica gel chromatography (hexane: ethyl acetate = 70: 30 → 50: 50) and concentration, 250 mL of toluene and 5 g of activated carbon were added and stirred. The activated carbon was filtered and the solvent was distilled off to obtain 20 g of a colorless liquid.
The resulting compound was bis (2,3-epoxypropyl) -adamantane-1,3-dicarboxylic acid ester.
Figure JPOXMLDOC01-appb-C000057
 The viscosity was 207 mPa · s at 25 ° C. This epoxy compound was designated as (i-12).
H-NMR (300 MHz, CDCl 3 ): δ = 4.43 to 4.38 (m, 2H), 3.96 to 3.90 (m, 2H), 3.23 to 3.17 (m, 2H) 2.86 to 2.83 (m, 2H), 2.66 to 2.63 (m, 2H), 2.18 to 1.70 (m, 14H)
GC-MS (CI): m / z = 336 (M)
　液状エポキシ化合物として式（７－５）の３，４－エポキシシクロヘキセニルメチル－３’、４’―エポキシシクロヘキセンカルボキシレートを準備した。このエポキシ化合物を（ｉ－１３）とした。
　液状エポキシ化合物として式（７－３）の水素添加ビスフェノールＡ型ジグリシジルエーテルを準備した。このエポキシ化合物を（ｉ－１４）とした。 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate of the formula (7-5) was prepared as a liquid epoxy compound. This epoxy compound was designated as (i-13).
A hydrogenated bisphenol A type diglycidyl ether of the formula (7-3) was prepared as a liquid epoxy compound. This epoxy compound was designated as (i-14).
〔光酸発生剤の準備〕
　スルホニウム塩の炭酸プロピレン溶液（式（８－２）、有効成分５０％、商品名ＣＰＩ－１０１Ａ、サンアプロ株式会社製）を準備した。これを光酸発生剤（ｉｉ－１）とした。
　スルホニウム塩の炭酸プロピレン溶液（式（８－１）、有効成分５０％、商品名ＣＰＩ－１００Ｐ、サンアプロ株式会社製）を準備した。これを光酸発生剤（ｉｉ－２）とした。 [Preparation of photoacid generator]
A sulfonium salt propylene carbonate solution (formula (8-2), active ingredient 50%, trade name CPI-101A, manufactured by San Apro Co., Ltd.) was prepared. This was designated as photoacid generator (ii-1).
　 A propylene carbonate solution of a sulfonium salt (formula (8-1), active ingredient 50%, trade name CPI-100P, manufactured by San Apro Co., Ltd.) was prepared. This was designated as photoacid generator (ii-2).
〔硬化性組成物の調製、及び光硬化性試験〕
　実施例１
　エポキシ化合物と光酸発生剤を表１に示す割合で配合し、攪拌と脱泡を行う装置（商品名：あわとり錬太郎、シンキ株式会社製）で混合し、脱泡して硬化性組成物を調製した。配合量は全て質量部で記載し、エポキシ化合物及び光酸発生剤は有効成分の質量部を記載した。炭酸プロピレン溶液の光酸発生剤（ｉｉ－１）、（ｉｉ－２）は、そのまま使用した。
　調製した硬化性組成物に９．５ｃｍの距離からＵＶ（紫外線）照射を行い、光硬化挙動をレオメーター（粘度計）で観測し、貯蔵弾性率が１０の４乗Ｐａ（１×１０4Ｐａ）に至った時間（秒）を硬化時間（秒）と定義した。ＵＶ照射は６００秒まで行った。
　レオメーターはレオロジカ社製（商品名ＶＡＲ－５０型）、ランプはＨｇ－Ｘｅランプを用い、照射するＵＶ波長は３６５ｎｍで、照射量は２０ｍＷ／ｃｍ2で行った。ＵＶ照射における照射窓材は３ｍｍ厚の硬質ガラスを用い、硬化性組成物から形成された塗膜の膜厚は５０μｍであった。硬化性組成物の光硬化時間を測定し、表１に記載した。 (Preparation of curable composition and photocurability test)
Example 1
An epoxy compound and a photoacid generator are blended in the proportions shown in Table 1, mixed with an apparatus (trade name: Awatori Rentaro, manufactured by Shinki Co., Ltd.) for stirring and defoaming, defoamed and curable composition Was prepared. All compounding amounts are described in parts by mass, and the epoxy compound and the photoacid generator are described in parts by mass of the active ingredient. The photoacid generators (ii-1) and (ii-2) in the propylene carbonate solution were used as they were.
The prepared curable composition was irradiated with UV (ultraviolet rays) from a distance of 9.5 cm, the photocuring behavior was observed with a rheometer, and the storage elastic modulus was 10 4 Pa (1 × 10 4 Pa). ) (Second) was defined as the curing time (second). UV irradiation was performed for up to 600 seconds.
The rheometer was manufactured by Rheologica (trade name VAR-50 type), the lamp was an Hg-Xe lamp, the irradiation UV wavelength was 365 nm, and the irradiation amount was 20 mW / cm 2 . The irradiation window material in UV irradiation used hard glass of 3 mm thickness, and the film thickness of the coating film formed from the curable composition was 50 μm. The photocuring time of the curable composition was measured and listed in Table 1.
　実施例２～実施例８及び比較例１～比較例５
　上記実施例１と同様に表１乃至表４に示す配合割合で硬化性組成物を調製し、硬化性組成物の光硬化時間を測定し、表１乃至表４に記載した。 Examples 2 to 8 and Comparative Examples 1 to 5
Similarly to Example 1, curable compositions were prepared at the blending ratios shown in Tables 1 to 4, and the photocuring time of the curable composition was measured. The results are shown in Tables 1 to 4.
Figure JPOXMLDOC01-appb-T000058
Figure JPOXMLDOC01-appb-T000058
Figure JPOXMLDOC01-appb-T000059
Figure JPOXMLDOC01-appb-T000059
Figure JPOXMLDOC01-appb-T000060
Figure JPOXMLDOC01-appb-T000060
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000061
　実施例９
　上記実施例１と同様に表５に示す配合割合で調製した硬化性組成物を７５μｍアプリケーターでＰＥＴフィルム（東洋紡　Ａ４１００　１２５μｍ）に塗布し、２６．５ｃｍの距離からＵＶ（紫外線）照射を下記の積算光量で行い、照射後すぐにタックフリー試験（指触乾燥時間試験）を行った。
　ＵＶ照射機は２ｋＷ×１灯用バッチ炉型紫外線硬化装置（アイグラフィックス社製）を用い、ランプはＨｇランプ（Ｈ０２－Ｌ４１　２．０ｋＷ　アイグラフィックス社製）を用い、照度は２０ｍＷ／ｃｍ２（３６５ｎｍ）で行った。ＵＶ照射における照射窓材は石英ガラスを用いた。硬化性組成物のタックフリータイムを評価し表５に記載した。 　 Example 9
The curable composition prepared at the blending ratio shown in Table 5 in the same manner as in Example 1 was applied to a PET film (Toyobo A4100 125 μm) with a 75 μm applicator, and UV (ultraviolet) irradiation was performed from the distance of 26.5 cm as shown in the following integration. A tack-free test (a finger touch drying time test) was performed immediately after irradiation.
The UV irradiator uses a batch furnace type ultraviolet curing device for 2 kW x 1 lamp (made by Eye Graphics), the lamp uses an Hg lamp (H02-L41 2.0 kW made by Eye Graphics), and the illuminance is 20 mW / cm. 2 (365 nm). Quartz glass was used as the irradiation window material in the UV irradiation. The tack-free time of the curable composition was evaluated and listed in Table 5.
　実施例１０、比較例６～比較例９
　上記実施例９と同様に表５に示す配合割合で硬化性組成物を調製し、硬化性組成物のタックフリータイムを評価し表５に記載した。
　なお、表５における評価基準は、硬化（◎）、少し張り付く（○）、指の跡が残る（△）、表面硬化しているが内部未硬化（△×）、未硬化（×）の５段階で評価した。 Example 10, Comparative Examples 6 to 9
The curable composition was prepared at the blending ratio shown in Table 5 in the same manner as in Example 9, and the tack-free time of the curable composition was evaluated and listed in Table 5.
　 The evaluation criteria in Table 5 are 5 for curing (（), sticking a little (◯), leaving a mark on the finger (Δ), surface curing but internal uncured (Δx), uncured (x). Rated by stage.
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000062
〔熱硬化物の作成〕
　実施例１１
　反応器に２４．６ｇのエポキシ化合物（ｉ－１）と３１．３ｇの酸無水物硬化剤リカシッドＭＨ－７００（商品名、新日本理化社製、成分は４－メチルヘキサヒドロ無水フタル酸とヘキサヒドロ無水フタル酸を７０：３０のモル比で混合したもの）を加えて減圧下、室温で３０分攪拌脱泡した。硬化促進剤として０．２５ｇのヒシコーリンＰＸ－４ＥＴ（商品名、日本合成化学工業社製、成分はテトラブチルホスホニウムジエチルホスホロジチオエート）を加えて更に５分攪拌脱泡した。この混合物を３ｍｍのシリコーンラバーを挟み込んだ離型剤処理したガラス板（離型剤ＳＲ－２４１０（商品名）東レ・ダウコーニング社製を用い１５０℃で１時間処理した。）の間に流し込んで、予備硬化１００℃で２時間、本硬化１５０℃で５時間の硬化を行った。 [Creation of thermoset]
Example 11
In the reactor, 24.6 g of epoxy compound (i-1) and 31.3 g of acid anhydride curing agent Rikacid MH-700 (trade name, manufactured by Shin Nippon Rika Co., Ltd., components are 4-methylhexahydrophthalic anhydride and hexahydro (Mixed phthalic anhydride in a molar ratio of 70:30) was added, and the mixture was degassed by stirring at room temperature for 30 minutes under reduced pressure. 0.25 g of Hishicolin PX-4ET (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., the component is tetrabutylphosphonium diethyl phosphorodithioate) was added as a curing accelerator, and the mixture was degassed with stirring for 5 minutes. This mixture was poured between glass plates treated with a release agent sandwiched with 3 mm silicone rubber (treated with release agent SR-2410 (trade name) manufactured by Toray Dow Corning Co., Ltd. for 1 hour at 150 ° C.). Precuring was performed at 100 ° C. for 2 hours, and main curing was performed at 150 ° C. for 5 hours.
　実施例１２
　９．４ｇのエポキシ化合物（ｉ－２）、１４．３ｇのリカシッドＭＨ－７００、０．１０ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Example 12
9.4 g of epoxy compound (i-2), 14.3 g of Ricacid MH-700, and 0.10 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　実施例１３
　１６．５ｇのエポキシ化合物（ｉ－３）、１８．７ｇのリカシッドＭＨ－７００、０．１７ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Example 13
16.5 g of epoxy compound (i-3), 18.7 g of Ricacid MH-700, and 0.17 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　実施例１４
　１０．２ｇのエポキシ化合物（ｉ－４）、１１．７ｇのリカシッドＭＨ－７００、０．１１ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Example 14
10.2 g of the epoxy compound (i-4), 11.7 g of Ricacid MH-700 and 0.11 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　実施例１５
　５．０２ｇのエポキシ化合物（ｉ－５）、４．６６ｇのリカシッドＭＨ－７００、　０．０６３ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Example 15
5.02 g of the epoxy compound (i-5), 4.66 g of Ricacid MH-700 and 0.063 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　実施例１６
　１３．５ｇのエポキシ化合物（ｉ－６）、１６．６ｇのリカシッドＭＨ－７００、０．１３ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Example 16
13.5 g of epoxy compound (i-6), 16.6 g of Ricacid MH-700 and 0.13 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　実施例１７
　７．６６ｇのエポキシ化合物（ｉ－７）、８．３８ｇのリカシッドＭＨ－７００、０．０７８ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Example 17
7.66 g of the epoxy compound (i-7), 8.38 g of Ricacid MH-700 and 0.078 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　実施例１８
　１４．２ｇのエポキシ化合物（ｉ－８）、２０．０ｇのリカシッドＭＨ－７００、　０．１５ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Example 18
14.2 g of the epoxy compound (i-8), 20.0 g of Ricacid MH-700, and 0.15 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　比較例１０
　１４．７ｇのエポキシ化合物（ｉ－５）、２４．１ｇのリカシッドＭＨ－７００、０．１５ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Comparative Example 10
14.7 g of the epoxy compound (i-5), 24.1 g of Ricacid MH-700 and 0.15 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　比較例１１
　１４．６ｇのエポキシ化合物（ｉ－６）、２０．９ｇのリカシッドＭＨ－７００、０．１５ｇのヒシコーリンＰＸ－４ＥＴを上記実施例１と同様に仕込み、硬化物を得た。 Comparative Example 11
14.6 g of epoxy compound (i-6), 20.9 g of Ricacid MH-700, and 0.15 g of Hishicolin PX-4ET were charged in the same manner as in Example 1 to obtain a cured product.
　得られた硬化物について、３点曲げ試験（曲げ強度と、曲げ弾性率）、透過率、線膨張率、ガラス転移温度を測定した。 The obtained cured product was measured for a three-point bending test (bending strength and bending elastic modulus), transmittance, linear expansion coefficient, and glass transition temperature.
（曲げ特性の測定）
　万能試験機によりＪＩＳ　Ｋ－６９１１に基づき測定した。
　試験片の高さ及び幅を測定し、試験片を支え、その中央に加圧くさびで荷重を加え、試験片が折れたときの荷重を測定し、曲げ強度（σ）を算出した。
　曲げ強度σ：（ＭＰａ）｛ｋｇｆ／ｍｍ2｝、
　Ｐ：試験片が折れたときの荷重（Ｎ）｛ｋｇｆ｝、
　Ｌ：支点間距離（ｍｍ）、
　Ｗ：試験片の幅（ｍｍ）、
　ｈ：試験片の高さ（ｍｍ）
とした。
　　σ＝（３ＰＬ）／（２Ｗｈ2）
　曲げ弾性率（Ｅ）：（ＭＰａ）｛ｋｇｆ／ｍｍ2｝は、Ｆ／Ｙ：荷重－たわみ曲線の直線部分のこう配（Ｎ／ｍｍ）｛ｋｇｆ／ｍｍ｝とすると、
　　Ｅ＝〔Ｌ3／（４Ｗｈ3）〕×〔Ｆ／Ｙ〕 (Measurement of bending properties)
Measured according to JIS K-6911 using a universal testing machine.
The height and width of the test piece were measured, the test piece was supported, a load was applied to the center with a pressure wedge, the load when the test piece was broken was measured, and the bending strength (σ) was calculated.
Bending strength σ: (MPa) {kgf / mm 2 },
P: Load when the test piece is broken (N) {kgf},
L: Distance between fulcrums (mm),
W: width of test piece (mm),
h: Height of test piece (mm)
It was.
σ = (3PL) / (2Wh 2 )
Flexural modulus (E): (MPa) {kgf / mm 2 } is F / Y: gradient of the linear portion of the load-deflection curve (N / mm) {kgf / mm}
E = [L 3 / (4 Wh 3 )] × [F / Y]
（透過率の測定）
　分光光度計を用いて４００ｎｍの透過率を測定した。 (Measurement of transmittance)
The transmittance at 400 nm was measured using a spectrophotometer.
（線膨張率の測定）
　線膨張率の測定は、ＪＩＳ　Ｋ－６９１１に基づき測定した。
　試験片の厚みを正確に測定してＴＭＡ（熱機械分析）膨張・圧縮法にて荷重０．０５Ｎ、昇温速度５℃／分で測定した。
　線膨張係数α１は３０－８０℃の長さの変化量（ΔＬ１）／試験片の初期の長さ（Ｌ）×５０＝α１で求めた。 (Measurement of linear expansion coefficient)
The linear expansion coefficient was measured based on JIS K-6911.
The thickness of the test piece was accurately measured and measured by a TMA (thermomechanical analysis) expansion / compression method at a load of 0.05 N and a temperature increase rate of 5 ° C./min.
The linear expansion coefficient α1 was obtained by the following equation: change in length of 30-80 ° C. (ΔL1) / initial length of test piece (L) × 50 = α1.
（ガラス転移温度（Ｔｇ）の測定）
　試験片の厚みを正確に測定してＴＭＡの膨張・圧縮法にて荷重０．０５Ｎ、昇温速度５℃／分で測定した。ガラス転移点の前後の曲線に接線を引き、この接線の交点からＴｇを求めた。 (Measurement of glass transition temperature (Tg))
The thickness of the test piece was measured accurately and measured by a TMA expansion / compression method at a load of 0.05 N and a temperature increase rate of 5 ° C./min. A tangent line was drawn on the curve before and after the glass transition point, and Tg was determined from the intersection of the tangent lines.
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
　本発明のエポキシ化合物を含む硬化性組成物は、光および熱硬化性を有し、基板に対する高い密着性、高透明性（可視光線に対する透明性）、ハードコート性、高耐熱性などの優れた特徴を持ち電子部品、光学部品、精密機構部品の被覆や接着に用いることができる。例えば携帯電話機やカメラのレンズ、発光ダイオード（ＬＥＤ）、半導体レーザー（ＬＤ）などの光学素子、液晶パネル、バイオチップ、カメラのレンズやプリズムなどの部品、パソコンなどのハードディスクの磁気部品、ＣＤ、ＤＶＤプレヤーのピックアップ（ディスクから反射してくる光情報を取り込む部分）、スピーカーのコーンとコイル、モーターの磁石、回路基板、電子部品、自動車などのエンジン内部の部品等の接着に用いることができる。
　自動車ボディー、ランプや電化製品、建材、プラスチックなどの表面保護のためのハードコート材向けとしては、例えば自動車、バイクのボディー、ヘッドライトのレンズやミラー、メガネのプラスチックレンズ、携帯電話機、ゲーム機、光学フィルム、ＩＤカード等への適用ができる。
　アルミニウム等の金属、プラスチックなどに印刷するインキ材料向けとしては、クレジットカード、会員証などのカード類、電化製品やＯＡ機器のスイッチ、キーボードへの印刷用インキ、ＣＤ、ＤＶＤ等へのインクジェットプリンター用インキへの適用が挙げられる。 The curable composition containing the epoxy compound of the present invention has light and thermosetting properties, and has excellent adhesion to the substrate, high transparency (transparency to visible light), hard coat properties, high heat resistance, and the like. It has characteristics and can be used for covering and bonding electronic parts, optical parts and precision mechanism parts. For example, cellular phones and camera lenses, optical elements such as light emitting diodes (LEDs) and semiconductor lasers (LD), liquid crystal panels, biochips, camera lenses and prisms, hard disk magnetic parts such as personal computers, CDs and DVDs It can be used for bonding player pickups (parts that capture optical information reflected from the disk), speaker cones and coils, motor magnets, circuit boards, electronic components, automotive internal components, and the like.
For car body, lamp, electrical appliance, building material, hard coat material for surface protection such as plastic, for example, automobile, motorcycle body, headlight lens and mirror, glasses plastic lens, mobile phone, game machine, Application to optical films, ID cards, etc. is possible.
For ink materials to be printed on metals such as aluminum and plastics, cards such as credit cards and membership cards, switches for electrical appliances and office automation equipment, ink for printing on keyboards, inkjet printers for CDs, DVDs, etc. Application to ink is mentioned.
　また、本発明の硬化性組成物は、３次元ＣＡＤと組み合わせて樹脂を硬化し複雑な立体物をつくる技術や、工業製品のモデル製作等の光造形への適用、光ファイバーのコーティング、接着、光導波路、厚膜レジスト（ＭＥＭＳ用）などへの適用が挙げられる。 In addition, the curable composition of the present invention is combined with a three-dimensional CAD to cure a resin to form a complex three-dimensional object, applied to optical modeling such as model production of industrial products, optical fiber coating, adhesion, light Application to waveguides, thick film resists (for MEMS) and the like can be mentioned.

Claims (14)

  1. 　下記式（１）：
    Figure JPOXMLDOC01-appb-C000001
     ［式（１）中、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ3は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表し、ｎ５は０又は１の整数を表し、ｎ６は０又は１の整数を表す。］で表されるエポキシ化合物。     Following formula (1):
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (1), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, an (n4) -valent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an (n4) -valent nitrogen A ring-containing group, a (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a (n4) -valent group in combination thereof, wherein R 1 and R 2 are each independently a hydrogen atom Or an alkyl group having 1 to 10 carbon atoms, R 3 represents an (n3 + 1) -valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, and n3 represents an integer of 2 to 5 N4 represents an integer of 2 to 8, n5 represents an integer of 0 or 1, and n6 represents an integer of 0 or 1. ] The epoxy compound represented by this.
  2. 　前記式（１）が、式（１－１）、式（１－２）、又は式（１－３）：
    Figure JPOXMLDOC01-appb-C000002
     ［式（１－１）及び式（１－３）中において、Ａは（ｎ４）価の炭素原子数２～１０の不飽和炭化水素基、（ｎ４）価の炭素原子数４～２０の環状炭化水素基、（ｎ４）価の窒素含有環基、（ｎ４）価の炭素原子数３～１０の鎖状炭化水素基、又はそれらを組み合わせた（ｎ４）価の基を表し、式（１－２）中において、Ａ’は（ｎ４）価の窒素含有環基を表し、Ｒ1及びＲ2は、それぞれ独立して、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｒ３は（ｎ３＋１）価の炭化水素基を表し、ｎ１は２の整数を表し、ｎ２は１の整数を表し、ｎ３は２～５の整数を表し、ｎ４は２～８の整数を表す。］で表される、請求項１に記載のエポキシ化合物。     Formula (1) is formula (1-1), formula (1-2), or formula (1-3):
    Figure JPOXMLDOC01-appb-C000002
     [In the formulas (1-1) and (1-3), A represents an (n4) -valent unsaturated hydrocarbon group having 2 to 10 carbon atoms, and (n4) a cyclic group having 4 to 20 carbon atoms. Represents a hydrocarbon group, an (n4) -valent nitrogen-containing cyclic group, an (n4) -valent chain hydrocarbon group having 3 to 10 carbon atoms, or a combination of these (n4) -valent groups. 2), A ′ represents a (n4) -valent nitrogen-containing cyclic group, R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 3 represents (N3 + 1) represents a valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2 to 8. The epoxy compound of Claim 1 represented by this.
  3. 　前記Ａがエチレン、プロピレン、又はノルボルネンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の不飽和炭化水素基である、請求項１又は請求項２に記載のエポキシ化合物。 The epoxy compound according to claim 1 or 2, wherein the A is an (n4) -valent unsaturated hydrocarbon group obtained by removing (n4) hydrogen atoms from ethylene, propylene, or norbornene.
  4. 　前記Ａがシクロブタン、シクロペンタン、シクロヘキサン、エポキシシクロヘキサン、アルキル置換されたエポキシシクロヘキサン、ビシクロヘプテン、ビシクロオクテン、又はアダマンタンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の環状炭化水素基である、請求項１又は請求項２に記載のエポキシ化合物。 A is a (n4) -valent cyclic hydrocarbon group in which (n4) hydrogen atoms have been removed from cyclobutane, cyclopentane, cyclohexane, epoxycyclohexane, alkyl-substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane, The epoxy compound according to claim 1 or 2.
  5. 　前記Ａがトリアルキルイソシアヌレートから（ｎ４）個の水素原子を取り除いた（ｎ４）価の窒素含有環基であり、前記Ａ’がイソシアヌル酸、シアヌル酸、ヒダントイン、又はバルビツール酸から（ｎ４）個の水素原子を取り除いた（ｎ４）価の窒素含有環基である、請求項１又は請求項２に記載のエポキシ化合物。 The A is a (n4) -valent nitrogen-containing cyclic group obtained by removing (n4) hydrogen atoms from a trialkyl isocyanurate, and the A ′ is (n4) from isocyanuric acid, cyanuric acid, hydantoin, or barbituric acid The epoxy compound according to claim 1 or 2, which is an (n4) -valent nitrogen-containing cyclic group from which one hydrogen atom has been removed.
  6. 　前記Ａがプロパン、ブタン、ペンタン、又はヘキサンから（ｎ４）個の水素原子を取り除いた（ｎ４）価の鎖状炭化水素基である、請求項１又は請求項２に記載のエポキシ化合物。 The epoxy compound according to claim 1 or 2, wherein the A is a (n4) -valent chain hydrocarbon group obtained by removing (n4) hydrogen atoms from propane, butane, pentane, or hexane.
  7. 　請求項１乃至請求項６のいずれか１項に記載のエポキシ化合物、及び硬化剤を含む硬化性組成物。 A curable composition comprising the epoxy compound according to any one of claims 1 to 6 and a curing agent.
  8. 　前記硬化剤が酸無水物、アミン、フェノール樹脂、ポリアミド樹脂、イミダゾール、又はポリメルカプタンである、請求項７に記載の硬化性組成物。 The curable composition according to claim 7, wherein the curing agent is an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, or a polymercaptan.
  9. 　前記エポキシ化合物のエポキシ基１当量に対して前記硬化剤を０．５～１．５当量の割合で含有する、請求項７又は請求項８に記載の硬化性組成物。 The curable composition according to claim 7 or 8, which contains the curing agent in a proportion of 0.5 to 1.5 equivalents relative to 1 equivalent of an epoxy group of the epoxy compound.
  10. 　請求項１乃至請求項６のいずれか１項に記載のエポキシ化合物、及び酸発生剤を含む硬化性組成物。 A curable composition comprising the epoxy compound according to any one of claims 1 to 6 and an acid generator.
  11. 　前記酸発生剤が光酸発生剤又は熱酸発生剤である、請求項１０に記載の硬化性組成物。 The curable composition according to claim 10, wherein the acid generator is a photoacid generator or a thermal acid generator.
  12. 　前記酸発生剤がオニウム塩である、請求項１１に記載の硬化性組成物。 The curable composition according to claim 11, wherein the acid generator is an onium salt.
  13. 　前記酸発生剤がスルホニウム塩化合物、又はヨードニウム塩化合物である、請求項１１に記載の硬化性組成物。 The curable composition according to claim 11, wherein the acid generator is a sulfonium salt compound or an iodonium salt compound.
  14. 　前記エポキシ化合物の質量に対して前記酸発生剤を０．１～２０質量％の割合で含有する、請求項１０乃至請求項１３のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 10 to 13, comprising the acid generator in a proportion of 0.1 to 20% by mass relative to the mass of the epoxy compound.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015053078A1 (en) * 2013-10-07 2015-04-16 株式会社ダイセル Curable epoxy resin composition
WO2017077846A1 (en) * 2015-11-05 2017-05-11 日産化学工業株式会社 Epoxy-based reactive diluent and epoxy resin composition including same
WO2019038977A1 (en) * 2017-08-24 2019-02-28 古河電気工業株式会社 Coating material for optical fiber, coated optical fiber, and method for producing coated optical fiber
WO2020079895A1 (en) * 2018-10-19 2020-04-23 Jnc株式会社 2-ethyl-2, 3-epoxybutyloxy compound

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9382472B2 (en) * 2013-12-18 2016-07-05 Rohm And Haas Electronic Materials Llc Transformative wavelength conversion medium
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KR20190140474A (en) * 2017-05-09 2019-12-19 닛산 가가쿠 가부시키가이샤 Method of producing epoxy compound
KR102475977B1 (en) * 2021-01-19 2022-12-09 한국화학연구원 The composition containing trifunctional cycloaliphatic epoxy compounds and the cured product using the same

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6465117A (en) * 1987-07-23 1989-03-10 Ciba Geigy Ag Curable epoxy resin composition containing tetraglycidyl ether of tetramethylol compound
JPH0370741A (en) * 1989-08-10 1991-03-26 Sumitomo Chem Co Ltd Fiber-reinforced composite material
JPH0881461A (en) * 1994-09-12 1996-03-26 Nissan Chem Ind Ltd New epoxy compound and its production
JP2003246835A (en) * 2002-02-26 2003-09-05 Nippon Steel Chem Co Ltd Novel multifunctional epoxy compound
JP2004231787A (en) * 2003-01-30 2004-08-19 Nippon Steel Chem Co Ltd Epoxy resin diluent, epoxy resin composition and epoxy resin cured product
JP2004528423A (en) * 2001-03-06 2004-09-16 バンティコ ゲーエムベーハー Highly functional polymer
JP2007177144A (en) * 2005-12-28 2007-07-12 Shin Etsu Chem Co Ltd Room temperature-curable fluorine-containing composition
JP2008101199A (en) * 2001-09-12 2008-05-01 Dow Global Technologies Inc Net polymer containing terminal epoxy ester
JP2009079015A (en) * 2007-09-27 2009-04-16 Idemitsu Kosan Co Ltd Adamantane-containing epoxy compound, method for producing the same and epoxy composition
JP2010001424A (en) * 2008-06-23 2010-01-07 Dic Corp Epoxy compound and cured epoxy product

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0725929B2 (en) * 1987-12-25 1995-03-22 新日本理化株式会社 Thermoplastic resin composition
JP2008274159A (en) * 2007-05-01 2008-11-13 Idemitsu Kosan Co Ltd Adamantane derivative, method for producing the same, resin composition containing the same, and use of the same
CN102317343B (en) * 2009-02-10 2013-07-31 日产化学工业株式会社 Long chain alkylene group-containing epoxy compound

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6465117A (en) * 1987-07-23 1989-03-10 Ciba Geigy Ag Curable epoxy resin composition containing tetraglycidyl ether of tetramethylol compound
JPH0370741A (en) * 1989-08-10 1991-03-26 Sumitomo Chem Co Ltd Fiber-reinforced composite material
JPH0881461A (en) * 1994-09-12 1996-03-26 Nissan Chem Ind Ltd New epoxy compound and its production
JP2004528423A (en) * 2001-03-06 2004-09-16 バンティコ ゲーエムベーハー Highly functional polymer
JP2008101199A (en) * 2001-09-12 2008-05-01 Dow Global Technologies Inc Net polymer containing terminal epoxy ester
JP2003246835A (en) * 2002-02-26 2003-09-05 Nippon Steel Chem Co Ltd Novel multifunctional epoxy compound
JP2004231787A (en) * 2003-01-30 2004-08-19 Nippon Steel Chem Co Ltd Epoxy resin diluent, epoxy resin composition and epoxy resin cured product
JP2007177144A (en) * 2005-12-28 2007-07-12 Shin Etsu Chem Co Ltd Room temperature-curable fluorine-containing composition
JP2009079015A (en) * 2007-09-27 2009-04-16 Idemitsu Kosan Co Ltd Adamantane-containing epoxy compound, method for producing the same and epoxy composition
JP2010001424A (en) * 2008-06-23 2010-01-07 Dic Corp Epoxy compound and cured epoxy product

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015053078A1 (en) * 2013-10-07 2015-04-16 株式会社ダイセル Curable epoxy resin composition
WO2017077846A1 (en) * 2015-11-05 2017-05-11 日産化学工業株式会社 Epoxy-based reactive diluent and epoxy resin composition including same
KR20180080200A (en) * 2015-11-05 2018-07-11 닛산 가가쿠 고교 가부시키 가이샤 Epoxy-based reactive diluent and epoxy resin composition containing the same
JPWO2017077846A1 (en) * 2015-11-05 2018-08-23 日産化学株式会社 Epoxy-based reactive diluent and epoxy resin composition containing the same
KR102629442B1 (en) * 2015-11-05 2024-01-25 닛산 가가쿠 가부시키가이샤 Epoxy-based reactive diluent and epoxy resin composition containing the same
WO2019038977A1 (en) * 2017-08-24 2019-02-28 古河電気工業株式会社 Coating material for optical fiber, coated optical fiber, and method for producing coated optical fiber
JPWO2019038977A1 (en) * 2017-08-24 2020-08-06 古河電気工業株式会社 Coating material for optical fiber, coated optical fiber, and method for manufacturing coated optical fiber
JP7129414B2 (en) 2017-08-24 2022-09-01 古河電気工業株式会社 Coating material for optical fiber, coated optical fiber, and method for producing coated optical fiber
WO2020079895A1 (en) * 2018-10-19 2020-04-23 Jnc株式会社 2-ethyl-2, 3-epoxybutyloxy compound

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