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WO2012128325A1 - Composé époxy polyfonctionnel - Google Patents

Composé époxy polyfonctionnel 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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WO
WIPO (PCT)
Prior art keywords
valent
group
epoxy compound
formula
integer
Prior art date
Application number
PCT/JP2012/057371
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English (en)
Japanese (ja)
Inventor
勇樹 遠藤
武山　敏明
佐代子 柳澤
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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 CN201280013358.7A priority Critical patent/CN103429632B/zh
Priority to KR1020137026460A priority patent/KR101926076B1/ko
Priority to JP2013506004A priority patent/JP5867749B2/ja
Publication of WO2012128325A1 publication Critical patent/WO2012128325A1/fr

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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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)

Abstract

Cette invention a pour objectif de pourvoir à une composition de résine époxy basse viscosité qui manifeste non seulement une aptitude élevée au thermodurcissage mais aussi une aptitude élevée au durcissage par voie cationique. Pour ce faire, la présente invention propose un composé époxy représenté par la formule (1), et une composition durcissable qui comprend le composé époxy et un générateur d'acide ou un agent de durcissage. Dans la formule (1), A est un groupe hydrocarbure C2-10 insaturé (n4)-valent, un groupe hydrocarbure cyclique C4-20 (n4)-valent, un groupe de type cycle contenant un atome d'azote (n4)-valent, un groupe hydrocarbure c3-10 linéaire (n4)-valent, ou un groupe (n4)-valent constitué d'une combinaison de deux des groupes précités ou plus, R1 et R2 sont chacun indépendamment un atome d'hydrogène ou un alkyle C1-10, R3 est un groupe hydrocarbure (n3+1)-valent, n1 est un entier valant 2, n2 est un entier valant 1, n3 est un entier de 2 à 5, n4 est un entier de 2 à 8, n5 est un entier valant 0 ou 1, et n6 est un entier valant 0 ou 1. Le générateur d'acide est un générateur de photoacide ou un générateur d'acide thermique, tandis que l'agent de durcissage est un anhydride d'acide ou une amine.
PCT/JP2012/057371 2011-03-23 2012-03-22 Composé époxy polyfonctionnel WO2012128325A1 (fr)

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WO2015053078A1 (fr) * 2013-10-07 2015-04-16 株式会社ダイセル Composition de résine époxy durcissable
WO2017077846A1 (fr) * 2015-11-05 2017-05-11 日産化学工業株式会社 Diluant réactif à base d'époxyde et composition de résine époxyde le comprenant
WO2019038977A1 (fr) * 2017-08-24 2019-02-28 古河電気工業株式会社 Matériau de revêtement pour fibre optique, fibre optique revêtue et procédé de production de fibre optique revêtue
WO2020079895A1 (fr) * 2018-10-19 2020-04-23 Jnc株式会社 Composé de 2-éthyl-2, 3-époxybutyloxy

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CN108349919B (zh) * 2015-11-05 2022-06-03 日产化学工业株式会社 多官能环氧化合物及含有其的硬化性组合物
CN110662740A (zh) * 2017-05-09 2020-01-07 日产化学株式会社 环氧化合物的制造方法
JP2021017505A (ja) * 2019-07-22 2021-02-15 積水化学工業株式会社 樹脂材料及び多層プリント配線板
KR102475977B1 (ko) * 2021-01-19 2022-12-09 한국화학연구원 삼관능성 지환족 에폭시 화합물을 포함하는 에폭시 수지 제조용 조성물 및 이를 이용한 경화물

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WO2015053078A1 (fr) * 2013-10-07 2015-04-16 株式会社ダイセル Composition de résine époxy durcissable
WO2017077846A1 (fr) * 2015-11-05 2017-05-11 日産化学工業株式会社 Diluant réactif à base d'époxyde et composition de résine époxyde le comprenant
KR20180080200A (ko) * 2015-11-05 2018-07-11 닛산 가가쿠 고교 가부시키 가이샤 에폭시계 반응성 희석제 및 이것을 포함하는 에폭시 수지 조성물
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WO2019038977A1 (fr) * 2017-08-24 2019-02-28 古河電気工業株式会社 Matériau de revêtement pour fibre optique, fibre optique revêtue et procédé de production de fibre optique revêtue
JPWO2019038977A1 (ja) * 2017-08-24 2020-08-06 古河電気工業株式会社 光ファイバ用被覆材料、被覆光ファイバ、及び被覆光ファイバの製造方法
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WO2020079895A1 (fr) * 2018-10-19 2020-04-23 Jnc株式会社 Composé de 2-éthyl-2, 3-époxybutyloxy

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CN103429632B (zh) 2016-07-06
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TWI545140B (zh) 2016-08-11
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